JP2007111940A - Near infrared absorbing material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an infrared absorbing material which simultaneously satisfies high visible transmittance and high near infrared absorption performance and is reduced in near infrared absorption degradation and lightfastness degradation even when stored in high humidity. <P>SOLUTION: In the near infrared absorbing material, at least one near infrared absorption layer is provided on a support, the near infrared absorption layer contains a compound indicating the maximum wavelength in a range of 750-1,100 nm, and the near infrared absorption layer or a layer adjoining the near infrared absorption layer contains a dihydroxy benzene derivative or a pyrazolidone derivative. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a near-infrared absorbing material.

  Conventionally, a plasma display panel (PDP) emits ultraviolet rays in a rare gas in a plasma state and emits phosphors with the ultraviolet rays. At this time, near-infrared rays are also emitted. There is a growing demand for shielding near-infrared emission from 800 nm to 1000 nm. Near-infrared rays cause malfunctions such as malfunctions to peripheral devices, and there are differences between peripheral devices, but remote controls for televisions and coolers for home appliances, special remote controls for business use, and communication and PDPs The wavelength emitted by each (plasma display) is the same wavelength.

  Therefore, peripheral devices in which the PDP is installed may cause malfunction due to the wavelength emitted by the PDP. In response to this requirement, the method of sticking a near-infrared absorbing film on the front glass of the PDP has become the mainstream because it is simple and advantageous in terms of cost.

  However, due to the heat generation and ultraviolet rays of the PDP, the deterioration of the near-infrared absorbing film is an issue, and the development of heat-resistant near-infrared absorbing pigments and the combined use of UV absorbers with good absorption efficiency are satisfactory. It is not performance.

  There is a non-aqueous coating method (for example, Patent Document 1) so that the deterioration of the near-infrared absorbing dye is not affected by water because of the influence of moisture, but in terms of occupational hygiene of organic solvent volatiles. In addition, there is a problem that it is susceptible to deterioration fluctuation due to residual organic solvent that volatilizes after production, and a dye is present during polymerization of a solvent-free hydrophobic resin, and a product formed from a monomer and a polymerization initiator is molded. There are methods to be used (for example, Patent Document 2), but there are problems such as difficulty in high-speed coating and poor productivity.

  A method (for example, Patent Document 3) in which a pigment is dispersed in a solid fine particle in an aqueous solvent has been proposed. However, this method has problems such as poor storage stability due to the influence of moisture.

In addition, gelatin-dispersed aqueous coating (for example, Patent Document 4) advantageous for high productivity by high-speed thin film coating is an aqueous coating in which a near-infrared absorbing dye is dispersed and coated in gelatin with good dispersibility. While high productivity can be obtained, it has a drawback that it is weak in storage stability. The current problem is that deterioration of the high-temperature and high-humidity storage of near-infrared absorbing dyes is unavoidable due to the water-holding property of gelatin, and there is a demand for solutions to the various problems described above. Yes.
Paragraph (59) of JP-A-10-186127 Paragraphs (42) to (43) of JP-A-11-109126 Paragraph (105) of JP-A-11-109560 Paragraphs (71) to (131) of JP-A-10-333295

  An object of the present invention is to provide a near-infrared absorbing material that exhibits high near-infrared absorbing performance and good storage stability.

  The above object of the present invention has been achieved by the following configurations 1 to 7.

1.
The support has at least one near-infrared absorbing layer, and the near-infrared absorbing layer contains a compound having a maximum wavelength in the range of 750 nm to 1100 nm, and the near-infrared absorbing layer or the near-infrared absorbing layer A near-infrared absorbing material, wherein a layer adjacent to the layer contains a dihydroxybenzene derivative or a pyrazolidone derivative.

2.
2. The near-infrared absorbing material according to 1 above, wherein the dihydroxybenzene derivative is a 1,4-dihydroxybenzene derivative.

3.
3. The near infrared ray absorbing material according to 1 or 2, wherein the pyrazolidone derivative is a 1-phenyl-3-pyrrolidone derivative.

4).
4. The near-infrared absorbing material according to any one of 1 to 3, wherein the near-infrared absorbing layer or an adjacent layer contains an alkali agent.

5.
5. The near-infrared absorbing material as described in 4 above, wherein the alkali agent is a metal salt selected from a metal group selected from alkali metals and alkaline earth metals.

6).
6. The near-infrared absorbing material according to any one of 1 to 5, wherein the compound is at least one selected from the group consisting of a phthalocyanine derivative, a nickel dithiol complex compound, a diimonium derivative, and a squalium derivative. .

7).
The structure layer has at least one layer selected from a functional layer group consisting of an antireflection layer, a high hardness layer, an adhesive layer, and an electromagnetic wave absorption layer. Near-infrared absorbing material.

  According to the present invention, a near-infrared absorbing material that exhibits high near-infrared absorbing performance and good storage stability can be provided.

  In the near-infrared absorbing material of the present invention, by using the configuration according to any one of claims 1 to 7, a near-infrared absorbing material that exhibits high near-infrared absorbing performance and good storage stability is provided. We were able to.

  Hereinafter, details of each component according to the present invention will be sequentially described.

<< Near-infrared absorbing layer >>
The near-infrared absorbing layer according to the present invention will be described.

  The near-infrared absorbing layer according to the present invention contains a compound having a maximum wavelength in the range of 750 nm to 1100 nm, and as the compound, a near-infrared absorbing dye is preferable, for example, polymethine-based, phthalocyanine-based, naphthalocyanine-based, Metal complex, aminium, imonium, diimonium, anthraquinone, dithiol metal complex, naphthoquinone, indolephenol, azo, and triallylmethane compounds.

  An example of an application in which the near-infrared absorbing material of the present invention is preferably used is an optical filter for PDP (plasma display). The near-infrared absorbing ability of the filter is mainly required for heat ray absorption and electron It is noise prevention of equipment. For this purpose, a dye having a near-infrared absorption ability having a maximum absorption wavelength of 750 nm to 1100 nm is preferable, and a metal complex compound, an aminium compound (aminium derivative), a phthalocyanine compound (phthalocyanine derivative), a naphthalocyanine compound ( Naphthalocyanine derivatives), diimonium compounds (diimonium derivatives), squalium compounds (squalium derivatives) and the like are particularly preferably used.

  Conventionally, the absorption maximum of a known nickel dithiol complex compound or a fluorinated phthalocyanine compound is 700 nm to 900 nm, and in practical use, usually an aminium compound having an absorption maximum in a longer wavelength region than the above compound. When used in combination with a compound, particularly a diimonium compound, an effective near-infrared absorption effect can be obtained.

  Examples of the diimonium derivative according to the present invention include compounds represented by the following general formula (1).

In the formula, R _{1 to} R ₈ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aralkyl group, which may be linear or branched, and R _{1 to} R _8. May be the same or different. X represents an anion.

In the general formula (1), examples of the alkyl group represented by R _{1 to} R ₈ include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, sec -Butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, tert-pentyl group, n-hexyl group, n-octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, 2-hydroxyethyl Group, 3-hydroxypropyl group, 4-hydroxybutyl group, 2-acetoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group Group, 3-sulfatepropyl group, 4-sulfatebutyl group, N- (methylsulfonyl) -carbamylmethy Group, 3- (acetylsulfamyl) propyl group, 4- (acetylsulfamyl) butyl group, cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, 2-cyanopropyl group, 4-cyanobutyl group, 3 -Cyanobutyl group, 2-cyanobutyl group, 5-cyanopentyl group, 4-cyanopentyl group, 3-cyanopentyl group, 2-cyanopentyl group, 6-cyanohexyl group, 5-cyanohexyl group, 4-cyanohexyl group , 3-cyanohexyl group, 2-cyanohexyl group and the like, and an alkyl group having 1 to 10 carbon atoms is preferably used.

In the general formula (1), examples of the cycloalkyl group represented by R _{1 to} R ₈ include a cyclopentyl group and a cyclohexyl group.

In the general formula (1), examples of the alkenyl group represented by R _{1 to} R ₈ include a vinyl group, an allyl group, and a propenyl group.

In the general formula (1), examples of the aralkyl group represented by R _{1 to} R ₈ include benzyl group, phenethyl group, α-naphthylmethyl group, β-naphthylmethyl group, carboxybenzyl group, sulfobenzyl group, hydroxy A benzyl group etc. are mentioned.

In the general formula (1), each group represented by R _{1 to} R ₈ may be further substituted with the above group, and a plurality of these groups are bonded to each other to form a ring. May be.

  In the general formula (1), X represents a monovalent anion or a divalent anion.

  In the general formula (1), examples of the monovalent anion represented by X include organic acid monovalent anions and inorganic monovalent anions.

  Examples of organic acid monovalent anions include acetate ions, lactate ions, trifluoroacetate ions, propionate ions, benzoate ions, oxalate ions, succinate ions, stearic acid ions, and other organic carboxylate ions, methanesulfonate ions, Organic sulfonate ions such as toluene sulfonate ion, naphthalene monosulfonate ion, chlorobenzene sulfonate ion, nitrobenzene sulfonate ion, dodecylbenzene sulfonate ion, benzene sulfonate ion, ethane sulfonate ion, trifluoromethane sulfonate ion, tetra And organic borate ions such as phenylborate ion and butyltriphenylborate ion, and preferably halogenoalkyl sulfate such as trifluoromethanesulfonate ion and toluenesulfonate ion. Phosphate ion or alkyl arylsulfonate ion.

  Examples of the inorganic monovalent anion include halogen ions such as fluorine ion, chlorine ion, bromine ion and iodine ion, thiocyanate ion, hexafluoroantimonate ion, perchlorate ion, periodate ion, nitrate ion and tetrafluoroboron. Acid ions, hexafluorophosphate ions, molybdate ions, tungstate ions, titanate ions, vanadate ions, phosphate ions, borate ions, and the like. Preferred are perchlorate ions, iodine ions, Tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion and the like can be mentioned.

  In the general formula (1), divalent anions represented by X include naphthalene-1,5-disulfonic acid, R acid, G acid, H acid, benzoyl H acid, p-chlorobenzoyl H acid, p -Toluenesulfonyl H acid, chloro H acid, chloroacetyl H acid, methanyl γ acid, 6-sulfonaphthyl-γ acid, C acid, ε acid, p-toluenesulfonyl R acid, naphthalene-1,6-disulfonic acid, 1 -Naphthalenedisulfonic acid derivatives such as naphthol-4,8-disulfonic acid, carbonyl J acid, 4,4'-diaminostilbene-2,2'-disulfonic acid, diJ acid, naphthalic acid, naphthalene-2,3- Dicarboxylic acid, diphenic acid, stilbene-4,4′-dicarboxylic acid, 6-sulfo-2-oxy-3-naphthoic acid, anthraquinone-1,8-disulfonic acid, 1,6-diaminoan Laquinone-2,7-disulfonic acid, 2- (4-sulfophenyl) -6-aminobenzotriazole-5-sulfonic acid, 6- (3-methyl-5-pyrazolonyl) -naphthalene-1,3-disulfonic acid, Examples thereof include divalent organic acid ions derived from 1-naphthol-6- (4-amino-3-sulfo) anilino-3-sulfonic acid and the like.

  Among these anions, preferred are, for example, perchlorate ion, iodine ion, tetrafluoroborate ion, hexafluorophosphate ion, hexafluoroantimonate ion, trifluoromethanesulfonate ion, toluenesulfonate ion Etc.

