JP2009203301A - Near-infrared ray absorbing adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a near-infrared ray absorbing adhesive composition having transparency in a visible area and high near-infrared ray absorbing ability. <P>SOLUTION: The near-infrared ray absorbing adhesive composition comprises (A) a diimonium pigment with the maximum absorption wavelength 1,060-1,200 nm in an acetone solution and (B) a resin with a calculated glass transition temperature of -20°C or less. Preferably, the diimonium pigment consists of a specific diimonium cation and a specific imide anion. Preferably, the acid value of the resin (B) is 25 or less. Preferably, a calculated solubility parameter of the resin (B) is 9.80 or less. This near-infrared ray absorbing adhesive composition is suitably used for an optical filter for a thin display, an optical filter for an optical semiconductor element, a thin display, and the like. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a near-infrared absorbing pressure-sensitive adhesive composition, a near-infrared absorbing material containing the near-infrared-absorbing pressure-sensitive adhesive composition, and an optical filter for a thin display using the near-infrared absorbing pressure-sensitive adhesive composition or the near-infrared absorbing material. And so on. In particular, the present invention provides a near-infrared absorbing adhesive composition excellent in transparency in the visible region and infrared absorbing ability, a near-infrared absorbing material containing the near-infrared absorbing adhesive composition, and the near-infrared absorbing adhesive composition. Alternatively, the present invention relates to an optical filter for an optical semiconductor element using a near-infrared absorbing material, an optical filter for a thin display using the near-infrared absorbing adhesive composition or the near-infrared absorbing material, and the like.

  In recent years, a thin liquid crystal display applicable to a large screen and a thin display such as a PDP (Plasma Display Panel) have attracted attention. The thin display generates near infrared rays having a wavelength of 800 nm to 1100 nm. There is a problem that this near infrared ray causes malfunction of the remote control for home appliances. Moreover, since the optical semiconductor element used for a CCD camera etc. has high sensitivity in the near infrared region, it is necessary to remove the near infrared ray. Therefore, there is a demand for a near-infrared absorbing material that has a high near-infrared absorbing ability and high transparency in the visible region.

  Conventionally, cyanine dyes, polymethine dyes, squarylium dyes, porphyrin dyes, metal dithiol complex dyes, phthalocyanine dyes, diimonium dyes or inorganic oxide particles are used as near infrared absorbing dyes that absorb near infrared rays. Has been. Among these, diimonium dyes are frequently used because they have a high near-infrared absorption ability and high transparency in the visible light region (see, for example, Patent Documents 1 and 2).

  The PDP generates a discharge in a rare gas, particularly a gas mainly composed of neon, enclosed in the panel, and R, G, B provided in the cells inside the panel by vacuum ultraviolet rays generated at that time. The phosphor is made to emit light. Therefore, electromagnetic waves unnecessary for the operation of the PDP are simultaneously emitted during this light emission process. It is necessary to shield this electromagnetic wave. Further, an antireflection film and an antiglare film (antiglare film) are also required to suppress reflected light. For this reason, an optical filter for plasma display is generally produced by laminating a near-infrared absorbing film, an electromagnetic wave shielding film and an antireflection film on glass or a shock absorbing material as a support. Such an optical filter for plasma display is placed on the front side of the PDP. Such an optical filter for plasma display may be used by being directly bonded onto glass or a shock absorbing material as a support using an adhesive or a pressure-sensitive adhesive.

  In recent years, attempts have been made to integrate a near-infrared absorbing film and a pressure-sensitive adhesive layer by incorporating a near-infrared absorbing dye into the pressure-sensitive adhesive for the purpose of thinning the optical filter and simplifying the optical filter manufacturing process. (Patent Document 3).

  JP-A-2005-325292 discloses a diimonium dye whose durability is improved by introducing a halogen atom into an alkyl group of a diimonium cation (Patent Document 4).

JP 2003-96040 A JP 2000-80071 A Japanese Patent No. 3621322 JP 2005-325292 A

  A diimonium-based dye capable of obtaining a high near-infrared absorptivity in a small amount has a great merit in terms of transparency and cost. It is more useful if such a diimonium dye can be used together with the adhesive resin. In a resin having a low glass transition point (Tg) such as a pressure-sensitive adhesive resin, a diimonium dye-containing pressure-sensitive adhesive that can obtain high near-infrared absorption ability in a small amount and has durability that can be put to practical use has not yet been obtained. It is not done.

  Then, an object of this invention is to provide the near-infrared absorption adhesive composition useful for producing the near-infrared absorber excellent in transparency and near-infrared absorptivity of visible region. Furthermore, an object of the present invention is to provide a near-infrared absorbing material, an optical filter for an optical semiconductor element, an optical filter for a thin display, and a thin display using the composition.

  The inventors of the present invention have intensively studied a combination of a diimonium dye and a resin. As a result, by combining a diimonium dye having a specific maximum absorption wavelength and a resin having a specific calculated glass transition temperature, the near-infrared absorption ability is excellent while having durability that can be put to practical use. It discovered that an infrared rays absorption adhesive composition was obtained. Furthermore, it has been found that the durability of the pigment is enhanced by regulating the acid value of the resin.

  That is, the above object is achieved by a near-infrared absorbing pressure-sensitive adhesive composition containing a diimonium dye having a maximum absorption wavelength of more than 1060 nm and not more than 1200 nm in an acetone solution and a resin having a calculated glass transition temperature of −20 ° C. or less. The

  The near-infrared absorbing material using the near-infrared absorbing adhesive composition of the present invention can obtain a high near-infrared absorbing ability with a small amount of addition. When this near-infrared absorbing adhesive composition is used for the production of an optical semiconductor element or an optical filter for a thin display, it becomes possible to make the optical filter thinner and to simplify the manufacturing process of the optical filter.

1. Diimonium dye The diimonium dye used in the present invention is a diimonium dye having a maximum absorption wavelength in an acetone solution of more than 1060 nm and 1200 nm or less. From the viewpoint of transparency in the visible region, the maximum absorption wavelength in the acetone solution of the diimonium dye is preferably 1065 nm or more, and more preferably 1070 nm or more. From the viewpoint of near infrared absorption ability, the maximum absorption wavelength in an acetone solution of a diimonium dye is more preferably 1100 nm or less, and further preferably 1080 nm or less.

  As a specific structure of the diimonium dye, a diimonium dye comprising a diimonium cation represented by the following formula (1) and an anion represented by the following formula (2) or (3) is exemplified.

However, in Formula (1), R < ¹ > -R < ⁸ > represents a hydrogen atom, a halogen atom, a C1-C10 alkyl group, or a C1-C10 alkyl group which has a substituent each independently. In formula (2), R ^a and R ^b each represent a fluoroalkyl group that may be the same or different. In formula (3), R ^c represents a fluoroalkylene group.

Examples of the alkyl group having 1 to 10 carbon atoms constituting the R ¹ to R ^8, a straight-chain, and a branched or alicyclic alkyl group. Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and 1-methylbutyl. Group, 1-ethylpropyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, neopentyl group, n-hexyl group, cyclohexyl group, and the like.

Further, Examples of the substituent which may be attached to an alkyl group of R ¹ to R ^8, cyano group; a hydroxyl group; a fluorine atom, a chlorine atom, a halogen atom such as a bromine atom; a methoxy group, an ethoxy group, n- propoxy radical, n An alkoxy group having 1 to 6 carbon atoms such as butoxy group; alkoxy having 2 to 8 carbon atoms such as methoxymethoxy group, ethoxymethoxy group, methoxyethoxy group, ethoxyethoxy group, methoxypropoxy group, methoxybutoxy group, ethoxybutoxy group, etc. Alkoxy group; C3-C15 alkoxyalkoxyalkoxy group such as methoxymethoxymethoxy group, methoxymethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group; allyloxy group; phenoxy group, tolyloxy group, xylyloxy group, naphthyloxy group Such as carbon number 6-12 Reeloxy group; C2-C7 alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group; methylcarbonyloxy group, ethylcarbonyloxy group, C2-C7 alkylcarbonyloxy groups such as n-propylcarbonyloxy group and n-butylcarbonyloxy group; methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, n-butoxycarbonyloxy group and the like And an alkoxycarbonyloxy group having 2 to 7 carbon atoms.

  The kind of anion in the diimonium dye is not particularly limited. A preferred anion is an imide anion. A more preferred anion is an anion represented by the above formula (2) or formula (3).

Regarding the above formula (2), examples of the fluoroalkyl group represented by R ^a or R ^b include perfluoroalkyl groups such as CF ₃ , C ₂ F ₅ , C ₃ F ₇ , and C ₄ F ₉ . R ^a and R ^b may be the same or different. Regarding the above formula (3), examples of the fluoroalkylene group represented by R ^c include (CF ₂ ) _n (where n is an integer of 2 to 12) and the like.

  Preferred imide anions include bis (trifluoromethanesulfone) imide ion, bis (pentafluoroethanesulfone) imide ion, 1,3-disulfonylhexafluoropropyleneimide, pentafluoroethanesulfone trifluoromethanesulfonimide ion, nonafluorobutanesulfone trifluoromethanesulfone Examples include imide ions. Furthermore, as the anion of the diimonium dye, one or more anions selected from the group consisting of a hexafluoroantimonate anion, a hexafluorophosphate anion, a tetrafluoroborate anion, and a perchlorate anion can also be used.

  Specific examples of the diimonium dye include those described in JP-A-2005-325292 described above.

  As the compound name of the diimonium dye, bis {bis (trifluoromethanesulfonyl) imidic acid} -N, N, N ′, N′-tetrakis- {p-di (n-butyl) aminophenyl} -p-phenylenediimonium ( 1073 nm), bis {tetrakis (pentafluorophenyl) boric acid} -N, N, N ′, N′-tetrakis- {p-di (n-butyl) aminophenyl} -p-phenylenediimonium (1079 nm), bis { Bis (trifluoromethanesulfonyl) imidic acid} -N, N, N ′, N′-tetrakis- {p-di (n-propyl) aminophenyl} -p-phenylenediimonium (1067 nm), bis {bis (trifluoromethanesulfonyl) ) Imido acid} -N, N, N ′, N′-tetrakis- {p-di (iso-propyl) amino Enyl} -p-phenylenediimonium (1072 nm), bishexafluoroantimonic acid-N, N, N ′, N′-tetrakis- {p-di (n-propyl) aminophenyl} -p-phenylenediimonium (1065 nm), Bishexafluoroantimonic acid-N, N, N ′, N′-tetrakis- {p-di (iso-propyl) aminophenyl} -p-phenylenediimonium (1070 nm), bishexafluoroantimonic acid-N, N, N ', N'-tetrakis- {p-di (n-butyl) aminophenyl} -p-phenylenediimonium (1071 nm), bishexafluoroantimonic acid-N, N, N', N'-tetrakis- {p-di (Iso-butyl) aminophenyl} -p-phenylenediimonium (1076 nm), bis { (Trifluoromethanesulfonyl) imidic acid} -N, N, N ′, N′-tetrakis- {p-di (iso-butyl) aminophenyl} -p-phenylenediimonium (1078 nm), bishexafluoroantimonic acid-N , N, N ′, N′-tetrakis- {p-di (n-hexyl) aminophenyl} -p-phenylenediimonium (1077 nm), bis {bis (trifluoromethanesulfonyl) imidic acid} -N, N, N ′ , N′-tetrakis- {p-di (n-hexyl) aminophenyl} -p-phenylenediimonium (1079 nm), bis {bis (trifluoromethanesulfonyl) imidic acid} -N, N, N ′, N′-tetrakis -{P-di (benzyl) aminophenyl} -p-phenylenediimonium (1086 nm), bis (1, 3-disulfonylhexafluoropropylimidic acid) -N, N, N ′, N′-tetrakis- {p- (iso-butyl) aminophenyl} -p-phenylenediimonium (1078 nm), bis {bis (pentafluoroethane) Sulfonyl) imidic acid} -N, N, N ′, N′-tetrakis- {p- (iso-butyl) aminophenyl} -p-phenylenediimonium (1078 nm), bis {bis (trifluoromethanesulfonyl) imidic acid}- N, N, N ′, N′-tetrakis- {p- (n-pentyl) aminophenyl} -p-phenylenediimonium (1082 nm), bis {bis (trifluoromethanesulfonyl) imidic acid} -N, N, N ′ , N′-Tetrakis- {p- (iso-pentyl) aminophenyl} -p-phenylenediimoni (1083 nm) and bis {bis (trifluoromethanesulfonyl) imidic acid} -N, N, N ′, N′-tetrakis- {p- (2,2-dimethylpropyl) aminophenyl} -p-phenylenediimonium (1087 nm ). In addition, the numerical value in a parenthesis shows the maximum absorption wavelength in an acetone solution.

