JP2007070605A - Near infrared absorbing composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a near infrared absorbing composition maintaining the transparency and near infrared absorbency in a visible region over a long period and hardly forming cracks. <P>SOLUTION: The near infrared absorbing composition comprises a near infrared absorbing dye composed of an anion having ≥250 molecular weight and a diimmonium cation and a resin having a low Tg. The composition maintains the transparency in the visible region and near infrared absorbency over the long period and hardly causes the cracks. Thereby, the composition is useful as an optical filter for a thin-type display. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a near-infrared absorbing composition, a near-infrared absorbing material containing the near-infrared absorbing composition, an optical filter for a thin display using the near-infrared absorbing composition or the near-infrared absorbing material, and the like. In particular, the present invention is a near-infrared absorbing composition that is excellent in transparency in the visible region and durability of infrared absorbing ability and hardly breaks, a near-infrared absorbing material containing the near-infrared absorbing composition, the near-infrared absorbing composition, or the near-infrared absorbing composition. The present invention relates to an optical filter for an optical semiconductor element using an infrared absorbing material, an optical filter for a thin display using the near infrared absorbing composition or the near infrared absorbing material, and the like.

  In recent years, thin displays such as liquid crystal displays and PDPs (Plasma Display Panels) that are thin and applicable to large screens 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, and 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, in order to suppress reflected light, an antireflection film and an antiglare film (antiglare film) are also required. 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.
JP 2003-96040 A JP 2000-80071 A

  However, the diimonium dye may have poor durability, and a decrease in the near-infrared absorption ability and coloring may be a serious problem when used in an optical semiconductor element or display application. In order to improve the durability of the diimonium dye, it is known that the glass transition point (Tg) of the resin fixing the dye should be increased (see, for example, JP-A No. 2003-167119).

  However, when the Tg of the resin is increased, cracking is likely to occur due to impacts, repeated heating and cooling, adhesion of chemicals, and the like. Therefore, the near-infrared absorbing film in which a resin containing a near-infrared absorbing pigment is applied to a film-like substrate has not been easy to handle.

  Therefore, the present invention has an object to provide a near-infrared absorbing composition useful for producing a near-infrared absorbing material having high transparency in the visible region and high durability of near-infrared absorbing ability and excellent flexibility. And

  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.

  As a result of intensive studies on the durability of the dye and the flexibility of the resin, the inventors have found that the durability of the dye can be improved by using a diimonium dye containing an anion having a large molecular weight and a resin having a low Tg. It has been found that it can be processed into a near-infrared absorbing film excellent in flexibility. Further, it has been found that the use of such a near-infrared absorbing composition as a near-infrared absorbing film facilitates handling and is useful for optical semiconductor elements, optical filters for thin displays, and thin displays.

  That is, the above object is achieved by a near-infrared absorbing composition containing a diimonium dye composed of an anion having a molecular weight of 250 or more and a resin having a Tg of 20 ° C. or more and 85 ° C. or less.

  The near-infrared absorbing material using the near-infrared absorbing composition of the present invention maintains the near-infrared absorbing ability of the dye for a long period of time and is excellent in flexibility. Therefore, when this near-infrared absorbing material is used for an optical semiconductor element or an optical filter for a thin display, the optical characteristics are improved and the handling becomes easy.

Hereinafter, the present invention will be described in detail.
The first of the present invention is a near-infrared absorbing composition containing a diimonium dye having an anion having a molecular weight of 250 or more and a resin having a Tg of 20 ° C. or more and 85 ° C. or less.

1. Diimonium dyes Diimonium dyes are excellent in transparency in the visible region and near infrared absorption ability. The diimonium dye used in the present invention is a salt comprising a diimonium cation represented by the formula (1) and an anion having a molecular weight of 250 or more.

R ^{1 to} R ⁸ in the above formula (1) each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms having a substituent. R ^{1 to} R ⁸ may be different or the same.

  Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Linear, branched, alicyclic alkyl such as 1-methylbutyl group, 1-ethylpropyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, neopentyl group, n-hexyl group, cyclohexyl group, etc. Groups and the like.

  Examples of the substituent that can be bonded to the optionally substituted alkyl group having 1 to 10 carbon atoms include cyano group; hydroxyl group; halogen atom such as fluorine atom, chlorine atom, bromine atom; methoxy group; C1-C6 alkoxy groups such as ethoxy group, n-propoxy group, n-butoxy group; methoxymethoxy group, ethoxymethoxy group, methoxyethoxy group, ethoxyethoxy group, methoxypropoxy group, methoxybutoxy group, ethoxybutoxy group An alkoxyalkoxy group having 2 to 8 carbon atoms, such as a methoxymethoxymethoxy group, a methoxymethoxyethoxy group, a methoxyethoxyethoxy group, an ethoxyethoxyethoxy group, or the like; an allyloxy group; a phenoxy group; Tolyloxy group, xylyloxy group, naphthylo group An aryloxy group having 6 to 12 carbon atoms such as a cis group; an alkoxycarbonyl group having 2 to 7 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, and an n-butoxycarbonyl group; C2-C7 alkylcarbonyloxy groups such as methylcarbonyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, n-butylcarbonyloxy group; methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyl Examples thereof include an alkoxycarbonyloxy group having 2 to 7 carbon atoms such as an oxy group and an n-butoxycarbonyloxy group.