Although the specific example of the diimonium derivative represented by General formula (1) below is shown, this invention is not limited to these.
(I-1) N, N, N ′, N′-tetrakis (4-di-n-butylaminophenyl) -1,4-benzoquinone-bis (imonium hexafluoroantimonic acid)
(I-2) N, N, N ′, N′-tetrakis (4-di-n-butylaminophenyl) -1,4-benzoquinone-bis (imonium / perchloric acid)
(I-3) N, N, N ′, N′-tetrakis (4-di-amylaminophenyl) -1,4-benzoquinone-bis (imonium hexafluoroantimonic acid)
(I-4) N, N, N ′, N′-tetrakis (4-di-n-propylaminophenyl) -1,4-benzoquinone-bis (imonium hexafluoroantimonic acid)
(I-5) N, N, N ′, N′-tetrakis (4-di-n-hexylaminophenyl) -1,4-benzoquinone-bis (imonium hexafluoroantimonic acid)
(I-6) N, N, N ′, N′-tetrakis (4-di-iso-propylaminophenyl) -1,4-benzoquinone-bis (imonium hexafluoroantimonic acid)
(I-7) 7N, N, N ′, N′-Tetrakis (4-di-n-pentylaminophenyl) -1,4-benzoquinone-bis (imonium hexafluoroantimonic acid)
(I-8) N, N, N ′, N′-tetrakis (4-di-methylaminophenyl) -1,4-benzoquinone-bis (imonium hexafluoroantimonic acid)
<Nickel dithiol complex compound>
The nickel dithiol complex compound according to the present invention will be described.

  As the nickel dithiol complex compound according to the present invention, a compound represented by the following general formula (2) is preferably used.

In the general formula (2), R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), an alkyl group (for example, , Methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, trifluoromethyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.), aryl group (for example, phenyl group, p- Nitrophenyl group etc.), hydroxy group, alkylthio group (eg methylthio group, ethylthio group, butylthio group etc.), arylthio group (eg phenylthio group, tolylthio group etc.), nitro group, cyano group, alkoxy group (eg methoxy) Group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec -Butoxy group, n-pentyloxy group, iso-pentyloxy group, etc.), aryloxy group (for example, phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, naphthoxy group, etc.), Alkylamino group (for example, methylamino group, ethylamino group, n-propylamino group, iso-propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, benzyl) Amino group, dimethylamino group, diethylamino group, di-n-propylamino group, di-iso-propylamino group, di-n-butylamino group, di-iso-butylamino group, di-n-pentylamino group, Di-iso-pentylamino group, di-n-hexylamino group, di-n-heptyl Amino group, di -n- octyl amino group, di - represents a (2-ethylhexyl) amino group, dibenzylamino group, etc.), diarylamino groups (e.g., diphenylamino group, ditolylamino group).

r represents an integer of 1 to 5. When r is plural, each R ₉ , R ₁₀ , R ₁₁ and R ₁₂ may be the same or different from each other.

  Although the specific example of the nickel dithiol complex concerning this invention is shown below, this invention is not limited to these.

[Phthalocyanine derivative (also called phthalocyanine compound)]
As the phthalocyanine derivative (phthalocyanine compound) according to the present invention, a compound represented by the following general formula (3) is preferable.

In the general formula (3), R _{13 to} R ₁₆ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group (also referred to as an aromatic hydrocarbon group or an aromatic carbocyclic group), aromatic Represents a heterocyclic group, an aryloxy group, an alkylthio group, or an arylthio group. When there are a plurality of groups represented by R _{13 to} R ₁₆ , they may be the same as each other or different from each other. M represents a divalent metal atom, a trivalent metal atom, a tetravalent metal atom, or an oxymetal.

  p represents an integer of 1 to 4. Moreover, when a substituent is adjacent, a 5-membered or 6-membered ring may be formed.

In the general formula (3), examples of the halogen atom represented by R _{13 to} R ₁₆ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the general formula (3), examples of the alkyl group represented by R _{13 to} R ₁₆ include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, sec -Butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, 1,2-dimethyl-propyl group, n-hexyl group, cyclohexyl group, 1,3-dimethyl-butyl group, 1-iso-propylpropyl group, 1,2-dimethylbutyl group, heptyl group, 1,4-dimethylpentyl group, 2-methyl 1-iso-propylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl Group, 2-ethylhexyl group, 3-methyl-1-iso-propylbutyl group, 2-methyl-1-iso-propyl group, 1-tert-butyl-2-methylpropyl group C1-C20 linear or branched alkyl group such as propyl group, n-nonyl group, methoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, γ-methoxypropyl group, γ -Ethoxypropyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, dimethoxymethyl group, diethoxymethyl group, dimethoxyethyl group, diethoxyethyl group and other alkoxyalkyl groups, alkoxyalkoxyalkyl groups, alkoxyalkoxyalkoxyalkyl groups, chloro Methyl group, 2,2,2-trichloroethyl group, trifluoromethyl group, 2,2,2-trichloroethyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group, etc. Halogenated alkyl group, alkylaminoalkyl group, dialkylaminoal Examples include a kill group, an alkoxycarbonylalkyl group, an alkylaminocarbonylalkyl group, and an alkoxysulfonylalkyl group. These groups may further have a substituent.

In the general formula (3), examples of the alkoxy group represented by R _{13 to} R ₁₆ include a methoxy group, an ethoxy group, an n-propyloxy group, an iso-propyloxy group, an n-butyloxy group, and an iso-butyloxy group. , Sec-butyloxy group, tert-butyloxy group, n-pentyloxy group, iso-pentyloxy group, neo-pentyloxy group, 1,2-dimethyl-propyloxy group, n-hexyloxy group, cyclohexyloxy group, 1 , 3-dimethyl-butyloxy group, 1-iso-propylpropyloxy group, 1,2-dimethylbutyloxy group, n-heptyloxy group, 1,4-dimethylpentyloxy group, 2-methyl-1-iso-propyl Propyloxy group, 1-ethyl-3-methylbutyloxy group, n-octyloxy group, 2 Carbon such as -ethylhexyloxy group, 3-methyl-1-iso-propylbutyloxy group, 2-methyl-1-iso-propyloxy group, 1-tert-butyl-2-methylpropyloxy group, n-nonyloxy group A linear or branched alkoxy group of formula 1 to 20, methoxymethoxy group, methoxyethoxy group, ethoxyethoxy group, propoxyethoxy group, butoxyethoxy group, γ-methoxypropyloxy group, γ-ethoxypropyloxy group, methoxyethoxyethoxy Groups, ethoxyethoxyethoxy groups, dimethoxymethoxy groups, diethoxymethoxy groups, dimethoxyethoxy groups, diethoxyethoxy groups, etc. alkoxyalkoxy groups, methoxyethoxyethoxy groups, ethoxyethoxyethoxy groups, butyloxyethoxyethoxy groups, etc. Coxyalkoxy group, alkoxyalkoxyalkoxyalkoxy group, chloromethoxy group, 2,2,2-trichloroethoxy group, trifluoromethoxy group, 2,2,2-trichloroethoxy group, 1,1,1,3,3, Examples include halogenated alkoxy groups such as 3, -hexafluoro-2-propyloxy group, alkylaminoalkoxy groups such as dimethylaminoethoxy group and diethylaminoethoxy group, and dialkylaminoalkoxy groups. These groups may further have a substituent.

In the general formula (3), examples of the aryl group represented by R _{13 to} R ₁₆ include a halogenated phenyl group such as a phenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a fluorinated phenyl group, and an iodinated phenyl group. Group, tolyl group, xylyl group, mesityl group, ethylphenyl group, methoxyphenyl group, ethoxyphenyl group and the like.

In the general formula (3), examples of the aromatic heterocyclic group represented by R _{13 to} R ₁₆ include a furyl group, a thienyl group, a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, an imidazolyl group, Examples include a pyrazolyl group, a thiazolyl group, a quinazolinyl group, and a phthalazinyl group. These groups may further have a substituent.

In the general formula (3), examples of the aryloxy group represented by R _{13 to} R ₁₆ include a phenoxy group and a naphthoxy group. These groups may further have a substituent.

In the general formula (3), examples of the alkylthio group represented by R _{13 to} R ₁₆ include a methylthio group, an ethylthio group, an n-propylthio group, an iso-propylthio group, an n-butylthio group, an iso-butylthio group, sec -Butylthio group, tert-butylthio group, n-pentylthio group, iso-pentylthio group, neo-pentylthio group, 1,2-dimethyl-propylthio group, n-hexylthio group, cyclohexylthio group, 1,3-dimethyl-butylthio group 1-iso-propylpropylthio group, 1,2-dimethylbutylthio group, n-heptylthio group, 1,4-dimethylpentylthio group, 2-methyl 1-iso-propylpropylthio group, 1-ethyl-3 -Methylbutylthio group, n-octylthio group, 2-ethylhexylthio group, 3-methyl- 1-iso-propylbutylthio group, 2-methyl-1-iso-propylthio group, 1-tert-butyl-2-methylpropylthio group, n-nonylthio group, etc. Alkylthio group, methoxymethylthio group, methoxyethylthio group, ethoxyethylthio group, propoxyethylthio group, butoxyethylthio group, γ-methoxypropylthio group, γ-ethoxypropylthio group, methoxyethoxyethylthio group, ethoxyethoxyethyl Alkoxyalkylthio groups such as thio group, dimethoxymethylthio group, diethoxymethylthio group, dimethoxyethylthio group, diethoxyethylthio group, alkoxyalkoxyalkylthio group, alkoxyalkoxyalkoxyalkylthio group, chloromethylthio group, 2,2,2-trichloro D Halogenated alkylthio groups such as tilthio group, trifluoromethylthio group, 2,2,2-trichloroethylthio group, 1,1,1,3,3,3-hexafluoro-2-propylthio group, dimethylaminoethyl Examples thereof include alkylaminoalkylthio groups such as thio group and diethylaminoethylthio group, and dialkylaminoalkylthio groups. These groups may further have a substituent.

In the general formula (3), examples of the arylthio group represented by R _{13 to} R ₁₆ include a phenylthio group, a naphthylthio group, and an alkylphenylthio group. These groups may further have a substituent.

  In the general formula (3), as a divalent metal atom represented by M (also referred to as a divalent metal), Cu (II), Zn (II), Co (II), Ni (II), Ru ( II), Rh (II), Pd (II), Pt (II), Mn (II), Mg (II), Ti (II), Be (II), Ca (II), Ba (II), 1d ( II), Hg (II), Pb (II), Sn (II) and the like.

In the general formula (3), a trivalent metal atom represented by M (also referred to as a trivalent metal, a tetravalent metal may have one substituent to form a trivalent metal) As, for example, Al-Cl, Al-Br, Al-F, Al-I, Ga-Cl, Ga-F, Ga-I, Ga-Br, In-Cl, In-Br, In-I, In -F, Tl-Cl, Tl- Br, Tl-I, Tl-F, Al-C 6 H 5 ( wherein, -C ₆ H ₅ represents a phenyl _{group), 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]} Fe-Cl, Ru-Cl and the like.

In the general formula (3), a tetravalent metal atom represented by M (also referred to as a tetravalent metal, and a hexavalent metal atom may have two substituents to form a tetravalent metal. ) May be, for example, CrC ₂ , SiCl ₂ , SiBr ₂ , SF ₂ , SiI ₂ , ZrCl ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ , GeF ₂ , SnCl ₂ , SnBr ₂ , SnF ₂ , TiCl ₂ , TiBr _2. , TiF ₂ , Si (OH) ₂ , Ge (OH) ₂ , Zr (OH) ₂ , Mn (OH) ₂ , Sn (OH) ₂ , TiR ₂ , CrR ₂ , SiR ₂ , SnR ₂ , GeR ₂ [R Represents an alkyl group, a phenyl group, a naphthyl group or a group derived therefrom], Si (OR ′) ₂ , Sn (OR ′) ₂ , Ge (OR ′) ₂ , Ti (OR ′) ₂ , Cr ( OR ') ₂ [R' is an alkyl group, a phenyl group, a naphthyl group, tri Rukirushiriru group, dialkyl alkoxysilyl group or a group derived _{therefrom], Sn (SR ") 2,} Ge (SR") 2 (R " is an alkyl group, a phenyl group, a naphthyl group or a group derived therefrom For example).

  In the general formula (3), examples of the oxymetal represented by M include VO, MnO, and TiO.