As a specific product of the diimonium dye according to the present invention, trade name “CIR-1085” manufactured by Nippon Carlit Co., Ltd. may be mentioned. This CIR-1085 has a maximum absorption wavelength of 1073 nm in an acetone solution. This CIR-1085 is the above-described bis {bis (trifluoromethanesulfonyl) imidic acid} -N, N, N ′, N′-tetrakis- {p-di (n-butyl) aminophenyl} -p-phenylenediimonium. is there. The structure of the diimonium cation of CIR-1085 is a structure in which R ¹ to R ⁸ in the above formula (1) are all n-butyl groups.

  The maximum absorption wavelength in the acetone solution is measured as follows. The dimonium dye to be measured is dissolved in a predetermined amount of acetone, and after confirming that there is no insoluble matter, the absorbance is measured. For the measurement of the spectrum, UV-3700 (manufactured by Shimadzu Corporation) is used. For the measurement, a measurement cell made of quartz and having an optical path length of 10 mm is used.

2. Resin The resin according to the present invention is not particularly limited as long as it has a calculated glass transition temperature of −20 ° C. or lower. The resin according to the present invention has adhesiveness. This tackiness enables direct adhesion between the near-infrared absorbing pressure-sensitive adhesive composition and the adherend. The near-infrared absorbing pressure-sensitive adhesive composition and the adherend can be bonded without interposing an adhesive. Hereinafter, this resin is also referred to as an adhesive resin.

2-1. Calculated glass transition temperature From the viewpoint of imparting adhesiveness to the adherend, the calculated glass transition temperature of the adhesive resin is preferably -20 ° C or lower, more preferably -30 ° C or lower, more preferably -34 ° C. It is as follows. When it is higher than −20 ° C., the tackiness may be insufficient. The calculated glass transition temperature Tg is obtained by the following Fox equation. The monomer used for the polymerization of the resin is not particularly limited as long as the calculated glass transition temperature Tg calculated using the Fox formula represented by the following formula satisfies a predetermined value.
1 / (Tg + 273) = Σ [Wi / (Tgi + 273)]: Fox formula Tg (° C.): calculated glass transition temperature Wi: weight fraction of each monomer Tgi (° C.): single weight of each monomer component Glass transition temperature of coalescence

2-2. Acid Value In general, a carboxyl group-containing monomer such as acrylic acid is copolymerized with the adhesive resin for the purpose of improving adhesion to the adherend and increasing adhesive strength. However, since a functional group such as a carboxyl group degrades the diimonium dye, the acid value of the pressure-sensitive adhesive is preferably 25 or less, preferably 0 or more and 20 or less, more preferably 0 or more and 10 or less, and most preferably 0. “Acid value” refers to the amount of mg of potassium hydroxide required to neutralize 1 g of the adhesive resin.

2-3. Calculated solubility parameter When the calculated solubility parameter of the pressure-sensitive adhesive resin is high, the durability of the dimonium dye may be inferior, so the solubility parameter is preferably 9.80 or less. The calculated solubility parameter is a value calculated by the method described on pages 147 to 154 of “POLYMER ENGINEERING AND SCIENCE” (1974, Vol. 14, No. 2). The method is outlined below.

The solubility parameter (δ) of the homopolymer is calculated by the following calculation method based on the evaporation energy (Δei) and the molar volume (Δvi) of the structural unit forming the polymer.
δ = (ΣΔei / ΣΔvi) ^1/2
Δei: i-component atom or atomic group evaporation energy Δvi: i-component atom or atomic group molar volume

  For the solubility parameter of the copolymer, the solubility parameter of each homopolymer of each constituent monomer constituting the copolymer is calculated from the above formula, and each constituent monomer is calculated as the solubility parameter. The product obtained by multiplying by the mole fraction is calculated as the square root.

2-4. Copolymer composition The adhesive resin may be a copolymer. As the adhesive resin according to the present invention, 5 to 40% by weight of a (meth) acrylic acid ester having an alicyclic, polycyclic alicyclic, aromatic or polycyclic aromatic cyclic alkyl group was copolymerized. The pressure-sensitive adhesive resin is preferable because the durability of the dimonium dye is good. The reason for this is unclear, but the heat resistance and heat and heat resistance of the alicyclic, polycyclic alicyclic, aromatic, and polycyclic aromatic cyclic alkyl groups and the diimonium dye form a stacking structure. It is thought to improve.

A more preferable adhesive resin is a resin obtained by copolymerizing the following (m1) and (m2), or a resin obtained by copolymerizing the following (m1) to (m3).
(M1) A (meth) acrylic acid ester having an alicyclic, polycyclic alicyclic, aromatic or polycyclic aromatic cyclic alkyl group.
(M2) A (meth) acrylic acid ester having an alkyl group. However, this alkyl group is linear or branched, and the alkyl group has 1 to 10 carbon atoms.
(M3) Other copolymerizable monomers.

  In the copolymer resin, the preferable ratio of the monomer is 5 to 40% by weight of the (meth) acrylic acid ester of (m1), and 60 to 95% by weight of the (meth) acrylic acid ester of (m2). And the other monomer of (m3) is 0 to 30% by weight.

  Examples of the (meth) acrylic ester of (m1) include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentenyloxyethyl (meth). Acrylate, dicyclopentanyl (meth) acrylate, tricyclodecanyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, 2-hydroxy-3-phenoxypropyl ( And (meth) acrylate.

  Examples of the (m2) (meth) acrylic acid ester of (m2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and t-butyl (meth). Examples include acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, i-octyl (meth) acrylate, and the like.

  Examples of the monomer (m3) include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, and the like. (Meth) acrylates; styrene monomers represented by α-methylstyrene, vinyl toluene, styrene, etc .; vinyl ether monomers represented by methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, etc .; fumaric acid; fumaric acid Monoalkyl ester of fumaric acid; maleic acid; monoalkyl ester of maleic acid; dialkyl ester of maleic acid; itaconic acid; monoalkyl ester of itaconic acid; dialkyl ester of itaconic acid (Meth) acrylonitrile; and the like vinylcarbazole, vinyl chloride, vinylidene chloride; vinyl acetate; vinyl ketones, vinyl pyridine. In addition, monomers having a functional group such as a carboxyl group, an oxazolinyl group, a pyrrolidonyl group, and a fluoroalkyl group may be copolymerized within a range that does not impair the object of the present invention.

  Commercially available products such as peroxides and azos can be used as the initiator used for the polymerization of the adhesive resin. Peroxide-based initiators include peroxyesters such as perbutyl O and perhexyl O (both manufactured by NOF); peroxydicarbonates such as PERROYL L and PEROIL O (both manufactured by NOF); Diacyl peroxides such as BW and Nyper BMT (both made by NOF); Peroxyketals such as perhexa 3M and perhexa MC (both made by NOF); perbutyl P, park mill D (both made by NOF) And hydroperoxides such as Park Mill P and Permenter H (both manufactured by NOF Corporation). Examples of the azo initiator include ABN-E, ABN-R, and ABN-V (all manufactured by Nippon Hydrazine Kogyo Co., Ltd.).

  In the polymerization of the pressure-sensitive adhesive resin, a chain transfer agent may be used as necessary. The chain transfer agent is not particularly limited, and thiol compounds such as normal dodecyl mercaptan, dithioglycol, octyl thioglycolate, and mercaptoethanol can be used.

  The polymerization of the pressure-sensitive adhesive resin may be performed without a solvent or in an organic solvent. When polymerizing in an organic solvent, aromatic solvents such as toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; other known organic solvents are used. it can. The type of organic solvent to be used is determined in consideration of the solubility of the obtained resin and the polymerization temperature, but the boiling point of toluene, ethyl acetate, methyl ethyl ketone, etc. is 120 ° C. or less in terms of the difficulty of remaining the residual solvent during drying. Organic solvents are preferred.

  The pressure-sensitive adhesive resin may be composed of a single composition, or may be a polymer alloy or polymer blend in which polymers having different compositions are combined.

  In order to obtain a branched resin, a macromonomer, a polyfunctional monomer, a polyfunctional initiator, and a polyfunctional chain transfer agent can be used. As the macromonomer, AA-6, AA-2, AS-6, AB-6, AK-5 (all manufactured by Toagosei Co., Ltd.) and the like can be used. Examples of the polyfunctional monomer include LIGHT EG EG, LIGHT SEL 1,4BG, LIGHT ESTER NP, LIGHT ESTER TMP (all manufactured by Kyoeisha Chemical Co., Ltd.) and the like. Examples of the polyfunctional initiator include Pertetra A, BTTB-50 (all manufactured by NOF Corporation), Trigonox 17-40MB, Parkadox 12-XL25 (all manufactured by Explosive Akzo), and the like. As the polyfunctional chain transfer agent, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate) or the like can be used.

3. Near-infrared-absorbing pressure-sensitive adhesive composition The near-infrared-absorbing pressure-sensitive adhesive composition of the present invention contains a diimonium dye having a maximum absorption wavelength in an acetone solution of more than 1060 nm and not more than 1200 nm. Excellent in performance. Since the near-infrared absorbing adhesive composition of the present invention contains an adhesive resin, it can be easily adhered to an adherend.

  Other near-infrared absorbing pigments may be added to the near-infrared absorbing adhesive composition of the present invention. Other near infrared absorbing dyes that can be used in combination include known cyanine dyes, polymethine dyes, squarylium dyes, porphyrin dyes, metal dithiol complex dyes, phthalocyanine dyes, diimonium dyes, inorganic oxide particles, and the like. Can be mentioned.

  When the near-infrared absorbing pressure-sensitive adhesive composition of the present invention is used as an optical filter for thin displays, a phthalocyanine dye having a maximum absorption wavelength of 800 to 950 nm and a cyanine dye having a maximum absorption wavelength of 800 to 950 nm together with the diimonium dye. It is preferable that a dye or a metal dithiol complex dye having a maximum absorption wavelength of 800 to 950 nm is used in combination. By this combined use, near infrared rays of 800 to 1100 nm can be effectively absorbed. From the viewpoint of obtaining a near-infrared absorbing pressure-sensitive adhesive composition having good durability, it is particularly preferable to use a phthalocyanine dye in combination.

  The phthalocyanine compound that can be used in the present invention is not particularly limited as long as it has excellent near-infrared absorption ability, and a known phthalocyanine compound can be used. Preferable phthalocyanine compounds include compounds represented by the following formula (A) or compounds represented by the following formula (I).

[Phthalocyanine compound represented by the formula (a)]

In the above formula ^{(A), A} 1 ^{~A 16} represents a functional group. In the formula (a), A ^{1 to} A ¹⁶ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxysulfonyl group, a carboxyl group, a thiol group, or an optionally substituted carbon atom having 1 to 20 carbon atoms. Alkyl groups, optionally substituted alkoxy groups having 1 to 20 carbon atoms, optionally substituted aryl groups having 6 to 20 carbon atoms, optionally substituted carbon atoms 6 to 20 Aryloxy groups, optionally substituted aralkyl groups having 7 to 20 carbon atoms, optionally substituted aralkyloxy groups having 7 to 20 carbon atoms, and optionally substituted carbon atoms 1-20 alkylthio groups, optionally substituted arylthio groups having 6-20 carbon atoms, optionally substituted aralkylthio groups having 7-20 carbon atoms, substituted An optionally substituted alkylsulfonyl group having 1 to 20 carbon atoms, an optionally substituted arylsulfonyl group having 6 to 20 carbon atoms, and an optionally substituted aralkylsulfonyl group having 7 to 20 carbon atoms Group, an optionally substituted acyl group having 1 to 20 carbon atoms, an optionally substituted alkoxycarbonyl group having 2 to 20 carbon atoms, and an optionally substituted carbon atom having 6 to 20 carbon atoms An aryloxycarbonyl group, an optionally substituted aralkyloxycarbonyl group having 2 to 20 carbon atoms, an optionally substituted alkylcarbonyloxy group having 2 to 20 carbon atoms, and optionally substituted. Arylcarbonyloxy group having 6 to 20 carbon atoms, optionally substituted aralkylcarbonyloxy group having 8 to 20 carbon atoms, substituted Carbon atoms optionally 2-20 heterocyclic group, a substituted amino group which may be, optionally substituted aminosulfonyl group or an optionally substituted aminocarbonyl group. The functional groups of A ^{1 to} A ¹⁶ may be the same type or different types, and may be the same or different in the same type, and the functional groups may be connected via a linking group. M ¹ represents two hydrogen atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or an oxy metal. In the present specification, the “acyl group” has the same definition as that described on page 17 of the third edition of the Dictionary of Science and Technology Terms published by the Nikkan Kogyo Shimbun. It is a group from which a group has been removed, and is a group represented by the formula: RCO— (where R is an aliphatic group, an alicyclic group or an aromatic group).