  Although it will not specifically limit if the molecular weight of an anion is 250 or more, 250-2000 are preferable, Most preferably, it is 250-1000. If the molecular weight of the anion is less than 250, the diimonium dye tends to deteriorate. If the molecular weight of the anion exceeds 2000, the gram extinction coefficient decreases and the amount of dye added increases, which is uneconomical.

  Moreover, the kind of anion is not specifically limited, For example, an imide anion, a metal dithiol complex anion, etc. are mentioned.

The imide anion is an anion represented by the formula (2) or the formula (3).

In the above formula (2), R ^a and R ^b each represent a fluoroalkyl group which may be the same or different. In the above formula (3), R ^c represents a fluoroalkylene group. 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. ^Examples of the fluoroalkylene group represented by R ^c include (CF ₂ ) _n (where n is an integer of 2 to 12).

Of the imide anions, bis (trifluoromethanesulfone) imide ion (Ra = Rb = CF ₃ molecular weight: 280), bis (pentafluoroethanesulfone) imide ion (R ^a = R ^b = C ₂ F ₅ molecular weight: 380) 1,3-disulfonylhexafluoropropyleneimide (R ^c = (CF ₂ ) ₃ molecular weight: 292).

A known metal dithiol complex anion can be used and is not particularly limited, and specific examples include an anion of the following formula (4).

M in the above formula (4) represents a transition metal atom, and R ^d and R ^e have an alkyl group having 1 to 6 carbon atoms, a morpholino group which may have a substituent, and a substituent. A piperidino group which may have a substituent, a pyrrolidino group which may have a substituent, a thiomorpholino group which may have a substituent, a piperazino group which may have a substituent, or a substituent Or a good phenyl group. R ^d and R ^e may be the same or different. A metal dithiol complex anion is not particularly limited, M is a copper ion, the anion is preferably is a morpholino group and R ^d and R ^e, the molecular weight of the metal dithiol complex anion is 642.

  The diimonium dye of the present invention comprising an anion having a molecular weight of 250 or more exhibits high durability. The reason why the durability is improved when combined with an anion having a large molecular weight is not clear, but it is considered that a diimonium cation having a strong soft property is stabilized by an anion having a strong soft molecular weight.

  In the case of a diimonium dye comprising a high molecular weight anion and having a melting point of 200 ° C. or higher, the durability is further improved. As such a diimonium dye, specifically, CIR-RL (Nippon Carlit bis (trifluoromethanesulfone) imide salt, melting point: 235 ° C.), CIR-1085F (Nippon Carlit bis (trifluoromethanesulfone) imide salt, melting point : 210 ° C).

2. Resin The resin used in the present invention is not particularly limited as long as Tg is 25 ° C. or higher and 85 ° C. or lower. The resin used in the present invention is preferably an acrylic resin, a polyester resin, or the like that can provide a highly transparent coating film after drying. Resins having a Tg of less than 25 ° C. are easily soiled or scratched. Resins having a Tg of 85 ° C. or higher are easily broken. In order to achieve both high cracking resistance and high durability, the Tg of the resin is preferably 65 to 85 ° C, and more preferably 70 to 80 ° C.

  A particularly preferable resin is a polymer obtained by polymerizing (meth) acrylic acid ester, and this (meth) acrylic acid ester is a linear, branched, alicyclic, polycyclic having 1 to 10 carbon atoms. It is a polymer having an alicyclic alkyl group. Specific examples include methyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, acrylic Examples thereof include polymers composed of octyl acid and the like. A monomer may use only 1 type or may copolymerize multiple types. The usage-amount of each monomer is not specifically limited, Tg of obtained resin should just be 25 to 85 degreeC.

  The molecular weight of the resin is not particularly limited. The molecular weight of the resin is a polystyrene-equivalent weight average molecular weight, preferably 10,000 to 3,000,000, more preferably 50,000 to 2,000,000, and particularly preferably 100,000 to 1,000,000. When the weight molecular weight is 10,000 or less, sufficient flexibility is hardly exhibited, and when the weight average molecular weight exceeds 3 million, the viscosity is too high and handling becomes difficult.

  In addition, a carboxyl group, hydroxyl group, oxazolinyl group, pyrrolidonyl group, fluoro, as well as a (meth) acrylic acid ester having a linear, branched, alicyclic or polycyclic alicyclic alkyl group having 1 to 10 carbon atoms. A monomer having a functional group such as an alkyl group or an aromatic group may be copolymerized as long as the object of the present invention is not impaired.