  The compound represented by the general formula (3) according to the present invention can be synthesized with reference to, for example, JP-A-2005-145896.

  Hereinafter, although the specific example of a compound represented by General formula (3) is shown, this invention is not limited to these.

《Squarium derivative (also referred to as squalium compound)》
As the squalium derivative (squarium compound) according to the present invention, a compound represented by the following general formula (4) is preferably used.

In the formula, R _{17 to} R ₂₇ each represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an aromatic heterocyclic group, or a heterocyclic group. X _{1 to} X ₄ each represent —N (R) —, —O—, and —S—. R represents an alkyl group, a cycloalkyl group, or an aryl group, and these groups are each an alkyl group, a cycloalkyl group, or an aryl group represented by R _{17 to} R ₂₇ in the general formula (4) described later. Synonymous with group.

In the general formula (4), the alkyl group represented by R _{17 to} R ₂₇ is an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, Hexyl group, undecyl group, etc.). The alkyl group includes a halogen atom (for example, F, Cl, Br, etc.), an alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, etc.), a hydroxy group, an alkoxy group (for example, methoxy group, ethoxy group, phenoxy). Group, isobutoxy group, etc.), acyloxy group (for example, acetyloxy group, butyryloxy group, hexyloxy group, benzoyloxy group, etc.), sulfo group (may be salt), carboxyl group (may be salt), etc. May be.

In the general formula (4), examples of the cycloalkyl group represented by R _{17 to} R ₂₇ include cyclopentyl and cyclohexyl.

In the general formula (4), examples of the aryl group represented by R _{17 to} R ₂₇ include a phenyl group, a p-chlorophenyl group, a mesityl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, an azulenyl group, and an acenaphthenyl group. Group, a fluorenyl group, a phenanthryl group, an indenyl group, a pyrenyl group, a biphenylyl group and the like are preferable, among which a group having 6 to 12 carbon atoms is preferable, and a phenyl group and a naphthyl group are particularly preferable.

  These aryl groups are alkyl groups having 1 to 8 carbon atoms (for example, methyl, ethyl, butyl), alkoxy groups having 1 to 6 carbon atoms (for example, methoxy, ethoxy), aryloxy groups (for example, phenoxy, p -Chlorophenoxy), halogen atom (F, Cl, Br), alkoxycarbonyl group (for example, methoxycarbonyl, ethoxycarbonyl), amino group (for example, methylamino, acetylamino, methanesulfonamide), cyano group, nitro group, It may be substituted with a carboxyl group (which may be a salt) and a sulfo group (which may be a salt).

In the general formula (4), the aralkyl group represented by R _{17 to} R ₂₇ is preferably an aralkyl group having 7 to 12 carbon atoms (for example, benzyl, phenylethyl).
, May have a substituent (for example, methyl, methoxy, chloro atom).

In the general formula (4), examples of the aromatic heterocyclic group represented by R _{17 to} R ₂₇ include a pyridyl group, pyrimidinyl group, thienyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, Pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group , Isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group (carboline ring of the above carbolinyl group) Is one in which one of the carbon atoms constituting is replaced by a nitrogen atom) Quinoxalinyl group, pyridazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group and the like.

  These aromatic heterocyclic groups may be further substituted with the above alkyl group, aryl group or the like.

In the general formula (4), examples of the heterocyclic group represented by R _{17 to} R ₂₇ include a pyrrolidyl group, an imidazolidyl group, a morpholyl group, and an oxazolidyl group.

  These heterocyclic groups may be further substituted with the above alkyl group, aryl group or the like.

  Further, adjacent substituents may be bonded to each other to form a cyclopentane or cyclohexane ring. m and n represent 0 or an integer of 1 to 6, and may be a mixture.

  The compound represented by the general formula (4) according to the present invention is D.I. J. et al. Gravesteijnetal: Optical Storage Media SPIE-420, p327, 1983 can be synthesized.

  Hereinafter, specific examples (S-1 to S-6, S-12, and S-13) of the squalium derivative represented by the general formula (4) and the general formula (4) are not included in the category. Although the specific example (S-7-S-11) of the squalium compound which may be used for invention is shown, this invention is not limited to these.

  Furthermore, as a near-infrared absorbing dye according to the present invention, as the diimonium derivative, IRG-022, IRG-040 (these are trade names manufactured by Nippon Kayaku Co., Ltd.) and the like, and as the nickel dithiol complex compound, SIR- 128, SIR-130, SIR-132, SIR-159, SIR-152, SIR-162 (these are trade names manufactured by Mitsui Chemicals, Inc.) and the like, and phthalocyanine derivatives include IR-10, IR-12 ( As described above, commercially available products such as Nippon Shokubai Co., Ltd. trade name) can be used.

  The near-infrared absorber may be used after being dissolved in an organic solvent such as alcohol solvents such as methanol, ethanol and isopropanol, ketone solvents such as acetone, methyl ethyl ketone and methyl butyl ketone, dimethylsulfoxide, dimethylformamide, dimethyl ether and toluene. It is preferable to apply fine particles having an average particle size of 0.01 μm to 10 μm with a fine particle machine, and the amount of addition is adjusted so that the optical density is in the concentration range of 0.05 to 3.0 at the maximum wavelength. It is preferable to use it.

  In addition, when making the color tone control layer contain the pigment | dye which has a near-infrared absorptivity, you may contain any 1 type in said pigment | dye, and may contain 2 or more types. Further, it is preferable to use an ultraviolet absorber in combination in order to avoid deterioration of the near infrared absorbing dye due to ultraviolet rays. The ultraviolet absorber may be used in the near-infrared absorbing layer, but may be the upper layer or lower layer of the layer, or may be set on the opposite side of the support.

  The near-infrared absorbing layer according to the present invention or the adjacent layer of the near-infrared absorbing layer (the adjacent layer will be described later but is also referred to as an intermediate layer) contains a dihydroxybenzene derivative or a pyrazolidone derivative.

<Dihydroxybenzene derivative>
The dihydroxybenzene derivative according to the present invention will be described.

  The dihydroxybenzene derivative used in the present invention is a compound having two hydroxy groups in the benzene ring. Among them, a compound represented by the following general formula (5) is preferably used in the present invention.

In the formula, R _{11 to} R ₁₄ each represent a hydrogen atom or a substituent.

In the general formula (5), each of the substituents represented by R _{11 to} R ₁₄ is an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group). Octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group etc.), alkenyl group (eg, vinyl group, allyl group etc.), alkynyl group (eg, Ethynyl group, propargyl group, etc.), aromatic hydrocarbon group (also called aromatic carbocyclic group, aryl group, etc.), for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group , Azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, Biphenylyl group), aromatic heterocyclic group (for example, furyl group, thienyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, imidazolyl group, pyrazolyl group, thiazolyl group, quinazolinyl group, phthalazinyl group, etc.), Heterocyclic group (for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, iso-propyloxy group, n-butyloxy group, iso-butyloxy group) , Sec-butyloxy group, n-pentyloxy group, iso-pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group, etc.), aryloxy Group ( For example, phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, naphthyloxy group, etc.), alkylthio group (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group) Group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl, etc.) Group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamo Group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthyl) Aminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, Phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butyl) Carbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (eg, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group) Cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc., carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethyl) Aminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, -Ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, Octylureido group, dodecylureido group, phenylureido group naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, Dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methyl Sulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group ( For example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group, methylamino group, n-propyl Amino group, iso-propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, benzylamino group, dimethylamino group, diethylamino group, di-n-propyl Propylamino group, di-iso-propylamino group, di-n-butylamino group, di-iso-butylamino group, di-n-pentylamino group, di-iso-pentylamino group, di-n-hexylamino group , Di-n-heptylamino group, di-n-octylamino group, di- (2-ethylhexyl) amino group, dibenzylamino group, dinaphthylamino group, diphenylamino group, ditolylamino group, etc.), halogen atom (for example, Fluorine atom, chlorine atom, bromine atom, etc.), fluorinated hydrocarbon group (eg, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl group, etc.), cyano group, nitro group, hydroxy group, Mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenoxy group) Le diethyl silyl group and the like), and the like.

  These substituents may be further substituted with the above substituents. In addition, a plurality of these substituents may be bonded to each other to form a ring (5- to 8-membered ring).

  Although the preferable specific example of the dihydroxybenzene derivative which concerns on this invention is shown below, this invention is not limited to these.

[Pyrazolidone derivatives (also called pyrazolidone compounds)]
The pyrazolidone derivative according to the present invention will be described.

The pyrazolidone derivative used in the present invention has a pyrazolidone skeleton structure in the mother nucleus, and preferred structures are 1-phenyl-3-pyrrolidones substituted at the 2-position, 4-position or 5-position, As each group, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 13 carbon atoms are preferable. These alkyl groups, aryl groups, and aralkyl groups may each have a substituent. Examples of each substituent include a hydroxy group, an alkoxy group, a hydroxyalkyl group, an amino group, a nitro group, a sulfonic acid group, A carboxy group and a halogen atom can be mentioned. Although the example of these specific compounds is given to the following, this invention is not limited to these.
(1) 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone (2) 1-p-tolyl-4,4-dihydroxymethyl-3-pyrazolidone (3) 1-phenyl-4-hydroxymethyl-4- Methyl-3-pyrazolidone (4) 1-phenyl-4,4-dimethyl-3-pyrazolidone (5) 1-phenyl-2-hydroxymethyl-4,4-dimethyl-3-pyrazolidone (6) 1-phenyl-2 -Morpholinomethyl-4,4-dimethyl-3-pyrazolidone (7) 1-phenyl-2-morpholinomethyl-4-methyl-3-pyrazolidone (8) 1-phenyl-2-hydroxymethyl-4-methyl- 3-pyrazolidone (9) 1-phenyl-5,5-dimethyl-3-pyrazolidone (10) 1-phenyl-5-methyl-3-pyrazolidone (11 1-p-Tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone (12) 1-p-hydroxyphenyl-4,4-dimethyl-3-pyrazolidone (13) 1-o-tolyl-4-methyl- 4-hydroxymethyl-3-pyrazolidone (14) 1-p-methoxyphenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone (15) 1- (3,5-dimethyl) phenyl-4-methyl-4- Hydroxymethyl-3-pyrazolidone (16) 1-phenyl-3-pyrazolidone The dihydroxybenzene derivative and the pyrazolidone derivative according to the present invention can be used alone or in combination. At the time of combined use, the compound represented by the general formula (1) with respect to the compound represented by the general formula (5) has a molar ratio of 0.01 to 20, preferably 0.1 to 10. It is preferable to adjust.

《Alkaline agent》
The alkaline agent according to the present invention will be described.

  The alkaline agent according to the present invention is preferably an alkali metal salt or an alkaline earth metal salt, and the salt is contained in the form of a salt such as hydroxide, carbonate, hydrogencarbonate, sulfite oxide, ammonium salt, and the like. be able to. Specific examples of preferable alkali agents include sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium sulfite, potassium sulfite, lithium sulfite and the like. It is. The usage-amount can be used in 1-1000 mol with respect to a near-infrared absorption pigment | dye. In use, the coating solution is preferably added so that the pH is in the range of 5 to 12, and more preferably added so that the pH is in the range of 6 to 11.

<< Near-infrared absorbing layer >>
The near-infrared absorbing dye layer according to the present invention is preferably a polymer in which 30% by mass or more of the total binder is derived from a latex described later, and more preferably 60% by mass or more is a polymer derived from the latex. .

  If necessary, a hydrophilic polymer such as gelatin, polyvinyl alcohol, methyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose or the like is added to the near infrared absorbing layer according to the present invention within a range of 60% by mass or less of the total binder. Also good. The amount of these hydrophilic polymers added is preferably 40% by mass or less of the total binder in the photosensitive layer. Polyvinyl alcohol (PVA) used for the near infrared absorption layer or adjacent layer according to the present invention includes the following compounds.