(When the terminal is a functional group other than an amino group)
In the above formula (a), examples of the halogen atom of the functional groups A ^{1 to} A ¹⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the optionally substituted alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, Examples thereof include linear, branched or cyclic alkyl groups such as t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group. It is not limited to. Examples of the optionally substituted alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butyloxy group, iso-butyloxy group, sec-butyloxy Group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, etc., linear, branched or cyclic Although an alkoxy group is mentioned, it is not limited to these. Examples of the optionally substituted aryl group having 6 to 20 carbon atoms include, but are not limited to, a phenyl group and a naphthyl group. Examples of the optionally substituted aryloxy group having 6 to 20 carbon atoms include phenoxy group and naphthoxy group, but are not limited thereto. Examples of the aralkyl group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, benzyl group, phenethyl group, diphenylmethyl group and the like. Examples of the aralkyloxy group having 7 to 20 carbon atoms which may be substituted include a benzyloxy group, a phenethyloxy group, a diphenylmethyloxy group and the like, but are not limited thereto. Examples of the optionally substituted alkylthio group having 1 to 20 carbon atoms include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, Examples thereof include linear, branched or cyclic alkylthio groups such as t-butylthio group, n-pentylthio group, n-hexylthio group, cyclohexylthio group, n-heptylthio group, n-octylthio group, 2-ethylhexylthio group, It is not limited to these. Examples of the optionally substituted arylthio group having 6 to 20 carbon atoms include a phenylthio group and a naphthylthio group, but are not limited thereto. Examples of the aralkylthio group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, a benzylthio group, a phenethylthio group, a diphenylmethylthio group and the like. Examples of the optionally substituted alkylsulfonyl group having 1 to 20 carbon atoms include methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, iso-propylsulfonyl group, n-butylsulfonyl group, iso-butylsulfonyl. Group, sec-butylsulfonyl group, t-butylsulfonyl group, n-pentylsulfonyl group, n-hexylsulfonyl group, cyclohexylsulfonyl group, n-heptylsulfonyl group, n-octylsulfonyl group, 2-ethylhexylsulfonyl group, etc. Examples include, but are not limited to, linear, branched, or cyclic alkylsulfonyl groups. Examples of the arylsulfonyl group having 6 to 20 carbon atoms which may be substituted include, but are not limited to, a phenylsulfonyl group and a naphthylsulfonyl group. Examples of the aralkylsulfonyl group which may be substituted include a benzylsulfonyl group, a phenethylsulfonyl group, a diphenylmethylsulfonyl group, and the like, but are not limited thereto. Examples of the optionally substituted acyl group having 1 to 20 carbon atoms include methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl group, straight chain such as sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, n-hexylcarbonyl group, cyclohexylcarbonyl group, n-heptylcarbonyl group, n-octylcarbonyl group, 2-ethylhexylcarbonyl group, Examples include, but are not limited to, branched or cyclic alkylcarbonyl groups, arylcarbonyl groups such as benzylcarbonyl groups and phenylcarbonyl groups, and aralkylcarbonyl groups such as benzoyl groups. Examples of the optionally substituted alkoxycarbonyl group having 2 to 20 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, iso-propyloxycarbonyl group, n-butyloxycarbonyl group, iso -Butyloxycarbonyl group, sec-butyloxycarbonyl group, t-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxy Examples thereof include, but are not limited to, a carbonyl group and a 2-ethylhexyloxycarbonyl group. Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, phenoxycarbonyl and naphthylcarbonyl groups. Examples of the aralkyloxycarbonyl group having 8 to 20 carbon atoms which may be substituted include, but are not limited to, benzyloxycarbonyl group, phenethyloxycarbonyl group, diphenylmethyloxycarbonyl group and the like. . Examples of the optionally substituted alkylcarbonyloxy group having 2 to 20 carbon atoms include acetyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxy group, and n-butylcarbonyloxy group. , Iso-butylcarbonyloxy group, sec-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, n-hexylcarbonyloxy group, cyclohexylcarbonyloxy group, n-heptylcarbonyloxy group, 3- A heptyl carbonyloxy group, n-octyl carbonyloxy group, etc. are mentioned, However, It is not limited to these. Examples of the arylcarbonyloxy group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, a benzoyloxy group. Examples of the aralkylcarbonyloxy group having 8 to 20 carbon atoms which may be substituted include, but are not limited to, a benzylcarbonyloxy group. Examples of the optionally substituted heterocyclic group having 2 to 20 carbon atoms include, but are not limited to, a pyrrole group, an imidazole group, a piperidine group, and a morpholine group.

In the above formula (a), the alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group, alkylthio group, arylthio group, aralkylthio group, alkylsulfonyl group of the functional groups A ^{1 to} A ¹⁶ An arylsulfonyl group, an aralkylsulfonyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, an alkylcarbonyloxy group, an arylcarbonyloxy group, an aralkylcarbonyloxy group or a heterocyclic group As the substituents present in these functional groups A ^{1 to} A ¹⁶ , for example, halogen atoms, acyl groups, alkyl groups, phenyl groups, alkoxy groups, halogenated alkyl groups, halogenated alkoxy groups, nitro groups, amino groups, Alkyl Mino group, alkylcarbonylamino group, arylamino group, arylcarbonylamino group, carbonyl group, alkoxycarbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, alkylthio group, carbamoyl group, aryloxycarbonyl group, cyano group, heterocyclic group However, it is not limited to these. A plurality of these substituents may be present. When a plurality of substituents are present, they may be the same or different, and even in the same case, they may be the same or different. Moreover, substituents may be connected through a linking group.

(When the terminal is an amino group)
In the above formula (a), the substituents on the optionally substituted amino group, the optionally substituted aminosulfonyl group, and the optionally substituted aminocarbonyl group of the functional groups A ^{1 to} A ¹⁶ are as follows: Hydrogen atom: linear, branched or cyclic such as methyl group, ethyl group, n-propyl group, n-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group and cyclohexyl group Alkyl group; aryl group such as phenyl group and naphthyl group; aralkyl group such as benzyl group and phenethyl group; acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso- Butylcarbonyl group, sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, n-hexyl A linear, branched or cyclic alkylcarbonyl group such as a sulfonyl group, a cyclohexylcarbonyl group, an n-heptylcarbonyl group, a 3-heptylcarbonyl group or an n-octylcarbonyl group; an arylcarbonyl group such as a benzoyl group or a naphthylcarbonyl group; Examples thereof include, but are not limited to, an aralkylcarbonyl group such as a carbonyl group, and these substituents may be further substituted with a substituent. These substituents may be present in the number of 0, 1 or 2, and when 2 are present, they may be the same or different from each other, and even in the same type, they may be the same or different. Also good. Moreover, when there are two substituents, the substituents may be connected via a linking group.

  Alkyl group, aryl group, aralkyl group, alkylcarbonyl group, arylcarbonyl which is a substituent to the above-mentioned optionally substituted amino group, optionally substituted aminosulfonyl group or optionally substituted aminocarbonyl group Group, aralkylcarbonyl group and the like, which may be further present as a substituent, for example, halogen atom, acyl group, alkyl group, phenyl group, alkoxy group, halogenated alkyl group, halogenated alkoxy group, nitro group, amino group, Alkylamino group, alkylcarbonylamino group, arylamino group, arylcarbonylamino group, carbonyl group, alkoxycarbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, alkylthio group, carbamoyl group, aryloxycarbonyl group, cyano group, complex Groups including but not limited to. A plurality of these substituents may be present. When a plurality of substituents are present, they may be the same or different, and even in the same case, they may be the same or different. Moreover, substituents may be connected through a linking group.

Examples of the divalent metal as the metal M ¹ include Cu (II), Co (II), Zn (II), Fe (II), Ni (II), Ru (II), and Rh (II). , Pd (II), Pt (II), Mn (II), Mg (II), Ti (II), Be (II), Ca (II), Ba (II), Cd (II), Hg (II) , Pb (II), Sn (II) and the like, but are not limited thereto. Examples of trivalent substituted metal atoms include Al-F, Al-Cl, Al-Br, Al-I, Fe-Cl, Ga-F, Ga-Cl, Ga-I, Ga-Br, 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), In-C 6 H 5, Mn (OH), Mn (OC 6 H 5), Mn [OSi _{(CH 3)} 3], Ru-Cl, etc. is Although it is mentioned, it is not limited to these. Examples of tetravalent substituted metal atoms include CrCl ₂ , SiF ₂ , SiCl ₂ , SiBr ₂ , SiI ₂ , ZrCl ₂ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ , SnF ₂ , SnCl ₂ , SnBr ₂ , TiF ₂ , TiCl ₂ , TiBr ₂ , Ge (OH) ₂ , Mn (OH) ₂ , Si (OH) ₂ , Sn (OH) ₂ , Zr (OH) ₂ , Cr (R ₁ ) ₂ , Ge (R ₁ ) ₂ , Si (R ₁ ) ₂ , Sn (R ₁ ) ₂ , Ti (R ₁ ) ₂ {R ₁ represents an alkyl group, a phenyl group, a naphthyl group, or a derivative thereof} Cr (OR ₂ ) ₂ , _{Ge (OR 2) 2, Si} (OR 2) 2, Sn (OR 2) 2, Ti (OR 2) 2, {R 2 is an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group, a dialkyl Alkoxysilyl represents a group or a derivative _{thereof}, Sn (SR 3) 2} , Ge (SR 3) 2 {R 3 is an alkyl group, a phenyl group, a naphthyl group or a derivative thereof} to but like these It is not limited. Examples of oxymetals include, but are not limited to, VO, MnO, TiO and the like.

[Phthalocyanine compound represented by the formula (I)]

In the above formula (A), B ^{1 to} B ²⁴ represent functional groups. B ^{1 to} B ²⁴ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxysulfonyl group, a carboxyl group, a thiol group, an optionally substituted alkyl group having 1 to 20 carbon atoms, or a substituted group. An optionally substituted alkoxy group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, an optionally substituted aryloxy group having 6 to 20 carbon atoms, and substitution An aralkyl group having 7 to 20 carbon atoms which may be substituted, an aralkyloxy group having 7 to 20 carbon atoms which may be substituted, and an alkylthio group having 1 to 20 carbon atoms which may be substituted , An optionally substituted arylthio group having 6 to 20 carbon atoms, an optionally substituted aralkylthio group having 7 to 20 carbon atoms, and an optionally substituted carbon atom 1-20 alkylsulfonyl groups, optionally substituted arylsulfonyl groups having 6-20 carbon atoms, optionally substituted aralkylsulfonyl groups having 7-20 carbon atoms, optionally substituted Good acyl group having 1 to 20 carbon atoms, optionally substituted alkoxycarbonyl group having 2 to 20 carbon atoms, optionally substituted aryloxycarbonyl group having 6 to 20 carbon atoms, substitution An aralkyloxycarbonyl group having 2 to 20 carbon atoms which may be substituted, an alkylcarbonyloxy group having 2 to 20 carbon atoms which may be substituted, and 6 to 20 carbon atoms which may be substituted Arylcarbonyloxy group, optionally substituted aralkylcarbonyloxy group having 8 to 20 carbon atoms, optionally substituted carbon atom 2-20 heterocyclic group, a substituted amino group which may be, optionally substituted aminosulfonyl group or an optionally substituted aminocarbonyl group. The functional groups of B ^{1 to} B ²⁴ may be the same or different, and may be the same or different in the same type, and the functional groups may be linked via a linking group. M ² represents two hydrogen atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or an oxy metal.