  Commercially available initiators such as peroxides and azos can be used for the polymerization. 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 manufactured by NOF); Peroxyketals such as perhexa 3M and perhexa MC (both manufactured by NOF); perbutyl P, park mill D (all manufactured 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 resin, a chain transfer agent may be used as necessary. The chain transfer agent is not particularly limited as long as it can be adjusted to a predetermined molecular weight, and thiol compounds such as normal dodecyl mercaptan, dithioglycol, octyl thioglycolate, and mercaptoethanol can be used.

  Further, the polymerization of the resin may be performed without a solvent or may be performed 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.

  Further, the resin may have a single composition, or may be a polymer alloy or a polymer blend in which polymers having different compositions are combined.

  The near-infrared absorbing composition of the present invention exhibits high flexibility when the Tg is 25 ° C. or higher and 85 ° C. or lower. In order to further prevent cracking, the polymer structure is preferably branched rather than linear. When the branched structure is used, even when the molecular weight is increased, the viscosity of the resin is low and the handling becomes easy.

  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 composition The near-infrared absorbing composition of the present invention contains a diimonium dye having an anionic molecular weight of 250 or more and a resin having a Tg of 25 ° C. or more and 85 ° C. or less. Infrared absorption is easy to sustain and hard to break. The near-infrared absorbing composition of the present invention facilitates handling when processed into a film.

  You may add another near-infrared absorption pigment | dye to the near-infrared absorption composition of this 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, etc. Can be mentioned.

  When the near-infrared absorbing composition of the present invention is used as an optical filter for a thin display, a phthalocyanine dye having a maximum absorption wavelength of 800 to 950 nm, a cyanine dye having a maximum absorption wavelength of 800 to 950 nm, or the diimonium dye A metal dithiol complex dye having a maximum absorption wavelength of 800 to 950 nm is preferably 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 composition having good durability, it is particularly preferable to use a phthalocyanine dye in combination.

  The phthalocyanine-based compound that can be used in the present invention is not particularly limited as long as it has excellent near-infrared absorption ability, and known phthalocyanine-based compounds 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.

  Specifically, the trade names EEX COLOR IR-10A, EEX COLOR IR-12, EEX COLOR IR-14, TX-EX-906B, TX-EX-910B, TX-EX-902K (all of which are Nippon Shokubai Co., Ltd.) Manufactured).

  Further, the near-infrared absorbing composition of the present invention may be used in combination with a cyanine dye 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 and 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. Similar to the diimonium dye of the present invention, an anion having a molecular weight of 250 or more may be used.

  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 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 absorbing composition of the present invention is used as a thin film having a thickness of about 10 μm, the amount 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 composition of the present invention is characterized by transparency in the visible region, sustainability of near-infrared absorbing ability, and good processability, and a dye that absorbs visible light may be added as necessary. 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 system, can be used widely.

  When the near-infrared absorbing composition of the present invention is used as an optical filter for PDP, it is preferable to use a visible absorption 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 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 composition of this invention may contain the 1 type (s) or 2 or more types of the solvent, the additive, and the hardening | curing agent in the range which does not lose the performance as needed.

  The near-infrared absorbing composition of the present invention may be a composition in which a near-infrared absorbing dye is mixed in the form of a solid (for example, a powder) in a resin, but in a solvent when used by coating on a film. Further, it is preferably in a dissolved, dispersed or suspended form.

  Examples of solvents that can be used in this case include 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; ester systems 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; glycol ethers such as butyl cellosolve, propylene glycol n-propyl ether, propylene glycol n-butyl ether and propylene glycol monomethyl ether acetate Systems; Amides such as formamide and N, N-dimethylformamide; Halogens 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, a solvent having a boiling point of 100 to 150 ° C. such as toluene, methyl isobutyl ketone, and 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. can be used, a dispersing agent, a leveling agent, an antifoamer, a viscosity modifier, a matting agent, Examples include tackifiers, antistatic agents, antioxidants, ultraviolet absorbers, light stabilizers, quenchers, curing agents, and antiblocking agents. 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 composition of the present invention includes optical, agricultural, architectural or vehicle near-infrared absorbing materials, image recording materials such as photosensitive paper, information recording materials such as optical disks, and dye-sensitized solar cells. It can be used as a light-sensitive material for preventing eye strain using a solar cell, a semiconductor laser beam or the like as a light source. The near infrared ray absorbing composition of the present invention is particularly preferably used in the form of a film or a sheet.

4). Near-infrared absorbing material The second of the present invention is a near-infrared absorbing material containing the near-infrared absorbing material of the present invention. The near-infrared absorbing material of the present invention may be formed by forming the near-infrared absorbing material into a film shape, or may be a laminate of a coating film containing the near-infrared absorbing material on a transparent substrate. Good.

  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. Further, 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 applied. 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 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.

  Of these, glass, PET film, easy-adhesive PET 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 preparing a resin plate or film by kneading the near-infrared absorbing material of the present invention into a resin and thermoforming; (II) presence of a polymerization catalyst for the near-infrared absorbing material of the present invention and a monomer or oligomer A method of producing a resin plate or film by cast polymerization below; (III) a method of coating the near-infrared absorbing material of the present invention on the transparent substrate, and the like.