  As the saponified product, PVA-124H [PVA content 93.5% by mass, saponification degree 99.6 ± 0.3 mol%, sodium acetate content 1.85% by mass, volatile matter 5.0% by mass, viscosity ( 4 mass%, 20 ° C.) 61.0 ± 6.0 CPS], PVA-CS [PVA content 94.0 mass%, saponification degree 97.5 ± 0.5 mol%, sodium acetate content 1.0 mass% , Volatile matter 5.0 mass%, viscosity (4 mass%, 20 ° C.) 27.5 ± 3.0 CPS], PVA-CST [PVA content 94.0 mass%, saponification degree 96.0 ± 0.5 mol %, Sodium acetate content 1.0% by mass, volatile matter 5.0% by mass, viscosity (4% by mass, 20 ° C.) 27.0 ± 3.0 CPS], PVA-HC [PVA content 90.0% by mass , Saponification degree 99.85 mol% or more, sodium acetate content 2.5% by mass, volatilization 8.5 wt%, a viscosity (4 mass%, 20 ℃) 25.0 ± 3.5CPS] (trade names manufactured by any Kuraray Co.). The pH of the final coating solution for the infrared absorbing layer or adjacent layer is preferably in the range of 5.0 to 7.8, particularly preferably in the range of 5.5 to 7.2.

<< Water-based coating liquid (including solution and dispersion) >>
The near-infrared absorbing layer according to the present invention is formed by applying an aqueous coating solution and then drying it. However, the term “aqueous” as used herein refers to a case where 30% by mass or more of the solvent (dispersion medium) of the coating solution is water.

  As components other than water in the coating solution, water-miscible organic solvents such as methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide, and ethyl acetate can be used.

  Specific examples of the solvent composition include the following. Water / methanol = 90/10, water / methanol = 70/30, water / ethanol = 90/10, water / isopropanol = 90/10, water / dimethylformamide = 95/5, water / methanol / dimethylformamide = 80 / 15/5, water / methanol / dimethylformamide = 90/5/5 (however, the number represents mass%).

The total binder amount per layer of the near-infrared absorbing layer according to the present invention is 0.2 g / m ^{2 to} 30 g / m ² , more preferably 1 g / m ^{2 in} terms of the coating amount per 1 m ^{2 of} the near-infrared absorbing material. A range of ˜15 g / m ² is preferred. The film thickness per layer of the near infrared absorbing layer is preferably 0.3 μm to 50 μm, more preferably 1.5 μm to 30 μm.

  The latex used in the present invention (latex will be described in detail later) is preferably used alone or with gelatin, and even when used with gelatin, the less gelatin is better. If the ratio by weight of gelatin used is large, the moisture resistance is greatly deteriorated, and if it is small, the coating is difficult to be uniform. Therefore, 50% or less of the latex resin is preferable. In the present invention, a polyvinyl butyral resin obtained by saponifying vinyl acetate such as polyvinyl butyral and crosslinking with an aldehyde may be dispersed in gelatin as a binder.

<< Preparation of dispersion for coating near-infrared absorbing layer >>
The near-infrared absorbing dye may be an aqueous solution when it is water-soluble, and may be added to the latex solution as a solution of an organic solvent miscible with water such as alcohols, esters, and ketones when water-insoluble. Moreover, when it does not melt | dissolve in these organic solvents, it can add to microparticles | fine-particles of 0.01 micrometer-10 micrometers with a ball mill, a sand mill, a bead mill, a jet mill etc., and can add. As a method for fine particle dispersion, a solid dispersion technique can be preferably applied. For example, a desired particle size can be obtained using a dispersing machine such as a ball mill, a planetary rotating ball mill, a vibrating ball mill, or a jet mill. When a surfactant is used at the time of dispersion, stability after dispersion can be improved.

  As a dispersion apparatus suitable for the present invention, microfluidizer M-110S-EH (with G10Z interaction chamber), M-110Y (with H10Z interaction chamber), M-140K (manufactured by Microfluidex International Corporation) G10Z interaction chamber), HC-5000 (with L30Z or H230Z interaction chamber), HC-8000 (with E230Z or L30Z interaction chamber) and the like. Using these devices, an aqueous dispersion containing at least a near-infrared absorbing dye is pressurized with a high-pressure pump or the like and fed into a pipe, and then passed through a thin slit provided in the pipe to obtain a desired pressure. It is possible to obtain an optimum near-infrared absorbing dye dispersion for the present invention by applying a pressure drop to the dispersion liquid by a method such as applying pressure and then rapidly returning the pressure in the pipe to atmospheric pressure. is there. Prior to the dispersion operation, the raw material liquid is preferably predispersed. As a pre-dispersing means, known dispersing means (for example, high speed mixer, homogenizer, high speed impact mill, Banbury mixer, homomixer, kneader, ball mill, vibration ball mill, planetary ball mill, attritor, sand mill, bead mill, colloid mill, jet mill) , Roller mill, tron mill, high-speed stone mill). In addition to mechanical dispersion, it may be coarsely dispersed in a solvent by controlling the pH, and then finely divided by changing the pH in the presence of a dispersion aid. At this time, an organic solvent may be used as a solvent used for the coarse dispersion, and the organic solvent is usually removed after the formation of fine particles.

In the near-infrared absorbing dye dispersion, it is possible to disperse to a desired particle size by adjusting the flow velocity, the differential pressure at the time of pressure drop and the number of treatments. From the viewpoint of the particle size, the flow velocity is 200 m / sec to 600 m. / sec, preferably in the range differential pressure of 900kg / cm ² ~3000kg / cm ² during the pressure drop, flow rate 300 meters / sec ～600M / sec, the pressure difference at the pressure drop is 1500kg / cm ² ~3000kg / cm ² More preferably, it is the range. The number of distributed treatments can be selected as necessary. Usually, a treatment number of 1 to 10 is selected, but a treatment number of about 1 to 3 is selected from the viewpoint of productivity. It is not preferable to raise the temperature of such an aqueous dispersion under high pressure from the viewpoint of dispersibility, and the particle size tends to increase at a high temperature exceeding 90 ° C. Therefore, the present invention includes a cooling step in the step before the conversion to the high pressure and the high flow rate, the step after the pressure drop, or both of these steps. It is preferable that the temperature is maintained in the range of from 0C to 90C, more preferably in the range of from 5C to 80C, and particularly preferably in the range of from 5C to 65C. In particular, at the time of high pressure dispersion in a range of 1500kg / cm ² ~3000kg / cm ² it is effective to install the cooling step. As the cooler, a double tube, a tube using a static mixer for the double tube, a multi-tube heat exchanger, a serpentine heat exchanger, or the like can be appropriately selected according to the required heat exchange amount.

  Further, in order to increase the efficiency of heat exchange, a suitable tube thickness, wall thickness, material, etc. may be selected in consideration of the operating pressure. As the refrigerant used for the cooler, from the amount of heat exchange, 20 ° C. well water, 5 ° C. to 10 ° C. chilled water treated with a refrigerator, and -30 ° C. ethylene glycol / water refrigerant as necessary You can also

  In the dispersion operation, it is preferable to disperse the near-infrared absorbing dye in the presence of an aqueous solvent-soluble dispersant (dispersion aid). Examples of the dispersing aid include polyacrylic acid, acrylic acid copolymer, maleic acid copolymer, maleic acid monoester copolymer, acrylomethylpropanesulfonic acid copolymer, and the like, carboxymethyl Semi-synthetic anionic polymers such as starch and carboxymethyl cellulose, anionic polymers such as alginic acid and pectic acid, compounds described in JP-A-7-350753, or known anionic, nonionic, cationic surfactants and other Known polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, or naturally occurring polymer compounds such as gelatin can be appropriately selected and used. Vinyl alcohol, particularly preferred water-soluble cellulose derivatives. The dispersion aid is generally mixed with the near-infrared absorbing dye powder or wet cake near-infrared absorbing dye before dispersion and sent to the disperser as a slurry. It is good also as a near-infrared absorption pigment powder or a wet cake by giving the heat processing and the process by a solvent in the state mixed with the pigment | dye. The pH may be controlled with an appropriate pH adjuster before, during or after dispersion. In addition to mechanical dispersion, it may be coarsely dispersed in a solvent by controlling the pH, and then finely divided by changing the pH in the presence of a dispersion aid. At this time, an organic solvent may be used as a solvent used for the coarse dispersion, and the organic solvent is usually removed after the formation of fine particles.

  The prepared dispersion is stored with stirring for the purpose of suppressing sedimentation of fine particles during storage, or stored in a highly viscous state (for example, in a jelly state using gelatin) by a hydrophilic colloid. You can also. In addition, a preservative can be added for the purpose of preventing the propagation of various bacteria during storage.

  The fine particle dispersion containing a near-infrared absorbing dye used in the present invention comprises at least a near-infrared absorbing dye and water. The ratio of the near-infrared absorbing dye and water is not particularly limited, but the ratio of the near-infrared absorbing dye in the fine particle dispersion is preferably 5% by mass to 50% by mass, particularly A range of 10% by mass to 30% by mass is preferable.

  In the preparation of the above fine particle dispersion, it is preferable to use the above dispersion aid, but it is preferable to use a minimum amount within a range suitable for minimizing the particle size. The range of 5 to 30% by mass, particularly 1 to 15% by mass is preferable.

  In the present invention, it is possible to produce a near-infrared absorbing material by mixing a near-infrared absorbing dye aqueous dispersion and an ultraviolet absorber aqueous dispersion, but the mixing ratio of the near-infrared absorbing dye and the ultraviolet absorber depends on the purpose. The ratio of the ultraviolet absorption to the near-infrared absorbing dye is preferably in the range of 0.01 to 30 mol%, more preferably in the range of 0.1 mol% to 10 mol%, particularly 0.5 mol% to 5 mol%. preferable. Mixing two or more near-infrared absorbing dyes and two or more ultraviolet absorbers when mixing is not limited.

  When providing the near-infrared absorbing layer, it is advantageous to obtain an antistatic effect in the order of adhesive layer / antistatic layer / near infrared absorbing dye-containing layer on the support. An average particle size of vinylidene chloride copolymer or styrene-glycidyl acrylate copolymer coated on corona-discharged support as an adhesive layer in a thickness of 0.1 μm to 1 μm, and then doped with indium or phosphorus as an antistatic layer A gelatin layer, an acrylic or methacrylic polymer layer, or a non-acrylic polymer layer containing 0.01 μm to 1 μm fine particles of tin oxide and vanadium pentoxide can be applied.

  Further, a styrene sulfonic acid / maleic acid copolymer can be provided by forming a film with the aforementioned aziridine or a carbonyl active type crosslinking agent. A pigment layer is provided on these antistatic layers to form a near infrared absorption layer. In the near-infrared absorption layer, colloidal silica or inorganic colloidal silica for the purpose of dimensional stability is coated with colloidal silica coated with non-acrylate polymer such as methacrylate, acrylate polymer, styrene polymer or acrylamide, etc. A filler, an anti-adhesion silica, a methyl methacrylate matting agent, a silicon-based slip agent or a release agent for controlling transportability can be contained.

  The transmittance of 820 nm to 1000 nm of the front plate necessary for absorption of near infrared rays of 820 nm, 850 nm to 900 nm and 950 nm to 1000 nm emitted from the plasma display is preferably 30% or less. However, if the transmittance is too low, the transmittance of the visible light portion also decreases, so that in addition to the near-infrared transmittance, the transmittance at a wavelength of 500 nm to 620 nm, which is the central wavelength of visible light, is 45% or more. It is preferable. More preferably, the transmittance at 500 nm to 620 nm is 50% or more. In particular, in addition to this, the transmittance at 450 nm, which is the blue light emitting region of the light emitter of the plasma display panel, is 45% or more.

  In addition, when the antireflection performance is provided on the transparent film, the reflection of external light is reduced and the transmittance of visible light is improved. Therefore, it is particularly preferable to provide the antireflection performance on the transparent film. Moreover, you may provide these performances to the transparent conductive film to be used, and you may laminate | stack the film which provided these performances on the single side | surface or both surfaces.