(When the terminal is a functional group other than an amino group)
In the above formula (A), examples of the halogen atom of the functional groups B ^{1 to} B ²⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the optionally substituted alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, Examples thereof include linear, branched or cyclic alkyl groups such as t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group. It is not limited to. Examples of the optionally substituted alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butyloxy group, iso-butyloxy group, sec-butyloxy Group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, etc., linear, branched or cyclic Although an alkoxy group is mentioned, it is not limited to these. Examples of the optionally substituted aryl group having 6 to 20 carbon atoms include, but are not limited to, a phenyl group and a naphthyl group. Examples of the optionally substituted aryloxy group having 6 to 20 carbon atoms include phenoxy group and naphthoxy group, but are not limited thereto. Examples of the aralkyl group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, benzyl group, phenethyl group, diphenylmethyl group and the like. Examples of the aralkyloxy group having 7 to 20 carbon atoms which may be substituted include a benzyloxy group, a phenethyloxy group, a diphenylmethyloxy group and the like, but are not limited thereto. Examples of the optionally substituted alkylthio group having 1 to 20 carbon atoms include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, Examples thereof include linear, branched or cyclic alkylthio groups such as t-butylthio group, n-pentylthio group, n-hexylthio group, cyclohexylthio group, n-heptylthio group, n-octylthio group, 2-ethylhexylthio group, It is not limited to these. Examples of the optionally substituted arylthio group having 6 to 20 carbon atoms include a phenylthio group and a naphthylthio group, but are not limited thereto. Examples of the aralkylthio group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, a benzylthio group, a phenethylthio group, a diphenylmethylthio group and the like. Examples of the optionally substituted alkylsulfonyl group having 1 to 20 carbon atoms include methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, iso-propylsulfonyl group, n-butylsulfonyl group, iso-butylsulfonyl. Group, sec-butylsulfonyl group, t-butylsulfonyl group, n-pentylsulfonyl group, n-hexylsulfonyl group, cyclohexylsulfonyl group, n-heptylsulfonyl group, n-octylsulfonyl group, 2-ethylhexylsulfonyl group, etc. Examples include, but are not limited to, linear, branched, or cyclic alkylsulfonyl groups. Examples of the arylsulfonyl group having 6 to 20 carbon atoms which may be substituted include, but are not limited to, a phenylsulfonyl group and a naphthylsulfonyl group. Examples of the aralkylsulfonyl group which may be substituted include a benzylsulfonyl group, a phenethylsulfonyl group, a diphenylmethylsulfonyl group, and the like, but are not limited thereto. Examples of the optionally substituted acyl group having 1 to 20 carbon atoms include methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl group, straight chain such as sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, n-hexylcarbonyl group, cyclohexylcarbonyl group, n-heptylcarbonyl group, n-octylcarbonyl group, 2-ethylhexylcarbonyl group, Examples include, but are not limited to, branched or cyclic alkylcarbonyl groups, arylcarbonyl groups such as benzylcarbonyl groups and phenylcarbonyl groups, and aralkylcarbonyl groups such as benzoyl groups. Examples of the optionally substituted alkoxycarbonyl group having 2 to 20 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, iso-propyloxycarbonyl group, n-butyloxycarbonyl group, iso -Butyloxycarbonyl group, sec-butyloxycarbonyl group, t-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxy Examples thereof include, but are not limited to, a carbonyl group and a 2-ethylhexyloxycarbonyl group. Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, phenoxycarbonyl and naphthylcarbonyl groups. Examples of the aralkyloxycarbonyl group having 8 to 20 carbon atoms which may be substituted include, but are not limited to, benzyloxycarbonyl group, phenethyloxycarbonyl group, diphenylmethyloxycarbonyl group and the like. . Examples of the optionally substituted alkylcarbonyloxy group having 2 to 20 carbon atoms include acetyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxy group, and n-butylcarbonyloxy group. , Iso-butylcarbonyloxy group, sec-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, n-hexylcarbonyloxy group, cyclohexylcarbonyloxy group, n-heptylcarbonyloxy group, 3- A heptyl carbonyloxy group, n-octyl carbonyloxy group, etc. are mentioned, However, It is not limited to these. Examples of the arylcarbonyloxy group having 7 to 20 carbon atoms which may be substituted include, but are not limited to, a benzoyloxy group. Examples of the aralkylcarbonyloxy group having 8 to 20 carbon atoms which may be substituted include, but are not limited to, a benzylcarbonyloxy group. Examples of the optionally substituted heterocyclic group having 2 to 20 carbon atoms include, but are not limited to, a pyrrole group, an imidazole group, a piperidine group, and a morpholine group.

In the above formula (I), the alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group, alkylthio group, arylthio group, aralkylthio group, alkylsulfonyl group, aryl of the functional groups B ^{1 to} B ²⁴ When a sulfonyl group, aralkylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, aralkylcarbonyloxy group or heterocyclic group is substituted, these as substituents present on the functional groups B ¹ .about.B ^24, for example, a halogen atom, an acyl group, an alkyl group, a phenyl group, an alkoxy group, a halogenated alkyl group, halogenated alkoxy group, a nitro group, an amino group, an alkylamino group Alkylcarbonylamino group, arylamino group, arylcarbonylamino group, carbonyl group, alkoxycarbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, alkylthio group, carbamoyl group, aryloxycarbonyl group, cyano group, heterocyclic group, etc. However, it is not limited to these. A plurality of these substituents may be present. When a plurality of substituents are present, they may be the same or different, and even in the same case, they may be the same or different. Moreover, substituents may be connected through a linking group.

(When the terminal is an amino group)
In the above formula (I), the substituents on the optionally substituted amino group, the optionally substituted aminosulfonyl group, and the optionally substituted aminocarbonyl group of the functional groups B ^{1 to} B ²⁴ are as follows: Hydrogen atom: linear, branched or cyclic such as methyl group, ethyl group, n-propyl group, n-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group and cyclohexyl group Alkyl group; aryl group such as phenyl group and naphthyl group; aralkyl group such as benzyl group and phenethyl group; acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso- Butylcarbonyl group, sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, n-hexyl A linear, branched or cyclic alkylcarbonyl group such as a sulfonyl group, a cyclohexylcarbonyl group, an n-heptylcarbonyl group, a 3-heptylcarbonyl group or an n-octylcarbonyl group; an arylcarbonyl group such as a benzoyl group or a naphthylcarbonyl group; Examples thereof include, but are not limited to, an aralkylcarbonyl group such as a carbonyl group, and these substituents may be further substituted with a substituent. These substituents may be present in the number of 0, 1 or 2, and when 2 are present, they may be the same or different from each other, and even in the same type, they may be the same or different. Also good. Moreover, when there are two substituents, the substituents may be connected via a linking group.

  The above-mentioned amino group which may be substituted, aminosulfonyl group which may be substituted, alkyl group, aryl group, aralkyl group, alkylcarbonyl group, arylcarbonyl which is a substituent to the optionally substituted aminocarbonyl group Group, aralkylcarbonyl group and the like, which may be further present as a substituent, for example, halogen atom, acyl group, alkyl group, phenyl group, alkoxy group, halogenated alkyl group, halogenated alkoxy group, nitro group, amino group, Alkylamino group, alkylcarbonylamino group, arylamino group, arylcarbonylamino group, carbonyl group, alkoxycarbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, alkylthio group, carbamoyl group, aryloxycarbonyl group, cyano group, heterocyclic ring Base Including but not limited to. A plurality of these substituents may be present. When a plurality of substituents are present, they may be the same or different, and even in the same case, they may be the same or different. Moreover, substituents may be connected through a linking group.

Examples of the divalent metal as the metal M ² include Cu (II), Co (II), Zn (II), Fe (II), Ni (II), Ru (II), and Rh (II). , Pd (II), Pt (II), Mn (II), Mg (II), Ti (II), Be (II), Ca (II), Ba (II), Cd (II), Hg (II) , Pb (II), Sn (II) and the like, but are not limited thereto. Examples of trivalent substituted metal atoms include Al-F, Al-Cl, Al-Br, Al-I, Fe-Cl, Ga-F, Ga-Cl, Ga-I, Ga-Br, 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), In-C 6 H 5, Mn (OH), Mn (OC 6 H 5), Mn [OSi _{(CH 3)} 3], Ru-Cl, etc. is Although it is mentioned, it is not limited to these. Examples of tetravalent substituted metal atoms include CrCl ₂ , SiF ₂ , SiCl ₂ , SiBr ₂ , SiI ₂ , ZrCl ₂ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ , SnF ₂ , SnCl ₂ , SnBr ₂ , _{TiF 2, TiCl 2, TiBr 2} , Ge (OH) 2, Mn (OH) 2, Si (OH) 2, Sn (OH) 2, Zr (OH) 2, Cr (R1) 2, Ge (R 1) ₂ , Si (R ₁ ) ₂ , Sn (R ₁ ) ₂ , Ti (R ₁ ) ₂ {R ₁ represents an alkyl group, a phenyl group, a naphthyl group, or a derivative thereof}, Cr (OR ₂ ) ₂ , Ge (OR ₂ ) ₂ , Si (OR ₂ ) ₂ , Sn (OR ₂ ) ₂ , Ti (OR ₂ ) ₂ {R ₂ is an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group, a dialkyl group. A alkoxysilyl group or a derivative thereof}, Sn (SR ₃ ) ₂ , Ge (SR ₃ ) ₂ {R ₃ represents an alkyl group, a phenyl group, a naphthyl group, or a derivative thereof}, etc. It is not limited to. Examples of oxymetals include, but are not limited to, VO, MnO, TiO and the like.

  As specific phthalocyanine-based compounds, trade names EEX COLOR IR-10A, EEX COLOR IR-12, EEX COLOR IR-14, TX-EX-906B, TX-EX-910B, TX-EX-902K (any Also made by Nippon Shokubai).

  In addition, a cyanine dye may be used in combination with the near-infrared absorbing adhesive composition of the present invention as a near-infrared absorbing dye. The cyanine dye is not particularly limited as long as it has an excellent near-infrared absorbing ability, but a salt composed of an indolium cation or a benzothiazolium cation and a counter anion can be preferably used. As the indolium cation or the benzothiazolium cation, cations represented by the above formulas (a) to (i) can be preferably used, but are not limited thereto.

  The counter anion of the indolium cation or benzothiazolium cation is not particularly limited, and chloride ion, bromide ion, iodide ion, perchlorate ion, nitrate ion, benzenesulfonate ion, p-toluenesulfonic acid Ion, methyl sulfate ion, ethyl sulfate ion, propyl sulfate ion, tetrafluoroborate ion, tetraphenylborate ion, hexafluorophosphate ion, benzenesulfinate ion, acetate ion, trifluoroacetate ion, propionate ion, benzoic acid Acid ion, oxalate ion, succinate ion, malonate ion, oleate ion, stearate ion, citrate ion, monohydrogen diphosphate ion, dihydrogen monophosphate ion, pentachlorostannate ion, chlorosulfonic acid Ion, fluorosulfo Acid ion, trifluoromethanesulfonate ion, hexafluoroarsenate ion, hexafluoroantimonate ion, molybdate ion, tungstate ion, titanate ion, zirconate ion, sulfate ion, vanadate ion, borate ion, etc. it can.

  More specifically, as a cyanine dye containing a cation represented by the above general formula (a), ADS812MI (counter anion is an iodide ion) manufactured by American Dye Source Co .; represented by the above general formula (b) S0712 manufactured by FEW Chemical Co. (counter anion is hexafluorophosphate ion) as a cyanine dye containing a cation; S0726 manufactured by FEW Chemical Co. as a cyanine dye containing a cation represented by the general formula (c) Counter anion is chloride ion); As cyanine-based dye containing a cation represented by the above general formula (d), ADS780MT manufactured by American Dice Source (counter anion is p-toluenesulfonic acid ion); As a cyanine dye containing a cation represented by the following formula: S0006 (counter anion is FEW Chemical) Chlorate ion); as a cyanine dye containing a cation represented by the above general formula (f), S0081 (counter anion is perchlorate ion) manufactured by FEW Chemical Co .; cation represented by the above general formula (g) As a cyanine dye containing F0 Chemical Co., S0773 (counter anion is tetrafluoroborate ion); As a cyanine dye containing a cation represented by the general formula (h), trade name S0772 manufactured by FEW Chemical Co., Ltd. (Counter anion is tetrafluoroborate ion); as a cyanine dye containing a cation represented by the above general formula (i), commercially available product name S0734 (counter anion is tetrafluoroborate ion) manufactured by FEW Chemical Co., Ltd. Can be used. By using a cyanine dye, a near-infrared absorbing adhesive composition having high transparency in the visible region can be obtained.