  As a production method of (I), the processing temperature, filming (resin plate) conditions and the like are slightly different depending on the resin used. Usually, the near-infrared absorbing material of the present invention is added to resin powder or pellets. Examples include a method of heating and dissolving at ˜350 ° C. and then forming to form a resin plate, and a method of forming a film (resin plate) with an extruder.

  As a preparation method of (II), the near-infrared absorbing material of the present invention and a monomer or oligomer are cast-polymerized in the presence of a polymerization catalyst, and a mixture thereof is injected into a mold and reacted and cured, or gold It is poured into a mold and solidified until it becomes a hard product in the mold. Many resins can be molded in this process, and 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.

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

  A known coating machine can be used when applying the near-infrared absorbing material 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 material 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. Since the near-infrared absorbing material of the present invention has higher durability, particularly heat resistance and heat-and-moisture resistance than conventional near-infrared absorbing materials, the appearance and near-infrared absorbing ability are maintained even during long-term storage and use. Furthermore, since the near-infrared absorbing material 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 material of the present invention can also be used for filters and films that need to cut infrared rays, such as agricultural films, heat insulating films, sunglasses, and optical recording materials.

5. Optical filter The near-infrared absorbing material of the present invention is suitable for an optical filter. Accordingly, a third aspect of the present invention is an optical filter for an optical semiconductor element or a thin display using the near-infrared absorbing material of the present invention. 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.

  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, a color adjustment layer, glass, in addition to the near infrared absorption layer comprising the above near infrared absorption material. A support such as the above may be provided.

  The configuration of each layer of the optical filter may be arbitrarily selected, and is preferably an optical filter in which at least one of an antireflection layer and an antiglare layer and at least two layers of a near infrared absorption layer are combined, and more preferably Is an optical filter having at least three layers combined with an electromagnetic wave shielding 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, and a bar coater are used. 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 antiglare layer and a near infrared absorption layer can be obtained by laminating a layer made of the near infrared absorber of the present invention on the back surface of the antireflection film or antiglare film. As a method of laminating, the near-infrared absorbing material of the present invention formed into a film and the antireflection film or the anti-glare film may be bonded together with an adhesive, or the near-infrared absorbing material of the present invention that has been made into a solution is antireflective. You may apply | coat directly on the back surface of a 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 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 absorption layer and an electromagnetic wave shielding layer can be obtained by combining an electromagnetic wave prevention material and a near infrared absorption material. As a method of combining, the near-infrared absorbing material of the present invention formed into a film and the electromagnetic shielding film may be bonded with an adhesive, or the solution of the near-infrared absorbing material of the present invention is directly applied to the electromagnetic shielding film. May be. Moreover, when smoothing the metal mesh on a film, the near-infrared absorption composition of this invention can also be used. Moreover, when embedding the fiber which vapor-deposited the metal, the near-infrared collection material of this invention can also be used.

  As an optical filter having three layers of a near-infrared absorbing layer, a reflection or glare-preventing layer and an electromagnetic wave shielding layer, a near-infrared absorbing film comprising the near-infrared absorbing material of the present invention, a reflection or glare-preventing film, and an electromagnetic shielding film A laminate of 3 sheets with an adhesive can be used. If necessary, a support such as glass or a functional film such as a color adjusting film may be laminated.

  In order to simplify the manufacturing process and film configuration of the optical filter, it is preferable to use a composite film having a plurality of functions. For example, an optical filter in which a composite film including a near-infrared absorbing layer and a reflection or anti-glare layer is bonded to an electromagnetic wave shielding film with an adhesive, or a composite film including a near-infrared absorbing layer and an electromagnetic wave shielding layer is reflected with an adhesive. Alternatively, an optical filter bonded to an anti-glare film, and an optical filter formed by bonding a composite film including an electromagnetic wave shielding layer and a reflection or anti-glare layer to a near-infrared absorbing film with an adhesive can be used.

  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 in which the near-infrared absorbing material of the present invention is laminated is mounted on a thin display, good image quality is maintained over a long period of time. Accordingly, a fourth aspect of the present invention is a thin display using the near-infrared absorbing material 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.

  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 to do.

  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.

  EXAMPLES Next, although an Example is given and this invention is demonstrated concretely, these Examples do not restrict | limit this invention at all. In addition, a part shows a mass part. Moreover, evaluation of near-infrared absorptivity, transparency of visible region, wet heat resistance, and bending resistance was as follows.

(1) Evaluation of near infrared absorptivity (near infrared transmittance)
For the measurement of the visible-near infrared spectrum, UV-3700 (manufactured by Shimadzu Corporation) was used, a transmission spectrum of 350 to 1250 nm was measured, and the transmittance at a wavelength of 1090 nm was evaluated.

(2) Evaluation of transparency in the visible region (total light transmittance)
A Σ90 system (manufactured by Nippon Denshoku) was used for measuring the total light transmittance.