(Solvent for coating solution adjustment)
The solvent for the near-infrared absorbing dye according to the present invention is not particularly limited. For example, water, organic solvents (for example, alcohols such as methanol and ethanol, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, amides such as formamide, etc. , Sulfoxides such as dimethyl sulfoxide, esters such as ethyl acetate, ethers, etc.), ionic liquids, and mixed solvents thereof. Oil droplet dispersion can be performed in which a solution dissolved in a solvent is dispersed in water. A dispersion dispersed as fine oil droplets having a diameter of 10 μm or less is called an oil droplet dispersion. The diameter of the fine oil droplets dispersed in water can be measured from an optical microscope or a pattern obtained by diffracting and scattering light emitted from a laser light source by the fine oil droplets. It is also preferable to add a near-infrared absorbing dye that is substantially insoluble in water to the latex liquid as a fine oil droplet dispersion. Any organic solvent may be used for dispersing the near-infrared absorbing dye in the form of oil droplets, and specific examples include benzene, toluene, xylene, benzyl alcohol, phenethyl alcohol, pyridine, and phenoxyethanol chloroform. Preferred are benzyl alcohol, phenethyl alcohol, and phenoxyethanol, and more preferred are benzyl alcohol and phenoxyethanol. In order to disperse a concentrated solution of a near-infrared pigment in water, various dispersers are effectively used. Specifically, a high speed stirrer, an attritor, an ultrasonic disperser, or the like is used. A surfactant can also be used when oil droplets of a concentrated solution of a near-infrared absorbing dye are refined in water. The temperature when the concentrated solution of the near-infrared absorbing dye is dispersed in water is in the range of 0 ° C to 100 ° C, preferably in the range of 20 ° C to -80 ° C, more preferably in the range of 40 ° C to 80 ° C. It is a range. The oil droplet dispersion of the near-infrared-absorbing dye can be mixed with a water-soluble polymer so as to have sedimentation resistance, and can be stored or refrigerated for a long time at a temperature of, for example, 30 ° C. or lower.

<< Filtration of coating liquid >>
Before the coating solution used in the present invention is coated, it is necessary to remove coarse particles present in the coating solution by filtration. “Filtration” described here is filtration by a filtration filter, and the details of the type and structure of the filtration filter are not particularly limited, and any filtration filter can be used as long as it can remove foreign matters that do not pass through a pore size of 2 μm to 10 μm. It may be a thing. The system for removing coarse particles using these filtration filters is not particularly limited, and is not particularly limited as long as no major problem occurs in filtration.

  Examples of materials for these filtration filters include paper, cloth, cellulose acetate polymer, polysulfone, polyethersulfone, polyacrylonitrile, polyether, fluorine (polyvinylidene fluoride) polymer, polyamide, polyimide, polyethylene, polypropylene, stainless steel, ceramic And so on. The form is a flat membrane, a cartridge membrane, a hollow fiber membrane and the like, and is not particularly limited. The filtration filter preferably used in the present invention is a flat membrane made of cloth or filter paper, and more preferably a cartridge type filtration filter or a ceramic filtration filter. In order to filter the coating solution for an image forming layer of the present invention with these membranes (disk type) or cartridge filtration filters, it is particularly preferable to use a housing in which the cartridge filtration filters are mounted.

  These filtration filters include Pole Epochell (various sizes), profile filters (2, 3, 5, 10 μm pore size, etc.) commercially available from Pall, CN03 (3 μm), CN06 (6 μm), etc. commercially available from Millipore. Can also be used. These filtration filters have a flat membrane with a pleated shape and a large area, and are compact and space-saving.

  When using these filtration filters, there is no particular limitation on the method of use, and it is sufficient that the coating liquid is not clogged and coarse particles can be removed. However, in general, the above filtration filter is effective without requiring an installation area by being mounted on a housing. Preferred devices for these housings include commercially available stainless steel and polypropylene. The size and shape of the housing are not particularly limited, and may be a circular shape, a square shape, or a single filter loading type, and two or more filters may be loaded at a time. Furthermore, it is possible to greatly increase the filtration filter area by connecting two or more filters. Furthermore, a flat membrane type can also be used in the present invention. These are used in a very common filtration method. A filtration filter is installed on the receiving part, and the device that becomes the liquid storage part is firmly fixed on it. The filter mounting part is tightened with a fastening member, and the filtrate is supplied. It is intended to prevent it from leaking. At this time, packing is installed in the filter installation part to prevent liquid leakage.

Next, in carrying out the filtration of the coating solution used for forming the near-infrared absorbing material of the present invention, there is no limitation on the pressure for liquid feeding, but generally the filter is passed through a filtration filter under increased pressure or reduced pressure. It is preferred to remove the particles. In particular, pressurization is often carried out by feeding the coating solution with a pump or the like, but it is also preferable to place the coating solution at a higher position than the filtration filter and filter it with natural pressure. Furthermore, it is also preferable to apply a pressure to the coating liquid with a gas, in which case the tank in which the coating liquid is present is actually a closed system. In the case of applying pressure with a pump at the time of liquid delivery, pressurization with its own weight or even pressurization with gas, especially if the filtration filter is damaged or clogged and the performance is not deteriorated. It is not limited. For example, pressure on the filtration filter, preferably ^{490Pa (0.005kg / cm 2) ~4.9MPa} (50kg / cm 2), more ^{preferably, 980Pa (0.01kg / cm 2)} ~0.98MPa ( 10 kg / cm ² ) is preferable, and 9806 Pa (0.1 kg / cm ² ) to 0.49 MPa (5 kg / cm ² ) is particularly preferable.

  Further, when the filtrate receiving part is decompressed and filtered, the degree of vacuum is preferably 100 kPa (750 mmHg) to 1.33 kPa (10 mmHg), more preferably 93 kPa (700 mmHg) to 13.3 kPa (100 mmHg), and particularly 93 kPa. (700 mmHg) to 53.3 kPa (400 mmHg) is preferable.

  In the preferred embodiment of the present invention, it is necessary to filter the coating solution before coating because it can reduce repelling failure and foreign matter failure. The time from filtration to application is not particularly limited. If the filtered coating solution does not form coarse particles, the coating solution may be filtered considerably before use. However, considering the production efficiency, in general, filtration is preferably within 12 months immediately before application, more preferably within 6 months immediately before application, and even more preferably within 1 month immediately before application. Particularly preferably, it is within 15 days from immediately before. Here, the term “immediately before application” includes the case where it exists in the middle of the liquid supply piping from the tank for storing the application liquid to the application Giesser. In this case, so-called online filtration is preferable. It should be noted that there is no problem even if the filtered coating solution is temporarily stored in a stock tank other than the final coating step.

  In the present invention, at least one layer of the coating solution is filtered. For this reason, when there are a plurality of layers, at least one of the coating liquids is filtered. The case where the coating liquid of all layers is filtered is preferable. The reason why the step of filtering the coating solution is an essential requirement in the present invention is that this step has the greatest influence on the quality. However, in addition to the infrared absorbing layer, examples of the layer that affects the coated surface include an adjacent layer, a protective layer, and other functional layers. Therefore, in this invention, it is very preferable that the coating liquid for forming layers other than these near-infrared absorption layers is filtered beforehand before apply | coating. In particular, when an additive material is added to a layer other than the near-infrared absorbing layer, it is preferable to filter in order to prevent image unevenness and pinhole defects.

  Adjacent layers (intermediate layer, protective layer, etc.) and functional layers, which will be described later, are generally composed mainly of latex and contain other water-soluble compounds and dispersion materials. For example, UV absorbers, film quality improvers (such as colloidal silica), surfactants, pH adjusters, and the like are not particularly limited.

  Among them, a slipping agent, a matting agent, a coating surfactant, an antistatic agent, and a film quality improving agent (such as colloidal silica) are added to impart surface characteristics.

  In filtering the coating solution of the functional layer other than these layers, the same filtration filter as described in the filtration of the coating solution of the near infrared absorption layer can be used. In addition to the above, CN25 (25 μm) commercially available from Millipore Corporation can also be used. The filtration pore diameter of the filtration filter at that time is preferably 2 μm to 30 μm, more preferably 2 μm to 10 μm, particularly preferably 2 μm to 5 μm, and in some cases, a filtration filter having a pore diameter of 2 μm to 3 μm is preferably used.

  In particular, the matting agent generally has large matting agent particles added to give a convex portion on the surface. Therefore, the pore size of the filtration filter requires a certain size, for example, preferably 2 μm to 30 μm, more preferably 5 micrometers-25 micrometers are preferable. In addition, when preparing the matting agent coating solution in advance, filter the matting agent solution separately with a filter with a large pore size, and filter the coating solution of other materials with a filtering filter with a small pore size. It is preferable to mix them together. In the present invention, it is essential to filter the coating solution before coating.

<< Near-infrared absorption layer, production method of adjacent layers (intermediate layer, protective layer, etc.) >>
In the present invention, it is preferable to prepare by applying an aqueous coating solution and drying it. However, “aqueous” as used herein means that 60% by mass or more of the solvent (dispersion medium) of the coating solution is water. Components other than water in the coating solution include methyl alcohol, ethyl alcohol, isopropyl alcohol, methyl cellosolve, ethyl cellosolve, dimethylformamide, ethyl acetate, diacetone alcohol, furfuryl alcohol, benzyl alcohol, diethylene glycol monoethyl ether, oxyethyl phenyl ether A water miscible organic solvent such as can be used.

  It is preferable to apply the near-infrared absorbing layer forming coating solution and the adjacent layer (for example, an intermediate layer or a protective layer forming coating solution) onto the support using a slide bead coater. At that time, the coating solution for forming the near-infrared absorbing layer and the coating solution for forming the adjacent layer (intermediate layer, protective layer, etc.) are applied while flowing a solution not containing latex along the coating width regulating plate of the slide bead coater. In addition, at least two types of coating liquid and latex-free liquid are sequentially stacked on the slide surface of the slide bead coater to obtain a steady flow rate, and then latex-free liquid is fed. It is also preferable to apply the coating solution on the support after stopping the process.

  Here, the viscosity of the liquid not containing latex is preferably lower than the viscosity of the coating liquid, and the surface tension of the liquid not containing latex is preferably equal to or lower than the surface tension of the coating liquid on the uppermost layer of the protective layer. .

  In the present invention, the near-infrared absorbing layer forming layer coating solution and the adjacent layer forming coating solution are simultaneously coated on the support, and then, for a period of ½ or less of the time from immediately after the coating to the end of the constant rate drying period. It is preferable to dry the coating film surface at a wind speed of 0.5 m / s to 10 m / s.

  The near-infrared absorbing material of the present invention is preferably dried by applying a drying theory in chemical engineering. It is necessary to appropriately select how to give the humidity when drying. This is because fast drying often deteriorates the performance by generating reticulation or deteriorating storage stability. The near-infrared absorbing material of the present invention is preferably dried at 20% RH or less and 30 ° C. to 90 ° C. within 10 seconds to 2 minutes, and further dried at 35 ° C. to 50 ° C. within 30 seconds to 50 seconds. Is preferred.