  The blending amount of the diimonium dye of the present invention or the total blending amount of the diimonium dye of the present invention and other near-infrared absorbing dyes can be appropriately selected depending on the type and use of the dye. When the near infrared ray absorbing pressure-sensitive adhesive composition of the present invention is used as a thin film having a thickness of 10 to 30 μm, the blending amount is preferably 0.01 to 10% by weight, more preferably 0.8%, based on the solid content of the resin. 1 to 5% by weight. For example, when a diimonium dye and a phthalocyanine dye are used in combination, the total amount of these dyes is preferably 0.01 to 10% by weight, more preferably 0.1%, based on the solid content of the resin. ~ 5% by weight. If the blending amount is less than 0.01% by weight, there is a possibility that sufficient near infrared absorption ability cannot be achieved. Conversely, if it exceeds 10% by weight, an effect commensurate with the addition cannot be obtained, and it is not economical, and conversely, transparency in the visible region may be impaired.

  The near-infrared absorbing pressure-sensitive adhesive composition of the present invention is characterized by transparency in the visible region, high near-infrared absorbing ability and its durability, and good adhesiveness. If necessary, a dye that absorbs visible light may be added to the near-infrared absorbing adhesive composition of the present invention. Examples of dyes that absorb visible light include cyanine, phthalocyanine, naphthalocyanine, porphyrin, tetraazaporphyrin, metal dithiol complex, squarylium, azurenium, diphenylmethane, triphenylmethane, oxazine, and azine. , Thiopyrylium, viologen, azo, azo metal complex, bisazo, anthraquinone, perylene, indanthrone, nitroso, indico, azomethine, xanthene, oxanol, indoaniline, quinoline A conventionally well-known pigment | dye, such as a system and a diketopyrrolopyrrole type | system | group, can be used widely.

  When the near-infrared absorbing pressure-sensitive adhesive composition of the present invention is used as an optical filter for PDP, it is preferable to use a visible absorbing dye having a maximum absorption wavelength of 550 to 650 nm in order to absorb unnecessary neon light emission. The type of the dye that absorbs neon light emission is not particularly limited, and a cyanine dye and a tetraazaporphyrin dye can be used. Specifically, Adeka Arcles TY-102 (Asahi Denka Kogyo Co., Ltd.), Adeka Arcles TY-14 (Asahi Denka Kogyo Co., Ltd.), Adeka Arcles TY-15 (Asahi Denka Kogyo Co., Ltd.), TAP-2 ( Yamada Chemical Industries), TAP-18 (Yamada Chemical Industries), TAP-45 (Yamada Chemical Industries), trade names NK-5451 (Hayashibara Biochemistry Laboratories), NK-5532 (Hayashibara Biochemistry Laboratories) ), NK-5450 (manufactured by Hayashibara Biochemical Research Institute) and the like. The addition amount of the dye for absorbing neon emission varies depending on the kind of the dye, but it is preferable to add so that the transmittance at the maximum absorption wavelength is about 20 to 80%.

  Moreover, in order to adjust the color tone of the thin film which consists of a near-infrared absorption adhesive composition, you may add the visible light absorption pigment | dye for toning. There are no particular limitations on the type of coloring pigment, but 1: 2 chromium complex, 1: 2 cobalt complex, copper phthalocyanine, anthraquinone, diketopyrrolopyrrole, and the like can be used. Specifically, Orazol Blue GN (manufactured by Ciba Specialty Chemicals), Orazol Blue BL (manufactured by Ciba Specialty Chemicals), Orazol Red 2B (manufactured by Ciba Specialty Chemicals), Orazol Red G (Ciba)・ Specialty Chemicals), Orazole Black CN (Ciba Specialty Chemicals), Orasol Yellow 2GLN (Ciba Specialty Chemicals), Orazole Yellow 2RLN (Ciba Specialty Chemicals), Microlith DPP Red BK (manufactured by Ciba Specialty Chemicals), and the like.

  Furthermore, the near-infrared absorption adhesive composition of this invention may contain the 1 type (s) or 2 or more types of the solvent, additive, and hardening | curing agent in the range which does not lose the performance as needed.

  The near-infrared-absorbing pressure-sensitive adhesive composition of the present invention may be one in which a near-infrared-absorbing dye is mixed in a resin in the form of a solid (for example, powder). When the near-infrared absorbing adhesive composition is coated on a film, the near-infrared absorbing dye is preferably dissolved, dispersed or suspended in a solvent.

  Solvents that can be used for coating include, for example, aliphatic systems such as cyclohexane and methylcyclohexane; aromatic systems such as toluene and xylene; ketone systems such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate and butyl acetate. Nitriles such as acetonitrile; alcohols such as methanol, ethanol and isopropyl alcohol; ethers such as tetrahydrofuran and dibutyl ether; butyl cellosolve, propylene glycol n-propyl ether, propylene glycol n-butyl ether, propylene glycol monomethyl ether acetate, etc. Glycol ether type; Amide type such as formamide and N, N-dimethylformamide; Halogen type such as methylene chloride and chloroform can be used.These may be used alone or in combination. In order to improve the durability of the dye, a solvent having a boiling point of 100 ° C. or less, such as methyl ethyl ketone and ethyl acetate, is suitable. Moreover, in order to improve the coating film appearance at the time of coating, the solvent whose boiling point is 100-150 degreeC, such as toluene, methyl isobutyl ketone, butyl acetate, is suitable. In order to improve the crack resistance of the coating film, a solvent having a boiling point of 150 to 200 ° C. such as butyl cellosolve, propylene glycol n-propyl ether, propylene glycol n-butyl ether, and propylene glycol monomethyl ether acetate is preferable.

  The viscosity of the coating agent is appropriately selected depending on the type of coating machine, but when coating is performed by a small-diameter gravure kiss reverse method such as a micro gravure coater, the coating is performed by an extrusion method such as a die coater. In this case, 100 to 10,000 mPa · s is common. The solid content of the coating agent is adjusted according to the viscosity of the paint.

  Moreover, as an additive, the conventionally well-known additive used for the resin composition which forms a film, a coating film, etc. may be used. These additives include dispersants, leveling agents, antifoaming agents, viscosity modifiers, matting agents, tackifiers, antistatic agents, antioxidants, UV absorbers, light stabilizers, quenchers, curing agents, A blocking agent etc. are mentioned. In addition, an isocyanate compound, a thiol compound, an epoxy compound, an amine compound, an imine compound, an oxazoline compound, a silane coupling agent, a UV curing agent, and the like can be used as the curing agent.

  The near-infrared absorbing adhesive composition of the present invention is a near-infrared absorbing material for optical, agricultural, architectural or vehicle use, an image recording material such as photosensitive paper, an information recording material such as an optical disc, and a dye-sensitized type. It can be used for a solar cell such as a solar cell, a photosensitive material using a semiconductor laser beam or the like as a light source, and an eye strain prevention material. The near infrared absorbing pressure-sensitive adhesive composition of the present invention is particularly preferably used in the form of a film or a sheet.

4). Near-infrared absorbing material The near-infrared absorbing material according to the present invention includes the near-infrared absorbing adhesive composition. The near-infrared absorbing material of the present invention may be a film obtained by forming the near-infrared absorbing adhesive composition into a film, and a coating film containing the near-infrared absorbing adhesive composition is laminated on a transparent substrate. It may be what you did.

  The transparent substrate is generally usable for optical materials and is not particularly limited as long as it is substantially transparent. Specific examples include glass; olefin polymers such as cyclopolyolefin and amorphous polyolefin; methacrylic polymers such as polymethyl methacrylate; vinyl polymers such as vinyl acetate and vinyl halides; polyesters such as PET; polycarbonate and butyral. Examples thereof include polyvinyl acetals such as resins; polyaryl ether resins. From the viewpoint of improving the durability of the diimonium dye, the material of the transparent substrate is preferably a resin, and more preferably PET. Resins such as PET are considered to have less ionic component elution than alkali glass such as soda lime glass. When the ionic component and the diimonium cation are bonded and the diimonium cation is not divalent (for example, becomes monovalent), the near infrared absorption ability of the diimonium dye is decreased. The combination of a resin such as PET with little ionic component elution and the dimonium dye of the present invention is considered to provide durability that can be practically used.

  The transparent substrate is subjected to surface treatment by a conventionally known method such as corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, chemical treatment, and coating such as an anchor coating agent and a primer. May be. The base resin constituting the transparent base material can be blended with known additives, heat aging inhibitors, lubricants, antistatic agents, and the like. The transparent substrate is formed into a film or a sheet using a known method such as injection molding, T-die molding, calendar molding, compression molding, or a method of casting by melting in an organic solvent. The base material constituting the transparent base material may be unstretched or stretched, and may be laminated with another base material.

  As a transparent substrate for obtaining a near infrared ray absorbing film by a coating method, a PET film is preferable, and a PET film subjected to an easy adhesion treatment is particularly preferable. Specifically, Cosmo Shine A4300 (manufactured by Toyobo), Lumirror U34 (manufactured by Toray), Melinex 705 (manufactured by Teijin DuPont) and the like can be mentioned. Functional films such as a lactone ring-containing resin film, a TAC (triacetylcellulose) film, an antireflection film, an antiglare film, an impact absorbing film, an electromagnetic wave shielding film, and an ultraviolet absorbing film can also be used as the transparent substrate. Thereby, the optical filter for thin displays and optical semiconductor elements can be produced simply. The transparent substrate is preferably a film.

  Among these, glass, PET film, easy-adhesion PET film, lactone ring-containing resin film, TAC film, antireflection film and electromagnetic wave shielding film are preferably used as the transparent substrate. When an inorganic base material such as glass is used as the transparent base material, a material having a small alkali component is preferable from the viewpoint of durability of the near-infrared absorbing dye.

  The thickness of the near-infrared absorbing material of the present invention is generally about 0.1 μm to 10 mm, but is appropriately determined according to the purpose. Further, the content of the near-infrared absorbing dye contained in the near-infrared absorbing material is also appropriately determined according to the purpose.

  Although it does not specifically limit as a method of producing the near-infrared absorber of this invention, For example, the following method can be utilized. For example, (I) a method of kneading a resin and a near-infrared absorbing adhesive composition according to the present invention and thermoforming them to produce a resin plate or film; (II) a near-infrared absorbing adhesive composition according to the present invention And a method of producing a resin plate or film by casting polymerization of a monomer or an oligomer in the presence of a polymerization catalyst; (III) a method of coating the near-infrared absorbing adhesive composition according to the present invention on the transparent substrate, etc. It is.

  As a production method of (I), although the processing temperature, filming (resin plate) conditions, etc. are slightly different depending on the resin used, the near-infrared absorbing pressure-sensitive adhesive composition according to the present invention is usually used as a resin powder or pellet. Examples thereof include a method of adding and heating and dissolving at 150 to 350 ° C. and then molding to prepare a resin plate, a method of forming a film (resin plate) with an extruder, and the like.

  As a preparation method of (II), the near-infrared absorbing pressure-sensitive adhesive composition according to the present invention and a monomer or oligomer are cast polymerized in the presence of a polymerization catalyst, and the mixture is injected into a mold and reacted to be cured. Or by pouring into a mold and solidifying until a hard product is formed in the mold. Many resins can be molded in this process. Specific examples of such resins include acrylic resins, diethylene glycol bis (allyl carbonate) resins, epoxy resins, phenol-formaldehyde resins, polystyrene resins, silicon resins, and the like. Among them, the casting method by bulk polymerization of methyl methacrylate, which can obtain an acrylic sheet excellent in hardness, heat resistance, and chemical resistance, is preferable.