(3) Evaluation of moisture and heat resistance The test specimen was left in a constant temperature and humidity chamber at 80 ° C. and 95% RH for 120 hours, and transmission spectra of 350 to 1250 nm before and after the test were measured. For the measurement of the transmission spectrum, UV-3700 (manufactured by Shimadzu Corporation) was used, and the change in transmittance at a wavelength of 1090 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.

(4) Flexibility The test specimen was conditioned in a thermostatic chamber at 23 ° C., and a flex resistance test was conducted by a cylindrical mandrel method. The test was performed with a cylinder having a diameter of 2 mm, and the presence or absence of cracks in the bent portion was observed with a magnifying glass (magnification 10 times).

(5) Solvent resistance The specimen was heated in a hot air dryer at 80 ° C. for 30 minutes. After heating, the mixture was allowed to stand at room temperature for 1 h, and then ethanol was dropped on the painted surface and air-dried. After drying, the presence or absence of cracks was visually observed.

(Example 1-1)
As a monomer, 371.5 g of methyl methacrylate, 59 g of normal butyl acrylate, and 69.5 g of butyl acrylate were mixed to obtain a monomer mixture 1. 6 g of Parkadox 12XL25 (manufactured by gunpowder Akzo) and 100 g of toluene were mixed to obtain an initiator solution 1. 350 g of this monomer mixture 1 and 225 g of toluene were placed in a flask, and a thermometer, a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a dropping funnel were set in the flask. 150 g of monomer mixture 1 and 31.8 g of initiator solution 1 were mixed and placed in the dropping funnel. While flowing nitrogen gas at a rate of 20 ml / min, the flask was heated to an internal temperature of 100 ° C. 74.2 g of initiator solution 1 was added to the flask to initiate the polymerization reaction. Ten minutes after the introduction of the polymerization initiator, the mixture in the dropping funnel (mixture of the monomer mixture 1 and the initiator solution 1) was added to the flask over 60 minutes. After the addition, the dropping funnel was washed with 75 g of toluene, and the washing solution was added to the flask. Thereafter, aging was performed for 60 minutes, and 150 g of toluene as a diluent solvent was added into the flask. The mixture was further aged for 60 minutes, and 150 g of toluene as a diluent solvent was added to the flask. The mixture was further aged for 60 minutes, and 150 g of toluene as a diluent solvent was added to the flask. It was aged for another 60 minutes. Thereafter, the temperature was raised to 108 ° C. and aged for 300 minutes. Furthermore, after adding 185.7 g of diluting solvent, it cooled to room temperature and obtained the resin solution 1. The solid content was 32.4%, Tg was 75 ° C., and the weight average molecular weight in terms of polystyrene was 220,000.

(Example 1-2)
N, N, N ′, N ′,-Tetrakis- (p-di (n-butyl) aminophenyl) -p-benzoquinone-bis-imonium bis (trifluoromethanesulfone) imide salt (anionic molecular weight 292, melting point 190) C.) was dissolved in methyl ethyl ketone to prepare a diimonium dye solution 1 having a solid content of 3%. Also, e-color IR-10A (manufactured by Nippon Shokubai) was dissolved in methyl ethyl ketone to prepare a phthalocyanine solution having a solid content of 3%. 9.1 parts of resin solution 1, 2.5 parts of diimonium dye solution 1, 2.5 parts of phthalocyanine solution, and 0.9 parts of methyl ethyl ketone were mixed to obtain near-infrared absorbing composition A1. .

(Example 1-3)
The near-infrared absorbing composition A1 was coated on a 100 μm thick easy-adhesion-treated PET film (Toyobo Cosmo Shine A4300) with a bar coater (No. 34) and dried in a hot air dryer at 120 ° C. for 3 minutes. Near-infrared absorbing material A1 was obtained. The visible-near infrared absorption spectrum is shown in FIG. The near-infrared transmittance, total light transmittance, wet heat resistance, flex resistance, and solvent resistance of the near-infrared absorbing material A1 were evaluated, and the results are shown in Table 1.

(Example 2-1)
As the resin, the resin solution 1 obtained in Example 1-1 was used.

(Example 2-2)
CIR-RL (manufactured by Nippon Carlit) was used as the diimonium dye. This dimonium dye was composed of a dimonium cation and a bis (trifluoromethanesulfone) imide anion and had a melting point of 235 ° C. CIR-RL was dissolved in methyl ethyl ketone to prepare a diimonium dye solution 2 having a solid content of 3%. 9.1 parts of resin solution 1, 2.5 parts of diimonium dye solution 2, 2.5 parts of the phthalocyanine solution prepared in Example 1-2, and 0.9 parts of methyl ethyl ketone are mixed to absorb near infrared rays. Composition A2 was obtained.

(Example 2-3)
A near-infrared absorbing material A2 was obtained in the same manner as in Example 1-3 using the near-infrared absorbing composition A2 instead of the near-infrared absorbing composition A1. This visible-near infrared absorption spectrum is shown in FIG. The near-infrared transmittance, total light transmittance, wet heat resistance, flex resistance, and solvent resistance of the near-infrared absorbing material A2 were evaluated, and the results are shown in Table 1.