  In particular, regarding the setting of temperature and humidity, constant rate drying and reduced rate drying should be preferably controlled. Constant rate drying is a process in which moisture is evaporated from the surface of the film and is called constant rate drying because the surface temperature is constant during this process. In this next process, since moisture evaporates from the inside of the film and dries, the process in which the wet bulb temperature approaches the surface temperature of the film, that is, the dry bulb temperature and finally becomes the same, is referred to as reduced rate drying. The drying of the gelatin film is the difference between constant rate drying and reduced rate drying in that the moisture content is 300 to 400 times the gelatin mass%. Drying conditions with a water content of 300 times or less have an important meaning as drying conditions for the reduced rate drying portion. Since the productivity is improved as the reduced rate drying portion can be dried at a high temperature and low humidity, it is preferable that the performance of the portion does not fluctuate little or does not deteriorate. In the region where the moisture content of the membrane during drying is 70% by mass to 3% by mass on a dry basis, the critical moisture content of the constant rate drying of the material of the present invention is about 300% by mass on the basis of the dry amount. It will be later in the rate of drying. Since the shrinkage of the coating film starts from around 70% by mass, it is desirable to limit the drying conditions thereafter. When the moisture content is between 70% and 3% by weight based on the dry weight, only the surface may be dried depending on the drying conditions, and the coating may be distorted due to rapid and non-uniform film shrinkage, resulting in dry reticulation. Moisture remains inside and causes adhesion. Therefore, during the moisture content of 70 to 3% by mass, the drying conditions are 10 ° C. ≦ dew point ≦ 33 ° C., 35% ≦ related temperature ≦ 85%, and dry bulb temperature is 36 ° C. or less. Is preferred. The selection of conditions within this range is selected depending on the rate at which latex / gelatin or other dry air hits the coating film, etc., but a more preferable range is 25 ° C. ≦ dry bulb temperature ≦ 34 ° C., 55% ≦ related temperature ≦ 75. %, Maximum dew point ≦ 33 ° C., and optimum conditions are 26 ° C. ≦ dry bulb temperature ≦ 30 ° C., 60% ≦ relation temperature ≦ 75%.

  In that sense, if the dew point falls below 10 ° C., the drying efficiency is lowered, which is not practical. Drying is promoted as the relative humidity decreases, and when the relative humidity is 85% or more, not only the drying rate becomes very slow but also there is a risk of causing an adhesion failure. Also, the higher the dry bulb temperature, the faster the drying speed. When the temperature exceeds 36 ° C., the coating film surface becomes over-dried and moisture can be reduced, but it is not preferable for the dimensional stability of the support. It is good to set to. Further, since the drying speed is greatly influenced by the speed at which the drying air velocity hits the object to be dried, the distance between the object to be dried and the drying air outlet is preferably 100 mm or more at a drying air speed of 100 m / second or less. More preferable conditions are a drying wind speed of 50 m / sec or less and a distance of 30 mm or more.

In the coating, drying, cutting, and packaging processes in production, dust and dirt stains impair the quality of the material of the present invention. Therefore, it is preferable that the cleanliness is performed in an environment of US federal standard 209d class 10,000 or less. The US federal standard 209d class here indicates a clean room standard, and the environment of the US federal standard 209d class 10,000 or less means that the cumulative number of particles having a particle size of 0.5 μm or more is 10,000. / Ft ³ or less and the cumulative number of particles having a particle size of 5.0 μm or more is 65 / ft ³ or less. However, it is preferable that the dust particles have a value close to 0 as in outer space. Production in a simple room requires equipment costs, so it is necessary to select the cleanliness as appropriate. In order to prevent dirt and scratches, the near infrared absorbing material of the present invention is not limited to use with a cover film of 20 μm to 60 μm peeled off when used. Since this method results in a release film that must be treated, it is economical to use as little release film as possible.

  After application, the near-infrared absorbing material of the present invention is seasoned for at least one day under the environmental conditions of 10 ° C. to 60 ° C. and 40% RH to 80% RH (relative humidity) in a roll state, and then shipped. At times, it is possible to make it easy to stick on the front panel of PDP (Plasma Display) by wrapping it so that the near-infrared absorbing layer is on the outside, thereby increasing the degree of crosslinking and preventing curling. Can be appropriately selected.

  For example, the conditions of temperature and humidity can be selected as appropriate, such as 3 days at 30 ° C. and 50% RH (relative humidity), 2 days at 35 ° C. and 40% RH (relative humidity).

"binder"
In the production (also referred to as preparation) of the near-infrared absorbing material of the present invention, the binder used for forming the near-infrared absorbing dye absorbing layer or other layers (adjacent layers, etc.) may be an aqueous solvent or an organic solvent solvent. It is preferable to use a binder for water-based coating with as little as possible. Although it is preferable to use latex as such a binder, it is not limited to these. The near-infrared pigment layer dispersed in the latex solution and other functional layers applied together are coated on a support and form a film by heating and drying. The drying temperature is usually between room temperature and about 100 ° C., and drying is performed at a temperature in this range.

(latex)
Latex is a resin that is stably dispersed in an aqueous medium. Latex refers to white milky sap collected from rubber trees, etc., but since the advent of emulsion polymers, including the aqueous dispersions of synthetic polymers, the polymer substance is stable in the aqueous medium. This designation is used because “dispersed” is now called latex. Examples of the water dispersible resin include polyvinylidene chloride, vinylidene chloride-acrylic acid copolymer, vinylidene chloride-itaconic acid copolymer, sodium polyacrylate, polyethylene oxide, acrylic acid amide-acrylic acid ester copolymer, A styrene-maleic anhydride copolymer, an acrylonitrile-butadiene copolymer, a vinyl chloride-vinyl acetate copolymer, or a monomer containing a carboxylic acid group such as acrylic acid, methacrylic acid, itaconic acid and maleic acid, or Examples thereof include styrene-butadiene copolymers and styrene-isoprene copolymers using a small amount of one or more monomers having a sulfonic acid group such as dimethylacrylamidepropanesulfonic acid and styrenesulfonic acid group.

  The latex is widely used as a binder for aqueous coating, and among them, a latex that improves water resistance is preferable as a binder. The amount of latex used for obtaining water resistance as a binder is determined in consideration of applicability, but the amount used is preferably higher from the viewpoint of moisture resistance, and is preferably 30% by mass to 100% by mass with respect to the total mass of the binder. Is preferable, and 60% by mass to 100% by mass is more preferable. Such resins can also be obtained from the market.

  For example, styrene resin is an industry standard product number of styrene-butadiene copolymer, and various brands such as # 1500, # 1502, # 1507, # 1712, # 1778, Sumitomo SBR latex (Sumitomo Chemical Co., Ltd.) and JSR latex ( Nippon Synthetic Rubber Co., Ltd.) or Nipol Latex (Nippon Zeon Co., Ltd.) can be used.

  The styrene-butadiene copolymer has a copolymerization ratio (% by mass) of styrene and butadiene of 10/90 to 90/10, more preferably 20/80 to 60/40. A high styrene latex having a ratio of 60/40 to 90/10 is used by mixing with a resin having a low styrene content (10/90 to 30/70), so that the scratch resistance and physical strength of the photosensitive layer are used. It is preferable for increasing the ratio. The mixing ratio (mass%) is preferably in the range of 20/80 to 80/20.

  As the high styrene latex, commercial products such as JSR0051 and 0061 (Nippon Synthetic Rubber Co., Ltd., trade name) and Nipol 2001, 2057, 2007 (Zeon Corporation, trade name) can be used.

  Examples of the latex having a low styrene content include conventional ones other than those listed as the high styrene latex, such as JSR # 1500, # 1502, # 1507, # 1712, and # 1778.

  Moreover, acrylic latex generally known as an acrylic resin, for example, Nipol AR31, AR32, or Hycar 4021 (both are trade names of Nippon Zeon Co., Ltd.) can be used.

  As the acrylic resin, a polymer or copolymer using the following acrylate monomer as a raw material can be used. In the following, the (meth) acryloyl group is used to mean an acryloyl group or a methacryloyl group.

  (A) Monomers having one (meth) acryloyl group in the molecule include methacrylic acid esters of aliphatic alcohols such as methyl methacrylate, ethyl methacrylate, octyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, etc. Aliphatic alcohol acrylic ester, cyclohexyl acrylate, cyclohexyl methyl acrylate and other alicyclic alcohol acrylic ester, cyclohexyl methacrylate, cyclohexyl methyl methacrylate and other alicyclic alcohol methacrylic ester, phenyl acrylate, 4-promophenyl acrylate , Acrylates containing aromatic groups such as benzyl acrylate and benzyl methacrylate, phenyl methacrylate, - chlorophenyl methacrylate, methacrylic acid ester containing an aromatic group such as benzyl methacrylate, 2-hydroxyethyl acrylate, hydroxyalkyl esters of acrylic acid or methacrylic acid such as 2-hydroxyethyl methacrylate.

  (B) Monomers having two or more (meth) acryloyl groups in the molecule include acrylics such as ethylene glycol diacrylate, propylene glycol diacrylate, diethylene glycol diacrylate, and 1,3-diaacryloxy-2-propanol polyethylene glycol diacrylate. Acrylic acid such as acid diester, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-dimethacryloxy-2-propanol, etc., glycerin triacrylate, trimethylolpropane triacrylate Such as triester, glycerin trimethacrylate, trimethylolpropane trimethacrylate Is methacrylic acid triester or the like.

  As the styrene resin, alkyl styrene monomers such as methyl styrene, ethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene, dimethyl styrene, trimethyl styrene, diethyl styrene, triethyl styrene, fluoro styrene, A halogenated styrene monomer such as chlorostyrene, bromostyrene, iodostyrene, dibromostyrene, a nitrostyrene monomer, an acetylstyrene monomer, a methoxystyrene monomer or the like is used alone or copolymerized with another monomer.

  The vinyl resin contains vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, vinyl acetate, acrylonitrile, vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene bromide or the like as a structural unit as a monomer. Moreover, you may include the monomer which has a 2 or more vinyl group in a molecule | numerator as a structural unit. Examples thereof include conjugated diene monomers such as divinylbenzene, butadiene, and chloroprene, isoprene adipate divinyl, divinyl sulfone, triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, and the like.

  These monomers can be emulsion polymerized as described above. As the water-soluble polymerization initiator used in this emulsion polymerization, any one can be selected, and examples thereof include 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 4,4′-azobis (4-cyano). Valeric acid), 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) Propane] dihydrochloride, 2,2′-azobisisobutyramide dihydrate, and the like. The amount of the water-soluble polymerization initiator used is preferably 0.001 mol% to 0.5 mol% with respect to all monomers.

  Moreover, the dispersant used for the emulsion polymerization is appropriately used to stabilize the system. Examples of the dispersion stabilizer or dispersant include polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, polymethacrylamide, hydroxyalkyl acrylate polymer, hydroxyalkyl methacrylate polymer, polyacrylic acid or salt thereof, polymethacrylic acid or salt thereof, and ethylene-acrylic acid. Copolymer or salt thereof, ethylene-methacrylic acid copolymer or salt thereof, ethylene-maleic acid copolymer or salt thereof, styrene-acrylic acid copolymer or salt thereof, styrene-methacrylic acid copolymer or salt thereof , Polyethyleneimine, polyalkylene glycol, polyalkylene oxide, methylolated polyamide, water-soluble melamine resin, water-soluble phenol resin, water-soluble urea resin, casein, gelatin, carboxymethylcellulose, methylcell , Hydroxyalkyl cellulose, carboxymethyl starch, cationized starch, dextrin, dextran, alginic acid or salt thereof, carrageenan, gellan gum, locust bean gum, gum arabic, tragacanth gum, glucomannan, zalep mannan, guar gum, plant mucus, etc. A single substance or a mixture of two or more kinds is used. The dispersant is preferably used in an amount of 0.01% by mass to 20% by mass with respect to the total amount of monomers used or the total amount of resin to be dispersed.