  As the polymerization catalyst, a known radical thermal polymerization initiator can be used, and examples thereof include peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide and diisopropyl peroxycarbonate, and azo compounds such as azobisisobutyronitrile. . The amount used is generally from 0.01 to 5% by weight, based on the total amount of the mixture. The heating temperature in thermal polymerization is generally 40 to 200 ° C., and the polymerization time is generally about 30 minutes to 8 hours. In addition to thermal polymerization, a method of photopolymerization by adding a photopolymerization initiator or a sensitizer can also be used.

  As the method of (III), a method of coating the near-infrared absorbing material of the present invention on a transparent substrate, a paint in which the near-infrared absorbing adhesive composition of the present invention is fixed to fine particles, and the fine particles are dispersed are used. There is a method of coating on a transparent substrate.

  A known coating machine can be used when applying the near-infrared absorbing adhesive composition to the substrate. Examples thereof include knife coaters such as comma coaters, fountain coaters such as slot die coaters and lip coaters, kiss coaters such as micro gravure coaters, roll coaters such as gravure coaters and reverse roll coaters, flow coaters, spray coaters and bar coaters. Prior to coating, the substrate may be surface treated by a known method such as corona discharge treatment or plasma treatment. As a drying / curing method, a known method such as hot air, far-infrared ray or UV curing can be used. You may wind up with a well-known protective film after drying and hardening.

  The drying method is not particularly limited, and hot air drying or far infrared drying can be used. The drying temperature may be determined in consideration of the length of the drying line, the line speed, the coating amount, the residual solvent amount, the type of substrate, and the like. If the substrate is a PET film, the general drying temperature is 50 to 150 ° C. When there are a plurality of dryers in one line, each dryer may be set to a different temperature and wind speed. In order to obtain a coating film having a good coating appearance, it is preferable that the drying condition on the inlet side is mild.

  The near-infrared absorbing pressure-sensitive adhesive composition of the present invention can be a constituent material of an excellent optical filter having high transparency in the visible region and high near-infrared absorbing ability. The near-infrared absorbing pressure-sensitive adhesive composition of the present invention has high near-infrared absorbing ability, and can exhibit practical durability in the pressure-sensitive adhesive composition. Furthermore, since the near-infrared absorbing adhesive composition of the present invention can be easily formed into a sheet or film, it is effective for thin displays and optical semiconductor elements. In addition, the near-infrared absorbing adhesive composition of the present invention can also be used in filters and films that need to cut infrared rays, such as agricultural films, heat insulating films, sunglasses, optical recording materials, and the like.

5. Optical filter The near-infrared absorbing adhesive composition of the present invention is suitable for an optical filter. This optical filter is formed using the near-infrared absorbing material. This optical filter is suitable as an optical filter for an optical semiconductor element or an optical filter for a thin display. Such an optical filter has a total light transmittance in the visible region of 40% or more, preferably 50% or more, more preferably 60% or more, and a near-infrared transmittance of a wavelength of 800 to 1100 nm is preferably 30% or less. Is 15% or less, more preferably 5% or less.

  In addition to the near-infrared absorbing layer comprising the above-mentioned near-infrared absorbing adhesive composition, the optical filter of the present invention includes an electromagnetic wave shielding layer, an antireflection layer, a glare prevention (antiglare) layer, a scratch prevention layer, and color adjustment. A support such as a layer or glass may be provided.

  What is necessary is just to select the structure of each layer of an optical filter arbitrarily. For example, an optical filter that preferably combines at least one of an antireflection layer and an antiglare layer and at least two layers of a near-infrared absorbing layer is preferable, and more preferably at least 3 that further combines an electromagnetic wave shielding layer. An optical filter having a layer.

  The antireflection layer or the glare prevention layer is preferably the outermost layer on the human side. The stacking order between the near infrared absorbing layer and the electromagnetic wave shielding layer is arbitrary. Moreover, other layers, such as a damage prevention layer, a color adjustment layer, a shock absorption layer, a support body, and a transparent base material, may be inserted between the three layers.

  When laminating each layer, physical treatment such as corona treatment and plasma treatment may be performed, and a known high-polarity polymer such as polyethyleneimine, oxazoline-based polymer, polyester or cellulose is used as an anchor coating agent. Also good.

  In order to make the optical filter for thin display easy to see, it is preferable to provide an antireflection layer or an antiglare layer on the outermost layer on the human side.

  The antireflection layer is for suppressing reflection of the surface and preventing reflection of external light such as a fluorescent lamp on the surface. The antireflection layer consists of a single layer of a resin with a different refractive index, such as an acrylic resin or a fluororesin, when it is made of an inorganic thin film such as a metal oxide, fluoride, silicide, boride, carbide, nitride, or sulfide. Alternatively, it may be composed of multi-layers, and as a manufacturing method in the former case, there is a method of forming an antireflection coating on a transparent substrate in the form of a single layer or a multilayer using vapor deposition or sputtering. is there. Further, as a manufacturing method in the latter case, on a transparent film, a knife coater such as a comma coater, a fountain coater such as a slot coater and a lip coater, a gravure coater, a flow coater, a spray coater, a bar coater, There is a method of applying an antireflection coating to the surface.

  The glare-preventing layer is formed by converting fine powders of silica, melamine resin, acrylic resin, etc. into ink, applying it on any layer of the filter of the present invention by a conventionally known coating method, and curing it by heat or photocuring. Is done. An antiglare-treated film may be attached on the filter.

  In addition, the scratch-preventing layer is a coating solution prepared by dissolving or dispersing an acrylate such as urethane acrylate, epoxy acrylate or polyfunctional acrylate and a photopolymerization initiator in an organic solvent by a conventionally known coating method, and any of the filters of the present invention. On this layer, it is formed by coating, drying and photocuring.

  An optical filter having an antireflection layer or an antiglare layer and a near infrared absorbing layer is provided with a layer made of the near infrared absorbing adhesive composition or the near infrared absorbing material of the present invention on the back surface of the antireflection film or the antiglare film. Obtained by laminating. As a method of laminating, the near-infrared absorbing layer according to the present invention in the form of a film and the antireflection film or the anti-glare film may be directly bonded together, or the near-infrared absorbing adhesive composition of the present invention in solution may be used. You may apply | coat directly on the back surface of an antireflection film or an anti-glare film. In the case where a near-infrared absorbing layer is provided on the back surface of the antireflection film or the antiglare film, it is preferable to use an ultraviolet absorbing film as a transparent substrate in order to suppress deterioration of the pigment due to ultraviolet rays. The near infrared ray absorbing pressure-sensitive adhesive composition of the present invention has adhesiveness. Therefore, when the near-infrared absorbing layer and another layer are bonded, a pressure-sensitive adhesive or an adhesive may be unnecessary. A near-infrared absorption layer is a layer containing the near-infrared absorption adhesive composition of this invention.

  The optical filter for plasma display is preferably provided with an electromagnetic wave shielding layer in order to remove electromagnetic waves generated from the panel.

  The electromagnetic wave shielding layer is a film in which a metal mesh is patterned on a film by etching, printing, etc., or a film in which a metal is deposited on a fiber mesh and embedded in a resin. used.

  An optical filter having two layers of a near-infrared absorbing layer and an electromagnetic wave shielding layer can be obtained by combining an electromagnetic wave preventing material and a near-infrared absorbing adhesive composition. As a composite method, the film form of the near-infrared absorbing adhesive composition of the present invention and the electromagnetic wave shielding film may be laminated, or the solution of the near-infrared absorbing adhesive composition of the present invention is used as an electromagnetic wave shielding film. You may apply directly. Moreover, when smoothing the metal mesh on a film, the near-infrared absorption adhesive composition of this invention can also be used. Moreover, when embedding the fiber which vapor-deposited the metal, the near-infrared absorption adhesive composition of this invention can also be used.

  As an optical filter having three layers of a near-infrared absorbing layer, a reflection or anti-glare layer and an electromagnetic wave shielding layer, a near-infrared absorbing film comprising the near-infrared absorbing adhesive composition of the present invention, a reflection or anti-glare film, an electromagnetic wave A laminate of three shielding films can be used. Preferably, an optical filter having a structure in which a near-infrared absorbing film made of the near-infrared absorbing adhesive composition of the present invention is sandwiched between a reflection or glare-preventing film and an electromagnetic wave shielding film is preferable. Since this optical filter is laminated | stacked using the adhesiveness of a near-infrared absorption film, it can abbreviate | omit the adhesive layer provided only for pasting of the films conventionally. If necessary, a support such as glass or a functional film such as a color adjusting film may be laminated.

  In order to further simplify the optical filter manufacturing process and film configuration, it is preferable to use a composite film having a plurality of functions. A preferable optical filter is an optical filter in which a near-infrared absorbing adhesive layer comprising the near-infrared absorbing adhesive composition of the present invention is bonded to a composite film including an electromagnetic wave shielding layer and a reflection or glare-preventing layer on a single film. It is.

  The thin display optical filter of the present invention may be installed away from the display device or may be directly attached to the display device. When installing away from the display device, it is preferable to use glass as the support. In the case of directly bonding to a display device, an optical filter that does not use glass is preferable.

6). Thin display When an optical filter laminated with the near-infrared absorbing adhesive composition of the present invention is mounted on a thin display, good image quality is maintained over a long period of time. The present invention relating to a thin display is a thin display comprising the near-infrared absorbing adhesive composition of the present invention, the near-infrared absorbing material of the present invention, or the optical filter of the present invention. A thin display in which an optical filter is directly bonded to the display body can provide clearer image quality. When the optical filter is directly attached, it is preferable to use tempered glass as the display glass or an optical filter provided with a shock absorbing layer.

  As an adhesive when the optical filter of the present invention is attached to a display device, rubber such as styrene butadiene rubber, polyisoprene rubber, polyisobutylene rubber, natural rubber, neoprene rubber, chloroprene rubber, butyl rubber, polymethyl acrylate, Examples include polyacrylic acid alkyl esters such as ethyl polyacrylate and butyl polyacrylate, and these may be used alone, or further added with piccolite, polyvale, rosin ester, etc. as a tackifier. It may be used. Moreover, although the adhesive which has an impact absorption capability can be used as shown by Unexamined-Japanese-Patent No. 2004-263084, it is not limited to this. Without using an adhesive, the optical filter of the present invention may be attached to the display device by utilizing the adhesiveness of the near-infrared absorbing layer.

  The thickness of this adhesive layer is usually 5 to 2000 μm, preferably 10 to 1000 μm. A release film is provided on the surface of the pressure-sensitive adhesive layer, and this release film protects the pressure-sensitive adhesive layer and prevents dust from adhering to the pressure-sensitive adhesive layer until the optical filter is attached to the surface of the thin display. Also good. In this case, a non-adhesive part is formed by forming a part where the adhesive layer is not provided or by sandwiching a non-adhesive film between the adhesive layer at the edge of the filter and the release film. If the part is a peeling start part, the work at the time of sticking is easy.

  The shock absorbing layer is for protecting the display device from external impact. It is preferably used in an optical filter that does not use a support. As the shock absorber, ethylene-vinyl acetate copolymer, acrylic polymer, polyvinyl chloride, urethane-based, silicon-based resin as disclosed in JP-A-2004-246365 and JP-A-2004-264416 However, it is not limited to these.

  In the following, the present invention will be specifically described by way of examples. These examples do not limit the invention in any way. The methods for evaluating near-infrared absorption, heat resistance, moist heat resistance, and acid value are as follows. In the following description, “part” means “part by weight” and “%” means “% by weight” unless otherwise specified.

(1) Evaluation of near-infrared absorptivity (near-infrared transmittance) The transmission spectrum of 350-1250 nm was measured for the test body using UV-3700 (made by Shimadzu Corporation). Near-infrared absorptivity was evaluated by transmittance at a wavelength of 1000 nm. In Table 2 below, the transmittance at a wavelength of 1000 nm is expressed as “1000 nm transmittance”.

(2) Evaluation of heat resistance The specimen was allowed to stand in a constant temperature and humidity chamber at 80 ° C for 500 hours, and transmission spectra of 350 to 1250 nm before and after the test were measured. UV-3700 (manufactured by Shimadzu Corporation) was used for measurement of the transmission spectrum. From the obtained transmission spectra before and after the test, the change in transmittance at a wavelength of 1000 nm was evaluated. In addition, a color difference was calculated from the obtained transmission spectra before and after the test, and the change in b * was evaluated. The evaluation results are shown in Table 3 below. The value obtained by subtracting the value before the test from the value after the test is shown in Table 3 below.