(Comparative Example 1-1)
As the resin, the resin solution 1 obtained in Example 1-1 was used.

(Comparative Example 1-2)
N, N, N ′, N ′,-tetrakis- (p-di (n-butyl) aminophenyl) -p-benzoquinone-bis-imonium hexafluoroantimonate (anionic molecular weight 236) is dissolved in methyl ethyl ketone. Then, a diimonium dye solution 3 having a solid content of 3% was prepared. 9.1 parts of the resin solution 1, 2.5 parts of the diimonium dye solution 3, 2.5 parts of the phthalocyanine solution prepared in Example 1-2, and 0.9 parts of methyl ethyl ketone are mixed to absorb near infrared rays. Composition B1 was obtained.

(Comparative Example 1-3)
A near-infrared absorbing material B1 was obtained in the same manner as in Example 1-3 using the near-infrared absorbing composition B1 instead of the near-infrared absorbing composition A1. This visible-near infrared absorption spectrum is shown in FIG. The near-infrared transmittance, total light transmittance, wet heat resistance, flex resistance, and solvent resistance of the near-infrared absorbing material B1 were evaluated, and the results are shown in Table 1.

(Comparative Example 2-1)
As a monomer, 453 g of methyl methacrylate and 47 g of normal butyl methacrylate were mixed to obtain a monomer mixture 2. 6 g of Parkadox 12XL25 (manufactured by gunpowder Akzo) and 100 g of toluene were mixed to obtain an initiator solution 2. 350 g of this monomer mixture 1, 225 g of toluene, and 0.5 g of normal dodecyl mercaptan were placed in a flask, and a thermometer, a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a dropping funnel were set in the flask. 150 g of monomer mixture 1 and 31.8 g of initiator solution 1 were mixed and placed in the dropping funnel. While flowing nitrogen gas at a rate of 20 ml / min, the flask was heated to an internal temperature of 100 ° C. 74.2 g of initiator solution 1 was added to the flask to initiate the polymerization reaction. Ten minutes after the introduction of the polymerization initiator, the mixture in the dropping funnel (mixture of the monomer mixture 1 and the initiator solution 1) was added to the flask over 60 minutes. After the addition, the dropping funnel was washed with 75 g of toluene, and the washing solution was added to the flask. Thereafter, aging was performed for 60 minutes, and 150 g of toluene as a diluent solvent was added into the flask. The mixture was further aged for 60 minutes, and 150 g of toluene as a diluent solvent was added to the flask. The mixture was further aged for 60 minutes, and 150 g of toluene as a diluent solvent was added to the flask. It was aged for another 60 minutes. Thereafter, the temperature was raised to 108 ° C. and aged for 300 minutes. Further, after adding 125 g of a diluting solvent, it was cooled to room temperature to obtain a resin solution 2. The solid content was 32.2%, the Tg was 106 ° C., and the weight average molecular weight in terms of polystyrene was 120,000.

(Comparative Example 2-2)
9.4 parts of resin solution 2, 2.5 parts of diimonium dye solution 1 prepared in Example 1-2, 2.5 parts of phthalocyanine solution prepared in Example 1-2, and 0.6 parts of methyl ethyl ketone Were mixed to obtain a near-infrared absorbing composition B2.

(Comparative Example 2-3)
A near-infrared absorbing material B2 was obtained in the same manner as in Example 1-3 using the near-infrared absorbing composition B2 instead of the near-infrared absorbing composition A1. This visible-near infrared absorption spectrum is shown in FIG. The near-infrared transmittance, total light transmittance, wet heat resistance, flex resistance, and solvent resistance of the near-infrared absorbing material B2 were evaluated, and the results are shown in Table 1.

(Comparative Example 3-1)
As a monomer, 312.8 g of methyl methacrylate, 72 g of cyclohexyl methacrylate, 9.2 g of 2-ethylhexyl acrylate, and 6 g of methacrylic acid were mixed to obtain a monomer mixture 3. Perbutyl O (made by NOF Corporation) 0.72g and ethyl acetate 72g were mixed, and the initiator solution 3 was obtained. 2.4 g of ABN-V (manufactured by Nippon Hydrazine Industry) and 24 g of toluene were mixed to obtain an initiator solution 4. 280 g of the monomer mixture 3 and 140 g of ethyl acetate were placed in a flask, and a thermometer, a stirrer, a nitrogen gas inlet tube, a reflux condenser, and a dropping funnel were set in the flask. 120 g of the monomer mixture 3 and 21.82 g of the initiator solution 3 were mixed and placed in the dropping funnel. While flowing nitrogen gas at a rate of 20 ml / min, the flask was heated to an internal temperature of 80 ° C. 50.9 g of the initiator solution 3 was added into the flask to initiate the polymerization reaction. Ten minutes after the introduction of the polymerization initiator, the mixture in the dropping funnel (mixture of the monomer mixture 3 and the initiator solution 3) was added to the flask over 60 minutes. After the addition, the dropping funnel was washed with 24 g of ethyl acetate, and the washing solution was added to the flask. Thereafter, the mixture was aged for 90 minutes, and 80 g of ethyl acetate as a diluent solvent was added to the flask. The mixture was further aged for 60 minutes, and 120 g of toluene was added to the flask as a diluent solvent. The mixture was aged for 30 minutes, and the temperature in the flask was raised to 91 ° C. over 30 minutes. Further, after aging for 30 minutes, 4.4 g of initiator solution 4 was added to the flask. The mixture was further aged for 30 minutes, and 80 g of toluene as a diluent solvent and 4.4 g of the initiator solution 4 were added to the flask. After aging for 30 minutes, 4.4 g of the initiator solution 4 was added to the flask. Further, the mixture was aged for 30 minutes, and 80 g of toluene and 4.4 g of the initiator solution 4 were added to the flask as a diluent solvent. After aging for 30 minutes, 4.4 g of the initiator solution 4 was added to the flask. After aging for 30 minutes, 4.4 g of the initiator solution 4 was added to the flask. After further aging for 120 minutes, 284 g of toluene as a diluent solvent was added to the flask. Then, it cooled to room temperature and obtained the resin solution 3. The solid content was 30.5%, the Tg was 94 ° C., and the weight average molecular weight in terms of polystyrene was 250,000.