  Furthermore, the surfactant used for the emulsion polymerization is not particularly limited as long as it does not adversely affect the polymerization reaction, and is an anionic surfactant, a cationic surfactant, an amphoteric surfactant or a nonionic surfactant. Any of the agents can be used. For example, sodium alkylbenzene sulfonate, higher alcohol sulfate sodium salt, higher α-olefin sulfonate sodium salt, higher fatty acid salt, higher alkylphenol alkylene oxide sodium sulfonate, higher alkyl amine salt, higher alkyl trimethyl ammonium salt, higher alkyl pyridinium salt Higher acylaminomethylpyridinium salt, higher acyloxymethylpyridinium salt, N, N-dipolyoxyethylene-N-higher alkylamine salt, higher alkylpolyethylenepolyamine salt, trimethyl higher alkylaniline sulfate, trimethyl higher alkylbenzylammonium salt, Higher alcohol ethylene oxide adduct, higher alkylphenol ethylene oxide adduct, higher fatty acid ethylene oxide addition Higher alkylamine ethylene oxide adducts, higher fatty acid amide ethylene oxide adducts, glycerin higher fatty acid esters, pentaerythritol higher fatty acid esters, higher fatty acid esters of sorbitol and sorbitan (or their ethylene oxide adducts), sucrose higher fatty acid esters, polyols Examples thereof include higher alkyl ethers, higher fatty acid amides of alkanolamines, amino acid type amphoteric activators, betaine type amphoteric activators and the like, or a mixture of two or more thereof. The surfactant is preferably used in an amount of 0.01% by mass to 20% by mass with respect to the total amount of monomers used or the total amount of resin to be dispersed.

  Regarding the latex used in the present invention, “synthetic resin emulsion (Hiraku Okuda, Hiroshi Inagaki, published by Kobunshi Publishing Co., Ltd. (1978))”, “application of synthetic latex (Takaaki Sugimura, Ikuo Kataoka, Junichi Suzuki, Keiji Kasahara, Published by Polymer Press (1993)), “Synthetic Latex Chemistry (written by Soichi Muroi, published by Polymer Press (1970))” and the like. The average particle size of the dispersed particles is preferably in the range of about 1 nm to 500 nm, more preferably about 5 nm to 100 nm. The particle size distribution of the dispersed particles is not particularly limited, and may have a wide particle size distribution or a monodispersed particle size distribution.

  The latex used in the present invention may be a so-called core / shell type latex in addition to a normal uniform latex. In this case, it may be preferable to change the glass transition temperature between the core and the shell.

  The minimum film-forming temperature (MFT) of the latex used in the present invention is preferably −30 ° C. to 90 ° C., more preferably about 0 ° C. to 70 ° C. A film-forming auxiliary may be added to control the minimum film-forming temperature. A film-forming aid, also called a plasticizer, is an organic compound (usually an organic solvent) that lowers the minimum film-forming temperature of the latex. For example, “Synthetic latex chemistry (written by Soichi Muroi, published by Kobunshi Shuppankai (1970)) "It is described in.

  The latex polymer used in the present invention has an equilibrium water content of 3% by mass or less, more preferably 1% by mass or less at 25 ° C. and 55% RH after forming the near infrared absorption layer. Preservability and weather resistance under high humidity can be improved. Although there is no restriction | limiting in particular in the minimum of this equilibrium moisture content, Preferably it is about 0.01 mass, More preferably, it is about 0.03 mass%. For the definition and measurement method of the equilibrium moisture content, for example, “Polymer Engineering Course 14, Polymer Material Testing Method (Edited by Polymer Society, Jinshokan)” can be referred to. Actual measurement can be performed as shown in the Examples described later.

<Ultraviolet absorber>
As the ultraviolet absorber, known ultraviolet absorbers such as salicylic acid compounds, benzophenone compounds, benzotriazole compounds, S-triazine compounds, and cyclic imino ester compounds can be preferably used. Of these, benzophenone compounds, benzotriazole compounds, and cyclic imino ester compounds are preferred. As what is blended with the polyester, a cyclic imino ester compound is particularly preferable.
As a preferable specific example,
(U-1) 2- (2-hydroxy-3,5-di-α-cumyl) -2H-benzotriazole,
(U-2) 5-chloro-2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -2H-benzotriazole,
(U-3) 5-chloro-2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H-benzotriazole (U-4) 5-chloro-2- (2-hydroxy-3) , 5-di-α-cumylphenyl) -2H-benzotriazole,
(U-5) 5-chloro-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole,
(U-6) 2- (3-tert-butyl-2-hydroxy-5- (2-isooctyloxycarbonylethyl) phenyl) -5-chloro-2H-benzotriazole,
(U-7) 5-trifluoromethyl-2- (2-hydroxy-3-α-cumyl-5-tert-octylphenyl) -2H-benzotriazole,
(U-8) 5-trifluoromethyl-2- (2-hydroxy-5-tert-octylphenyl) -2H-benzotriazole,
(U-9) 5-trifluoromethyl-2- (2-hydroxy-3,5-di-tert-octylphenyl) -2H-benzotriazole,
(U-10) 5-Trifluoromethyl-2- (2-hydroxy-3-α-cumyl-5-tert-butylphenyl) -2H-benzotriazole (U-11) 2,4-bis (4-biphenyl) Yl) -6- (2-hydroxy-4-octyloxycarbonylethylideneoxyphenyl) -s-triazine (U-12) 2,4-bis (2,4-dimethylphenyl) -6- [2-hydroxy-4 -(3-nonyloxy * -2-hydroxypropyloxy) -5-α-cumylphenyl] -s-triazine (* represents a mixture of octyloxy group, nonyloxy group and decyloxy group)
(U-13) 2,4,6-Tris (2-hydroxy-4-isooctyloxycarbonylisopropylideneoxyphenyl) -s-triazine (U-14) hydroxyphenyl-2H-benzotriazole (U-15) 2 -(2-hydroxy-5-methylphenyl) -2H-benzotriazole,
(U-16) 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -2H-benzotriazole and the like.

<< Adjacent layer (also called protective layer, intermediate layer, etc.) >>
The upper layer (uppermost layer or protective layer) of the near-infrared absorbing color layer or an intermediate layer between the near-infrared absorbing layer and the upper layer will be described.

(Binder constituting the adjacent layer)
Hereinafter, various binders applicable to the formation of the adjacent layer are shown, but the present invention is not limited thereto. Examples of the polymer for the binder include gelatin, polyvinyl alcohol, casein, agar, gum arabic, hydroxyethyl cellulose, cellulose acetate, cellulose acetate butyrate, polyvinyl chloride, polymethacrylic acid, polyvinylidene chloride, and polyvinyl acetate. can do.

  Of these, gelatin is most preferable as the hydrophilic polymer. Any gelatin such as lime-processed gelatin or acid-processed gelatin may be used. Further, a gelatin derivative may be used. Further, as a binder, in addition to a hydrophilic polymer, a homo or copolymer latex such as styrene, methyl methacrylate, acrylic acid, butyl acrylate, ethyl acrylate, or the like may be added. These latexes include nonionic groups (polyesters of polyethylene glycol and acrylic acid) for improving water resistance, anionic groups (for example, monomers having carboxylic acid groups such as itaconic acid and acrylic acid, sulfonic acid groups (for example, styrene). When a monomer having sulfonic acid or N-dimethylsulfopropaneacrylamide) is copolymerized in the range of 1 mol% to 20 mol%, water dispersibility can be improved.

(Adjacent layer thickness)
The thickness of the adjacent layer according to the present invention is preferably in the range of 0.1 μm to 10 μm, more preferably 0.5 μm to 5 μm per layer. The adjacent layer according to the present invention is preferably formed by applying the aforementioned aqueous coating solution and then drying it.

《Matting agent》
As the matting agent used in the adjacent layer according to the present invention, fine particles such as polystyrene, polymethyl methacrylate, and silica are preferable. The shape of the particles is not particularly limited, but spherical fine particles are preferable. The particle size of the matting agent is preferably 0.2 μm to 20 μm, more preferably 0.5 μm to 10 μm.

The addition amount of the matting agent cannot be generally specified depending on the layer structure, thickness and purpose of use of the material of the present invention, but it is expressed as a coating amount per 1 m ² and is 10 mg / m ^{2 to} 200 mg / m ² , more preferably 20 mg / m. ^{About 2 to} 100 mg / m ² is preferable.

  Examples of the smoothing agent used in the uppermost layer include silicon compounds (for example, dimethylsiloxane polymer), higher fatty acid amides (for example, stearic acid amide, behenic acid amide, arachidic acid amide, etc.), higher fatty acid phthalates (for example, phthalic acid) Dilauryl ester), higher fatty acid and higher alcohol esters, paraffin, and other compounds known in the art may be used. Preferred examples of known slip agents include higher aliphatic amides described in US Pat. No. 4,275,146, higher fatty acids or metal salts thereof described in US Pat. No. 3,933,516, and other higher slip agents. Examples thereof include alcohol and derivatives thereof, polyethylene wax, paraffin wax, microcrystalline wax, polyoxyethylene alkylphenyl ether compound and the like. Further, natural oils and fats, waxes, oils such as beeswax can be used in combination. Furthermore, examples of preferable known slip agents that can be used in combination include silicone compounds that are commercially available or can be obtained by synthesis. Even in the case of silicone compounds, polyorganosiloxanes are preferred. For use in these aqueous solutions, it is preferable to add them in the form of a dispersion.

《Slip agent》
The slip agent used in the present invention is added to the slip agent layer in the form of a dispersion in an aqueous solution. In this case, other organic solvents can be appropriately selected and contained in the aqueous dispersion. Examples of organic solvents that can be used include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), alcohols (lower alcohols having 1 to 8 carbon atoms, such as methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl). Alcohol, hexyl alcohol, octyl alcohol, etc.), glycol derivatives (cellosolve, ethylene glycol diethyl ether, propylene glycol monomethyl ether, etc.), lower fatty acid esters having 1 to 5 carbon atoms (ethyl acetate, butyl acetate, ethyl propionate, etc.) , Haloalkanes (methylene dichloride, ethylene dichloride, trichlene, trichloromethane, trichloroethane, carbon tetrachloride, etc.), hydrocarbons (octane, solventona) Turpentine oil, petroleum ether, thinner, petroleum benzine, benzene, toluene, xylene, etc., phenols (phenol, resorcinol, etc.), ethers (tetrahydrofuran, dioxane, etc.), phosphate esters (trimethyl phosphate, triethyl phosphate, Tributyl phosphate, etc.), amide-based DMF and DMSO. Preferred are alcohols, ketones, glycol derivatives, lower fatty acid esters, haloalkanes, and hydrocarbons. In particular, in a solvent system in which water is mixed and used, it is a solvent selected from alcohols, ketones and glycol derivatives that are water and a uniform solvent. When water is not used, hydrocarbons, ketones , Lower fatty acid esters and haloalkanes are preferred.

In this case, the ratio of water to the organic solvent is 100 to 50: 0 to 50 (volume%), more preferably 100 to 75: 0 to 25 (volume%). With these, the stability of the dispersion of the slip agent in the aqueous coating solution, the coating property, the smoothness of the resulting coating film, the prevention of adhesion of photosensitive material debris, dust, etc., the improvement of repellency during development processing, and excellent scratch resistance It is. In addition, you may use said organic solvent in mixture of 2 or more types with the same or different kind of solvent. The fine dispersion can be obtained by a known dispersion technique, for example, dispersion by mechanical shearing force, ultrasonic dispersion, or precipitation by two-liquid mixing. The amount of the slipping agent, indicates the coating amount per near-infrared-absorbing material ^{1m 2, 0.2mg / m 2 ~500mg} / m 2, more preferably 1mg / m ² ~300mg / m ² is preferred. Only one type of sliding agent may be used, or two or more types may be used in combination.

  Since the slipping agent can suppress the generation of scratches when the film is conveyed on the stainless roller, the dynamic friction coefficient is preferably adjusted to a range of 0.3 to 0.1.

  In terms of the slipperiness of the outermost layer on the formation layer side having the near-infrared absorbing layer, the dynamic friction coefficient is preferably 0.03 to 0.4, and more preferably from the viewpoint of enabling highly accurate conveyance. It is 05 to 0.35, more preferably 0.05 to 0.3, and particularly preferably 0.05 to 0.2. Evaluation of the dynamic friction coefficient is as follows: a stainless hard ball having a diameter of 5 mm with a load of 100 g is moved on a near infrared absorbing material at a speed of 60 mm / second in an environment of 25 ° C. and 60% RH. The dynamic friction with the outermost layer of the near-infrared absorbing material is measured.