(3) Evaluation of heat-and-moisture resistance The test body was left in a constant temperature and humidity chamber of 60 ° C. and 90% RH for 500 hours, and transmission spectra of 350 to 1250 nm before and after the test were measured. UV-3700 (manufactured by Shimadzu Corporation) was used for measurement of the transmission spectrum. From the obtained transmission spectra before and after the test, the change in transmittance at a wavelength of 1000 nm was evaluated. In addition, a color difference was calculated from the obtained transmission spectra before and after the test, and the change in b * was evaluated. The evaluation results are shown in Table 3 below. The value obtained by subtracting the value before the test from the value after the test is shown in Table 3 below.

(4) Measurement of acid value 0.5 g of the pressure-sensitive adhesive resin solution was precisely weighed, and 50 g of toluene was added and dissolved uniformly. Two to three drops of phenolphthalein / alcohol solution was added as an indicator and titrated with 0.1N potassium hydroxide / alcohol solution. The end point was when the redness of the liquid did not disappear in about 30 seconds. The acid value was determined from the titration amount at this time and the solid content of the resin. The acid value is expressed in mg of potassium hydroxide necessary to neutralize 1 g of resin solids.

[Synthesis Example 1]:
As a monomer, 286.65 parts of 2-ethylhexyl acrylate, 162.50 parts of n-butyl acrylate, 195.0 parts of cyclohexyl methacrylate, and 5.85 parts of hydroxyethyl acrylate were mixed to obtain a monomer mixture 1. Initiator solution 1 was obtained by mixing 0.13 part of BMT-K40 (manufactured by NOF Corporation) and 5.40 parts of ethyl acetate. 260.0 parts monomer mixture 1 and 167.90 parts ethyl acetate were placed in a flask, and a thermometer, stirrer, inert gas inlet tube, reflux condenser and dropping funnel were set in the flask, 0.2 Part of BMT-K40 and 17.36 parts of ethyl acetate were mixed to make a dropping initiator solution 2, and 390.00 parts of the monomer mixture 1 was mixed with the dropping initiator solution 2 Placed in dropping funnel. The inside of the flask was heated while flowing nitrogen gas at 20 ml / min, and the temperature in the flask was 90 ° C. Initiator solution 1 was added to the flask to initiate the polymerization reaction. Ten minutes after the introduction of the initiator solution 1, the mixture in the dropping funnel (a mixture of the monomer mixture 1 and the dropping initiator solution 2) was added to the flask over 90 minutes. Thereafter, aging was performed for 300 minutes while maintaining the reflux temperature while appropriately diluting with ethyl acetate in accordance with the increase in viscosity to obtain a resin solution 1. This resin solution 1 was diluted with ethyl acetate so that the non-volatile content was about 45% to obtain a pressure-sensitive adhesive resin 1. This pressure-sensitive adhesive resin 1 had a calculated glass transition temperature (Tg) of −34.7 ° C. and a calculated solubility parameter (Sp) of 9.64. The pressure-sensitive adhesive resin 1 had a weight average molecular weight (Mw) of 420,000.

[Synthesis Example 2]:
As a monomer, 286.65 parts of 2-ethylhexyl acrylate, 162.50 parts of n-butyl acrylate, 195.0 parts of benzyl acrylate, and 5.85 parts of hydroxyethyl acrylate were mixed to obtain a monomer mixture 2. A resin solution 2 was obtained in the same manner as the resin solution 1 except that the monomer mixture 2 was used in place of the monomer mixture 1. This resin solution 2 was diluted with ethyl acetate so that the non-volatile content was about 40% to obtain a pressure-sensitive adhesive resin 2. This adhesive resin 2 had a calculated glass transition temperature (Tg) of −47.2 ° C. and a calculated solubility parameter of 9.80. This pressure-sensitive adhesive resin 2 had a weight average molecular weight (Mw) of 930,000.

[Synthesis Example 3]:
As a monomer, 351.65 parts of 2-ethylhexyl acrylate, 162.50 parts of n-butyl acrylate, 130.0 parts of cyclohexyl methacrylate and 5.85 parts of hydroxyethyl acrylate were mixed to obtain a monomer mixture 3. A resin solution 3 was obtained in the same manner as the resin solution 1 except that the monomer mixture 3 was used in place of the monomer mixture 1. This resin solution 3 was diluted with ethyl acetate so that the non-volatile content was about 45% to obtain a pressure-sensitive adhesive resin 3. This pressure-sensitive adhesive resin 3 had a calculated glass transition temperature (Tg) of −46.2 ° C. and a calculated solubility parameter of 9.73. This pressure-sensitive adhesive resin 3 had a weight average molecular weight (Mw) of 590,000.

[Synthesis Example 4]:
As a monomer, 323.05 parts of 2-ethylhexyl acrylate, 325.0 parts of n-butyl acrylate and 1.95 parts of hydroxyethyl acrylate were mixed to obtain a monomer mixture 4. A resin solution 4 was obtained in the same manner as the resin solution 1 except that the monomer mixture 4 was used in place of the monomer mixture 1. This resin solution 4 was diluted with ethyl acetate so that the non-volatile content was about 40%, whereby an adhesive resin 4 was obtained. This pressure-sensitive adhesive resin 4 had a calculated glass transition temperature (Tg) of −62.6 ° C. and a calculated solubility parameter of 9.50. The pressure-sensitive adhesive resin 4 had a weight average molecular weight (Mw) of 830,000.

  “Composition” in Table 1 indicates the weight percentage of each monomer relative to the weight of the entire monomer mixture. In Table 1, 2EHA represents 2-ethylhexyl acrylate (Tg: -70 ° C), BA represents n-butyl acrylate (Tg: -55 ° C), and CHMA represents cyclohexyl methacrylate (Tg: 83 ° C). , BzA represents benzyl acrylate (Tg: 6 ° C.), and HEA represents hydroxyethyl acrylate (Tg: −15 ° C.).

Example 1:
“CIR-1085” (manufactured by Nippon Carlit Co., Ltd.) having a bis (trifluoromethanesulfone) imide anion as a diimonium dye and having a maximum absorption wavelength of 1073 nm in an acetone solution is dissolved in methyl ethyl ketone, and a diimonium solution having a solid content of 5% 1 was adjusted. Next, a trade name “EEX Color IR-10A” (manufactured by Nippon Shokubai), which is a phthalocyanine dye, was dissolved in toluene to prepare a phthalocyanine solution 1 having a solid content of 5%. Further, coronate L-55E (manufactured by Nippon Polyurethane Co., Ltd.) as a crosslinking agent and di-n-butyltin dilaurate as a crosslinking accelerator are each dissolved in methyl ethyl ketone, and a crosslinking agent solution 1 having a solid content of 1% and a solid content of 1%. A crosslinking accelerator solution 1 was prepared. The pressure-sensitive adhesive resin 1, the diimonium solution 1, the phthalocyanine solution 1, the cross-linking agent solution 1 and the cross-linking accelerator solution 1 obtained in Synthesis Example 1 were mixed at a solid content weight ratio of 100 / 1.46 / 1.1 / 0.5. /0.05 to obtain a near-infrared absorbing adhesive composition A1. The weight ratio of the solid content is indicated in the order of (adhesive resin 1 / diimonium solution 1 / phthalocyanine solution 1 / crosslinking agent solution 1 / crosslinking accelerator solution 1).

  The near-infrared absorbing pressure-sensitive adhesive composition A1 was coated on an easy-adhesion-treated PET film (manufactured by Toyobo Co., Ltd., Cosmo Shine A4300) with an applicator. The coating thickness was set so that the thickness after drying was 25 μm. Subsequently, it was dried in a hot air circulating oven at 100 ° C. for 2 minutes. A release film (silicone-treated PET film) was laminated to the layer comprising this near-infrared absorbing adhesive composition A1, and then cured at 23 ° C. for 7 days to obtain a near-infrared absorbing material A1. After peeling off the release film, this near-infrared absorbing material A1 was affixed to a PET film to obtain a test body according to Example 1. About this test body, near-infrared transmittance was evaluated. The evaluation results are shown in Table 2 below.

Examples 2 to 4:
In the same manner as in Example 1 except that the pressure-sensitive adhesive resin 1 was changed from pressure-sensitive adhesive resin 2 to 4, from near-infrared absorbing pressure-sensitive adhesive compositions A2 to A4, near-infrared absorbing materials A2 to A4 and from example 2 4 was obtained. These specimens were evaluated in the same manner as in Example 1. The specifications and evaluation results of Examples 2 to 4 are shown in Table 2 below.

Synthesis example of dimonium dye A:
1.05 parts of sodium tetrakis (pentafluorophenyl) borate (trade name “TEPBNa” manufactured by Nippon Shokubai) and bishexafluoroantimonic acid-N, N, N ′, N′-tetrakis- {p-di (n -Butyl) aminophenyl} -p-phenylenediimonium (trade name “IRG-022” manufactured by Nippon Kayaku Co., Ltd.) 0.70 part was dissolved in 10 parts of methyl ethyl ketone (MEK) at a temperature of 25 ° C. Solution 1 was prepared. Subsequently, the borate solution 1 was added all at once to 500 parts of deionized water and allowed to stand at 25 ° C. for 1 hour. The produced precipitate was collected by filtration and dried at 80 ° C. to obtain 0.83 part of a black solid. This black solid has a tetrakis (pentafluorophenyl) borate anion and has a maximum absorption wavelength of 1079 nm in an acetone solution. Bis {tetrakis (pentafluorophenyl) boric acid} -N, N, N ′, N′-tetrakis -{P-di (n-butyl) aminophenyl} -p-phenylenediimonium. Hereinafter, this bis {tetrakis (pentafluorophenyl) boric acid} -N, N, N ′, N′-tetrakis- {p-di (n-butyl) aminophenyl} -p-phenylenediimonium is also referred to as diimonium dye A. Called.

Example 5:
As the diimonium dye, the diimonium dye A obtained in the above synthesis example was used. This dimonium dye A was dissolved in methyl ethyl ketone to prepare a dimonium solution 2 having a solid content of 5%. The pressure-sensitive adhesive resin 1, the diimonium solution 2, the phthalocyanine solution 1, the cross-linking agent solution 1 and the cross-linking accelerator solution 1 obtained in Synthesis Example 1 were mixed at a solid content weight ratio of 100 / 1.46 / 1.1 / 0.5 / It mixed so that it might be set to 0.05, and near-infrared absorption adhesive composition A5 was obtained. The weight ratio of the solid content is indicated in the order of (adhesive resin 1 / diimonium solution 2 / phthalocyanine solution 1 / crosslinking agent solution 1 / crosslinking accelerator solution 1). A test body according to near-infrared absorbing material A5 and Example 5 was obtained in the same manner as in Example 1 except that this near-infrared absorbing composition A5 was used in place of the near-infrared absorbing adhesive composition A1. These specimens were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2 below. In Tables 2 and 3, the above bis {tetrakis (pentafluorophenyl) boric acid} -N, N, N ′, N′-tetrakis- {p-di (n-butyl) aminophenyl} -p-phenylene Diimonium is described as “Diimonium Dye A”

Comparative Example 1:
“CIR-1085F” (manufactured by Nippon Carlit Co., Ltd.) having a bis (trifluoromethanesulfone) imide anion and having a maximum absorption wavelength of 1049 nm in an acetone solution was used as a diimonium dye. This “CIR-1085F” was dissolved in methyl ethyl ketone to prepare a diimonium solution 3 having a solid content of 5%. The pressure-sensitive adhesive resin 1, the diimonium solution 3, the phthalocyanine solution 1, the crosslinking agent solution 1 and the crosslinking accelerator solution 1 obtained in Synthesis Example 1 were mixed at a solid content weight ratio of 100 / 1.46 / 1.1 / 0.5. /0.05 was mixed to obtain a near-infrared absorbing adhesive composition B1. The weight ratio of the solid content is indicated in the order of (adhesive resin 1 / dimonium solution 3 / phthalocyanine solution 1 / crosslinking agent solution 1 / crosslinking accelerator solution 1). A test body according to the near-infrared absorbing material B1 and the comparative example 1 is obtained in the same manner as in Example 1 except that this near-infrared absorbing adhesive composition B1 is used instead of the near-infrared absorbing adhesive composition A1. It was. This test body was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2 below.