(Comparative Example 3-2)
Cyanine dye S0712 (manufactured by FEW CHMICALS) was dissolved in methyl ethyl ketone to prepare a cyanine dye solution having a solid content of 3%. 9.8 parts of resin solution 3, 2.8 parts of diimonium dye solution 1 prepared in Example 1-2, 0.43 part of cyanine dye solution, and 1.7 parts of methyl ethyl ketone were mixed, and near infrared rays were mixed. Absorbent composition B3 was obtained.

(Comparative Example 3-3)
A near-infrared absorbing material B3 was obtained in the same manner as in Example 1-3 using the near-infrared absorbing composition B3 instead of the near-infrared absorbing composition A1. This visible-near infrared absorption spectrum is shown in FIG. The near-infrared transmittance, total light transmittance, wet heat resistance, flex resistance, and solvent resistance of the near-infrared absorbing material B3 were evaluated, and the results are shown in Table 1.

(Comparative Example 4-1)
As a monomer, 2-ethylhexyl acrylate (264.4 g), butyl acrylate (150 g), cyclohexyl methacrylate (180 g) and hydroxyethyl acrylate (5.4 g) were weighed and mixed well to obtain monomer mixture 4. 40% by mass of the monomer mixture 4 and ethyl acetate (160 g) were placed in a flask equipped with a thermometer, a stirrer, an inert gas introduction tube, a reflux condenser, and a dropping funnel. A monomer mixture for dropping composed of 60% by mass of the monomer mixture 4, ethyl acetate (16 g), and NIPER BMT-K40 (0.15 g) as a polymerization initiator was put in a dropping funnel and mixed well. While flowing nitrogen gas at a rate of 20 ml / min, the internal temperature of the flask was raised to 84 ° C., and Niper BMT-K40 (0.15 g) as a polymerization initiator was charged into the flask to initiate the polymerization reaction. Thirty minutes after the introduction of the polymerization initiator, the dropping of the dropping monomer mixture in the dropping funnel was started. The monomer mixture for dripping was dripped uniformly over 60 minutes. After completion of dropping, ethyl acetate (100 g) was charged into the flask. Thereafter, the reaction solution was aged at reflux for 6 hours. After completion of the reaction, the reaction solution was diluted with ethyl acetate so that the nonvolatile content was about 45%, and a resin solution 4 was obtained. The resin solution 4 had a calculated Tg of −35 ° C. and a polystyrene-equivalent weight average molecular weight of 440,000.

(Comparative Example 4-2)
6.8 parts of resin solution 4, 2.5 parts of diimonium dye solution 1 prepared in Example 1-2, 2.5 parts of phthalocyanine solution prepared in Example 1-2, and 3.2 parts of methyl ethyl ketone Were mixed to obtain a near-infrared absorbing composition B4.

(Comparative Example 4-3)
The near-infrared absorbing composition 1 was coated on an easy-adhesion-treated PET film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm with a bar coater (No. 34) and dried in a hot air dryer at 120 ° C. for 3 minutes. . An easy-adhesion-treated PET film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm was laminated on the coated surface using a roller to obtain a near-infrared absorbing material B4. This visible-near infrared absorption spectrum is shown in FIG. The near-infrared transmittance, total light transmittance, and wet heat resistance of the near-infrared absorbing material B4 were evaluated, and the results are shown in Table 1.

  From the results shown in Table 1, the near-infrared absorbing material A1 of the present invention has the same bending resistance and solvent resistance as compared to the near-infrared absorbing material B1 using a diimonium dye composed of an anion having a molecular weight of less than 250. However, the transmittance change and b * change during the heat and humidity resistance test were significantly small, suggesting that the near-infrared absorbing material of the present invention hardly deteriorates. Further, near-infrared absorbing material A2 composed of an anion having a molecular weight of 250 or more and having a melting point of 235 ° C. uses near-infrared absorbing material A1, which is a change in transmittance in the near-infrared region during the wet heat resistance test, compared to near-infrared absorbing material A1. And b * change was further reduced, and it was confirmed that deterioration was less likely.