Comparative Example 2:
The pressure-sensitive adhesive resin 2, the diimonium solution 3, the phthalocyanine solution 1, the cross-linking agent solution 1 and the cross-linking accelerator solution 1 obtained in Synthesis Example 2 were mixed at a solid content weight ratio of 100 / 1.46 / 1.1 / 0.5. /0.05 was mixed to obtain a near-infrared absorbing pressure-sensitive adhesive composition B2. The weight ratio of the solid content is indicated in the order of (adhesive resin 2 / diimonium solution 3 / phthalocyanine solution 1 / crosslinking agent solution 1 / crosslinking accelerator solution 1). A test body according to the near-infrared absorbing material B2 and Comparative Example 2 was obtained in the same manner as in Example 1 except that this near-infrared absorbing adhesive composition B2 was used instead of the near-infrared absorbing adhesive composition A1. It was. This test body was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2 below.

  About the test body which concerns on the said Examples 1-4, heat resistance and heat-and-moisture resistance were evaluated. These evaluation methods are as described above. These evaluation results are shown in Table 3 below.

  In addition to Examples 1 to 4, the following Comparative Example 3 was also evaluated for heat resistance and moist heat resistance.

Comparative Example 3:
The pressure-sensitive adhesive resin 2, the diimonium solution 3, the phthalocyanine solution 1, the cross-linking agent solution 1 and the cross-linking accelerator solution 1 obtained in Synthesis Example 2 were mixed at a solid content weight ratio of 100 / 1.88 / 1.1 / 0.5. /0.05 was mixed to obtain a near-infrared absorbing adhesive composition B3. The weight ratio of the solid content is indicated in the order of (adhesive resin 2 / diimonium solution 3 / phthalocyanine solution 1 / crosslinking agent solution 1 / crosslinking accelerator solution 1). The near-infrared absorption adhesive composition B3 is used in place of the near-infrared absorption adhesive composition A1, and near-infrared absorption is performed in the same manner as in Example 1 except that glass is used in place of the PET film. The test body which concerns on material B3 and the comparative example 3 was obtained. This test body was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2 below.

  As understood from the results of Table 2, the Example has a transmittance of 1000 nm smaller than that of the comparative example, and is excellent in near infrared absorption ability. The weight part of the solid content of the diimonium dye is the same in the examples and comparative examples. Under the condition that the weight part of the solid content of the diimonium dye is the same, the examples are more excellent in near-infrared absorption than the comparative examples. If the 1000 nm transmittance is the same between the example and the comparative example, the amount of the diimonium dye in the example can be reduced. Thus, an Example has high near-infrared absorptivity. Further, as can be understood from the results in Table 3, the examples have such durability that they can be put to practical use. It can be understood from the results of Comparative Example 3 that the examples have practical durability. That is, in Comparative Example 3, CIR-1085F, which is excellent in heat resistance and moist heat resistance, is used, but the Example is an evaluation result close to Comparative Example 3.

(Example 6)
1. Synthesis of polymerizable polysiloxane (M-1) In a 300 ml four-necked flask equipped with a stirrer, a thermometer and a condenser tube, 144.5 parts of tetramethoxysilane, 23.6 parts of γ-methacryloxypropyltrimethoxysilane, water 19.0 parts, 30.0 parts of methanol, and 5.0 parts of Amberlyst 15 (trade name: cation exchange resin manufactured by Organo) were added and stirred at 65 ° C. for 2 hours for reaction. After cooling the reaction mixture to room temperature, a distillation column, a cooling tube connected to the distillation column, and an outlet are provided instead of the cooling tube, and the temperature inside the flask is raised to about 80 ° C. over 2 hours under normal pressure. It was kept at the same temperature until it did not flow out. Further, the reaction was further proceeded by maintaining methanol at a temperature of 90 ° C. under a pressure of 2.67 × 10 kPa until methanol no longer flowed out. After cooling to room temperature again, Amberlyst 15 was filtered to obtain polymerizable polysiloxane (M-1) having a number average molecular weight of 1,800.

2. Synthesis of organic polymer (P-1) Into a 1 liter flask equipped with a stirrer, a dripping port, a thermometer, a cooling tube and an N2 gas inlet, 260 parts of n-butyl acetate as an organic solvent was introduced, and N2 gas was introduced. While stirring, the flask internal temperature was heated to 110 ° C. Then, 12 parts of polymerizable polysiloxane (M-1), 19 parts of tert-butyl methacrylate, 94 parts of butyl acrylate, 67 parts of 2-hydroxyethyl methacrylate (light ester FM-108, manufactured by Kyoeisha Chemical Co., Ltd.) ) A solution in which 48 parts and 2.5 parts of 2,2′-azobis- (2-methylbutyronitrile) were mixed was dropped from the dropping port over 3 hours. After the dropwise addition, stirring was continued at the same temperature for 1 hour, and then 0.1 part of tert-butylperoxy-2-ethylhexanoate was added twice every 30 minutes, followed by further heating for 2 hours for copolymerization. It was. As a result, a solution in which an organic polymer (P-1) having a number average molecular weight of 12,000 and a weight average molecular weight of 27,000 was dissolved in n-butyl acetate was obtained. The solid content of the obtained solution was 48.2%.

3. Synthesis of organic polymer composite inorganic fine particle dispersion (S-1) In a 500 ml four-necked flask equipped with a stirrer, two dropping ports (dropping port α and dropping port β), a thermometer, 200 parts of n-butyl acetate and 500 parts of methanol was added and the internal temperature was adjusted to 40 ° C. Next, while stirring the inside of the flask, a mixed solution (raw material solution A) of 10 g of an organic polymer (P-1) n-butyl acetate solution, 30 parts of tetramethoxysilane and 5 parts of n-butyl acetate was added from the dropping port α for 2 hours. At the same time, 5 parts of 25% ammonia water, 10 parts of deionized water and 15 parts of methanol (raw material liquid B) were dropped from the dropping port β over 2 hours. After dropping, a distillation column, a cooling pipe connected to the distillation column and an outlet are provided instead of the cooling pipe, and the temperature inside the flask is raised to 100 ° C. under a pressure of 40 kPa, and ammonia, methanol and n-butyl acetate are solidified. The mixture was distilled off until the content became 30%, to obtain a dispersion (S-1) in which the organic polymer composite inorganic fine particles were dispersed in n-butyl acetate. In this dispersion (S-1), the ratio of the inorganic fine particles to the organic polymer in the organic polymer composite inorganic fine particles was 70/30. This ratio is a weight ratio. The average particle diameter of the obtained organic polymer composite inorganic fine particles was 23.9 nm. The ratio of the inorganic fine particles to the organic polymer in the organic polymer composite inorganic fine particles was determined by conducting an elemental analysis on the organic polymer composite fine particle dispersion dried at 130 ° C. for 24 hours under a pressure of 1.33 × 10 kPa, and calculating the ash content. It calculated | required as organic polymer composite inorganic fine particle content. Further, the average particle size was determined by photographing particles with a transmission electron microscope using a solution obtained by diluting 1 part of the organic polymer composite inorganic fine particle dispersion (S-1) with 99 parts of n-butyl acetate. The diameter of the particles was read and the average was determined as the average particle diameter.

4). Reflective film Dipentaerythritol hexaacrylate (DPE-6A, manufactured by Kyoeisha Chemical Co., Ltd.) 8 parts and pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) 2 parts are mixed to prepare a solution dissolved in methyl ethyl ketone 40 parts. did. A solution obtained by dissolving 0.5 part of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy Co., Ltd.) in 2 parts of methyl ethyl ketone was added to this solution to prepare a hard coat layer coating solution.

  Organic polymer composite inorganic fine particle dispersion (S-1) 9 parts, Desmodur N3200 (trade name, isocyanate curing agent manufactured by Sumika Bayer Urethane Co., Ltd.) 0.3 parts, dilauric acid di-n-butyltin 0.003 parts and 110 parts of methyl isobutyl ketone was mixed to prepare a low refractive index layer coating solution.

The hard coat layer coating solution was applied to a 188 μm thick polyethylene terephthalate film (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.) using a bar coater to obtain a coating layer h. The coating layer h was dried at 100 ° C. for 15 minutes and then cured by irradiating with 200 mJ / cm ² of ultraviolet light with a high-pressure mercury lamp to form a hard coat layer having a thickness of 5 μm. A low refractive index coating solution was coated on the hard coat layer using a bar coater to form an antireflection film on the polyethylene terephthalate film.

  The surface of the film opposite to the antireflection film side was roughened with steel wool. Black ink was applied to the roughened surface. The specular reflection spectrum of the surface on the antireflection film side at an incident angle of 5 ° is measured using an ultraviolet-visible spectrophotometer (UV-3100, manufactured by Shimadzu Corporation), and the wavelength at which the reflectance shows the minimum value and the reflectance at that wavelength. (Minimum reflectance) was determined. In the obtained antireflection film, the wavelength at which the reflectance showed a minimum value was a wavelength of 550 nm, and the reflectance at that wavelength (minimum reflectance) was 0.45%.

5. Optical filter On the back surface side of the obtained antireflection film, the near-infrared absorbing adhesive composition A1 obtained in Example 1 was coated and dried in the same manner as in Example 1 to obtain an optical filter 1. The near-infrared transmittance, total light transmittance, heat resistance, crack resistance and solvent resistance of the optical filter 1 were good.

  The near-infrared-absorbing pressure-sensitive adhesive composition of the present invention is useful as an optical filter for thin displays because of its high near-infrared absorption ability and high transparency in the visible region. It can also be used as an optical information recording material.

Claims (13)

(A) A near-infrared absorbing pressure-sensitive adhesive composition comprising a diimonium dye having a maximum absorption wavelength in an acetone solution exceeding 1060 nm and 1200 nm or less and (B) a resin having a calculated glass transition temperature of −20 ° C. or less. The near-infrared-absorbing pressure-sensitive adhesive composition according to claim 1, wherein the dimonium dye comprises a dimonium cation represented by the following formula (1) and an anion represented by the following formula (2) or (3).

However, in Formula (1), R < ¹ > -R < ⁸ > represents a hydrogen atom, a halogen atom, a C1-C10 alkyl group, or a C1-C10 alkyl group which has a substituent each independently. In formula (2), R ^a and R ^b each represent a fluoroalkyl group that may be the same or different. In formula (3), R ^c represents a fluoroalkylene group.
  The near-infrared absorbing pressure-sensitive adhesive composition according to claim 1, wherein the acid value of the resin (B) is 25 or less.   The near-infrared absorbing adhesive composition according to any one of claims 1 to 3, wherein the calculated solubility parameter of the resin (B) is 9.80 or less. The near-infrared absorbing adhesive composition according to any one of claims 1 to 4, wherein the resin (B) is a polymer obtained by copolymerizing the following monomers (1) to (3) at the following ratio.
(1) (Meth) acrylic acid ester having an alicyclic, polycyclic alicyclic, aromatic or polycyclic aromatic cyclic alkyl group: 5 to 40% by weight
(2) (Meth) acrylic acid ester having 1 to 10 carbon atoms and having a linear or branched alkyl group: 60 to 95% by weight
(3) Other copolymerizable monomers: 0 to 30% by weight   Furthermore, the near-infrared absorption adhesive composition in any one of Claim 1 to 5 containing a phthalocyanine type pigment | dye.   The near-infrared absorber containing the near-infrared absorption adhesive composition in any one of Claim 1 to 6.   The near-infrared absorbing material according to claim 7, wherein the near-infrared absorbing adhesive composition according to claim 1 is laminated on a transparent substrate.   The near-infrared absorbing material according to claim 8, wherein the transparent substrate is glass, PET film, easy-adhesive PET film, lactone ring-containing resin film, TAC film, antireflection film or electromagnetic wave shielding film.   The near-infrared absorbing material according to claim 9, wherein the transparent substrate is a PET film or an easily adhesive PET film.   An optical filter for a thin display, comprising the near-infrared absorbing material according to claim 7.   The optical filter for optical semiconductor elements which uses the near-infrared absorber in any one of Claims 7-10.   A near-infrared absorbing adhesive composition according to any one of claims 1 to 6, a near-infrared absorbing material according to any one of claims 7 to 10, or a thin display comprising the optical filter according to claim 11. .