  Further, the near-infrared absorbing material A1 of the present invention does not generate cracks even in the bending resistance test and the solvent resistance test, compared to the near-infrared absorbing materials B2 and B3 using a resin having a Tg exceeding 85 ° C. It was suggested that the near-infrared absorbing material of the present invention exhibits high flexibility.

  Moreover, the near-infrared absorbing material A1 of the present invention has a higher initial near-infrared absorbing ability than the near-infrared absorbing material B4 using a resin having a Tg of less than 25 ° C., and the near-infrared absorbing material of the present invention is high. It was suggested to show near infrared absorption ability.

(Example 3)
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 stirrer organic polymers (P-1), dropping inlet, a thermometer, a 1-liter flask equipped with a condenser and N2 gas inlet was placed 260 parts of acetic acid n- butyl as an organic solvent, introducing the N ₂ gas The temperature inside the flask was heated to 110 ° C. while stirring. 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 prepared by mixing 48 parts and 2.5 parts of 2,2′-azobis- (2-methylbutyronitrile) was added dropwise 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 and further heated for 2 hours to carry out copolymerization. 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 mass 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 were mixed and dissolved in 40 parts of methyl ethyl ketone. A solution obtained by dissolving 0.5 part of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) in 2 parts of methyl ethyl ketone was added 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 opposite to the antireflection film side of the film is roughened with steel wool, further coated with black ink, and the specular reflection spectrum at an incident angle of 5 ° on the surface of the antireflection film side is measured with an ultraviolet-visible spectrophotometer (UV- 3100, manufactured by Shimadzu Corporation), and the minimum value of the reflectance was determined as the wavelength at which the reflectance shows the minimum value. The reflectance of the obtained antireflection film was 0.45% at a wavelength of 550 nm.

5. Optical filter On the back side of the obtained antireflection film, the near-infrared absorbing composition A1 obtained in Example 1-2 was applied and dried in the same manner as in Example 1-3 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 composition of the present invention is useful as an optical filter for thin displays because it has high near-infrared absorbing ability and transparency in the visible region, and is excellent in heat resistance and moist heat resistance. It can also be used as an optical information recording material.

It is a graph which shows the visible-near-infrared absorption spectrum of near-infrared absorber A1 obtained in Example 1-3. It is a graph which shows the visible-near-infrared absorption spectrum of near-infrared absorber A2 obtained in Example 2-3. It is a graph which shows the visible-near-infrared absorption spectrum of near-infrared absorber B1 obtained by Comparative Example 1-3. It is a graph which shows the visible-near-infrared absorption spectrum of near-infrared absorber B2 obtained by Comparative Example 2-3. It is a graph which shows the visible-near-infrared absorption spectrum of near-infrared absorber B3 obtained by Comparative Example 3-3. It is a graph which shows the visible-near-infrared absorption spectrum of near-infrared absorber B4 obtained by Comparative Example 4-3.

Claims (11)

  A near-infrared absorbing composition containing a diimonium dye having an anion having a molecular weight of 250 or more and a resin having a Tg of 20 ° C or higher and 85 ° C or lower. 2. The near-infrared absorbing composition according to claim 1, wherein the diimonium dye comprises a diimonium cation represented by the following formula (1) and an anion represented by the following formula (2) or the following formula (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 composition according to claim 1 or 2, wherein the melting point of the dimonium dye is 200 ° C or higher. The near-infrared absorbing composition contains a polymer obtained by polymerizing a (meth) acrylic acid ester and a near-infrared absorbing dye,
The (meth) acrylic acid ester has an alkyl group having 1 to 10 carbon atoms, and the alkyl group is a linear, branched, alicyclic or polycyclic alicyclic alkyl group. To 3. The near-infrared absorbing composition according to any one of items 1 to 3.   Furthermore, the near-infrared absorption composition in any one of Claim 1 to 4 containing a phthalocyanine type pigment | dye.   The near-infrared absorber containing the near-infrared absorption composition in any one of Claim 1 to 5.   The near-infrared absorbing material according to claim 6, wherein the near-infrared absorbing composition according to any one of claims 1 to 5 is laminated on a transparent substrate.   The near-infrared absorbing material according to claim 7, wherein the transparent substrate is glass, a PET film, an easily adhesive PET film, a TAC film, an antireflection film, or an electromagnetic wave shielding film.   An optical filter for a thin display, comprising the near-infrared absorbing material according to claim 6.   The optical filter for optical semiconductor elements which uses the near-infrared absorber in any one of Claim 6 to 8.   A thin display comprising the near-infrared absorbing composition according to any one of claims 1 to 5, the near-infrared absorbing material according to any one of claims 6 to 8, or the optical filter according to claim 9.

Images