  When the adjacent layer of the infrared absorption layer according to the present invention is provided as the outermost protective layer, the latex contained in the outermost protective layer has a glass transition temperature of 20 ° C. or higher and lower than 70 ° C., and contains the latex The amount is 65% by mass to 100% by mass of the total binder amount of the outermost protective layer. By forming the outermost protective layer satisfying such conditions, it is possible to provide an infrared absorbing material with improved water resistance and excellent blocking properties.

  The water resistance of the outermost protective layer can be evaluated by an increase in the thickness of the infrared absorbing material after water is dropped on the surface of the infrared absorbing material and left at 25 ° C. for 1 minute, that is, the amount of swelling. The swelling amount is 2 μm or less. The later swelling amount is more preferably 1.5 μm or less, and further preferably 1 μm or less.

  Examples of the water-soluble polymer used in the outermost protective layer of the near-infrared absorbing material of the present invention include gelatin, polyvinyl alcohol (PVA), polyacrylamide, water-soluble (meth) acrylic polymer, and water-soluble saccharide polymer. Preferably, PVA or a water-soluble saccharide polymer is used. As PVA, normal commercial PVA having a saponification degree of 80 to 99% and a polymerization degree of 200 to 5000, various modified polyvinyl alcohols (alkyl-modified PVA, anion-modified PVA, silane-modified PVA, thiol-modified PVA, hydrophobic group-modified PVA, etc. ) Etc. can be used. As the water-soluble saccharide polymer, water-soluble starch, dextran, pectin, agar, mannan, xanthan, carrageenan, pullulan, alginic acid, water-soluble cellulose derivatives (methylcellulose, hydroxycellulose, carboxymethylcellulose, hydroxypropylcellulose) and the like can be used. .

  Examples of the latex used in combination with the water-soluble polymer in the outermost protective layer of the present invention include, for example, methyl methacrylate / ethyl acrylate / methacrylic acid copolymer latex, methyl methacrylate / 2-ethylhexyl acrylate / styrene / acrylic acid copolymer latex, styrene / Mention latex of butadiene / acrylic acid copolymer, latex of styrene / butadiene / divinylbenzene / methacrylic acid copolymer, latex of methyl methacrylate / vinyl chloride / acrylic acid copolymer, latex of vinylidene chloride / ethyl acrylate / acrylonitrile / methacrylic acid copolymer, etc. Can do.

  The latex used for the outermost protective layer of the near-infrared absorbing material of the present invention preferably has a glass transition temperature (Tg) of 20 ° C. or higher and lower than 70 ° C., more preferably 20 ° C. or higher and lower than 60 ° C. If the Tg of the latex is too low, adhesion failure tends to occur when stored repeatedly, and water resistance tends not to be expressed.

  In the outermost protective layer of the near-infrared absorbing material of the present invention, the latex content is preferably 65% by mass to 100% by mass, more preferably 70-90% by mass of the total binder of the outermost protective layer. . Higher polymer latex content is preferable for water resistance. However, if the content is too high, surface skinning tends to occur during the drying process, causing coating failures such as reticulation, wrinkles, and cracks. It tends to be difficult to adjust the liquid viscosity.

In the outermost protective layer of the near infrared absorbing material of the present invention, the coating amount of the water-soluble polymer and polymer latex, the total of both is the outermost protective layer per 0.3g / m ² ~4.0g / m ² it is preferred, more preferably from ^{0.3g / m 2 ~2.0g / m 2} .

  A protective layer can be made into two or more layers as needed. For example, water resistance and adhesion can be improved by providing two layers of protective layers and providing a layer formed from a coating solution to which latex is added on the side close to the infrared absorption layer. In addition, by reducing the pH of the coating solution on the side closer to the infrared absorption layer and making the pH of the coating solution on the surface side layer higher than 5, it is possible to achieve both infrared absorption performance and manufacturing suitability. By selecting the additive layer involved in infrared absorption properties, film surface pH adjuster, charge control agent, ultraviolet absorber, slip agent, hardener, etc. It can be designed to be compatible with absorption performance.

In the present invention, a matting agent can be added to the outermost protective layer in order to improve blocking resistance and transportability. In addition, it can also add to the layer which functions as an outermost protective layer, or the layer close | similar to an outer surface. The matting agent is described in paragraph numbers 0126 to 0127 of JP-A No. 11-65021. Preferably the amount of the matting agent is 1 m ^{2 per, 1mg / m 2 ~400mg / m} 2, more preferably from ^{5mg / m 2 ~300mg / m 2} . The mat degree of the outermost layer of the near-infrared absorbing layer can be increased as long as the occurrence of haze is not a problem. Usually, the Beck smoothness is preferably 30 seconds to 2000 seconds, more preferably. Is 40 seconds to 1500 seconds. The back surface has a matte degree of preferably Beck smoothness of 10 seconds to 1200 seconds, more preferably 20 seconds to 800 seconds, and further preferably 40 seconds to 500 seconds. In other words, the outermost surface of the near-infrared absorbing material has a Ra in the range of 0.1 μm to 10 μm, preferably in the range of 0.3 μm to 5 μm, and more preferably in the range of 0.3 μm to 5 μm. A range of 5 μm to 3 μm is preferable. Thus, by making Ra within a certain range, it is difficult to attach a fingerprint and the peelability during conveyance can be controlled.

The total binder amount of the near-infrared absorbing layer is preferably in the range of 0.2 to 30 g / m ² , more preferably 1.0 to 15 g / m ² . The total binder amount of the protective layer is preferably in the range of 0.2 to 10.0 g / m ² , more preferably 0.5 to 6.0 g / m ² . The total binder amount of the layer (back layer) on the opposite side of the infrared absorption layer is preferably in the range of 0.01 to 10.0 g / m ² , more preferably 0.05 to 5.0 g / m ² .

  Each of these layers may be provided in two or more layers. When there are two or more infrared absorbing layers, it is preferable to use latex as a binder for all layers. The protective layer is a layer provided on the image forming layer, and there may be two or more layers, but it is preferable to use latex for at least one, particularly the outermost protective layer. Further, the back layer is a layer provided on the undercoat layer on the back surface of the support, and there may be two or more layers, but it is preferable to use latex for at least one layer, particularly the outermost back layer.

  In the present invention, each layer has a first latex into which functional groups described in paragraphs [0023] to [0041] of JP-A No. 2000-19678 are introduced, and a functional group capable of reacting with the first latex. It can also be formed using a crosslinking agent having a group and / or a second latex. Specific examples of the functional group include a carboxyl group, a hydroxyl group, an isocyanate group, an epoxy group, an N-methylol group, an oxazolinyl group, an amino group, and a vinylsulfonyl group, and the crosslinking agent includes an epoxy compound, an isocyanate compound, and a blocked isocyanate compound. , Methylol compounds, hydroxy compounds, carboxyl compounds, amino compounds, ethyleneimine compounds, aldehyde compounds, halogen compounds and the like. Specific examples of the crosslinking agent include isocyanate compounds: hexamethylene isocyanate, Duranate WB40-80D, WX-1741 (Asahi Kasei Kogyo Co., Ltd.), Bihijoule 3100 (Sumitomo Bayer Urethane Co., Ltd.), Takenate WD725 (Takeda Pharmaceutical Co., Ltd.) Aquanate 100, 200 (manufactured by Nippon Polyurethane Co., Ltd.), water-dispersed polyisocyanate and amino compound described in JP-A-9-160172: Sumitex Resin M-3 (Sumitomo Chemical Co., Ltd.) Product), epoxy compound: Denacol EX-614B (manufactured by Nagase Kasei Kogyo Co., Ltd.), halogen compound: 2,4 dichloro-6-hydroxy-1,3,5-triazine sodium and the like.

  As the crosslinking agent for the resin of the present invention, known crosslinking agents such as epoxy compounds, isocyanate compounds and melamine compounds can be used. When the binder is gelatin, aldehyde-based, cyanuric acid-based or vinylsulfone-based crosslinking agents such as glyoxal and glutaraldehyde can be used in combination. The addition amount of the crosslinking agent is usually 0.1 to 20% by mass of the binder, more preferably about 1 to 10% by mass. The use of a crosslinking agent is necessary to increase the strength of the film and interlayer adhesion, and the pencil hardness on the outermost surface is preferably 3H or less, preferably 2H or less. It is preferable to select the amount and method of use of the crosslinking agent.

<Support>
In the present invention, a plastic film, a plastic plate, glass or the like can be used as the support. Examples of raw materials for plastic films and plastic plates include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), vinyl resins such as polyethylene (PE), polypropylene (PP), and polystyrene, and polycarbonate (PC). Triacetyl cellulose (TAC) or the like can be used.

  From the viewpoint of transparency, heat resistance, ease of handling, and price, the plastic film is preferably PET, PEN, or TAC.

  Since the infrared absorbing material for display requires transparency, it is desirable that the support has high transparency. In this case, the total visible light transmittance of the plastic film or plastic plate is preferably 70 to 100%, more preferably 80 to 100%, and still more preferably 90 to 100%. Moreover, in this invention, what colored the said plastic film and the plastic board to the extent which does not interfere with the objective of this invention can also be used as a color tone regulator.

(Thickness of the support)
The thickness of the support of the near-infrared absorbing material of the present invention is preferably 5 μm to 200 μm, and more preferably 30 μm to 150 μm. If it is the range of 5 micrometers-200 micrometers, the transmittance | permeability of a desired visible light is obtained and handling is also easy.

<Functional layer>
In the present invention, a functional layer having functionality may be separately provided as necessary. This functional layer can have various specifications for each application. For example, as an electromagnetic shielding material for display, an antireflection layer provided with an antireflection function with an adjusted refractive index or film thickness, a non-glare layer or an antiglare layer (both having a glare prevention function) in a specific wavelength range Layers that have a color tone adjustment function that absorbs visible light, antifouling layers that have the ability to easily remove dirt such as fingerprints, hard-coat layers that are difficult to scratch, layers that have an impact absorption function, and glass scattering when glass is broken A layer having a prevention function or the like can be provided.

  These functional films may be directly bonded to the PDP, or may be bonded to a transparent substrate such as a glass plate or an acrylic resin plate separately from the plasma display panel main body. These functional films can be called optical filters (or simply filters).

  In order to suppress reflection of external light and suppress a decrease in contrast, an antireflection layer provided with an antireflection function contains inorganic substances such as metal oxides, fluorides, silicides, borides, carbides, nitrides and sulfides. , Vacuum deposition method, sputtering method, ion plating method, ion beam assist method, etc., a method of laminating a single layer or a multilayer, such as a method of laminating a resin having different refractive index such as acrylic resin, fluorine resin, etc. There is. Moreover, the film which gave the antireflection process can also be affixed on this filter. Further, a non-glare-treated or anti-glare-treated film can be pasted on the filter. Further, if necessary, a hard coat layer can be provided.

  A layer having a color tone adjustment function that absorbs visible light in a specific wavelength range is displayed in blue because the PDP has a characteristic that the phosphor that emits blue light emits red light in addition to blue. There is a problem that a portion to be displayed is displayed in a purplish color, and as a countermeasure against this, it is a layer that corrects colored light and contains a dye that absorbs light at around 595 nm.

  Specific examples of the dye that absorbs such a specific wavelength include, for example, azo, condensed azo, phthalocyanine, anthraquinone, indigo, perinone, perylene, dioxazine, quinacridone, methine, Well-known organic pigments such as isoindolinone-based, quinophthalone-based, pyrrole-based, thioindigo-based, metal complex-based, organic pigments, and inorganic pigments can be used. Among these, phthalocyanine-based and anthraquinone-based dyes are particularly preferable because of their good weather resistance.

  As the pressure-sensitive adhesive for sticking the near-infrared absorbing material of the present invention to a PDP, a highly transparent material is preferable. For example, vinyl acetate, epoxy, urethane, ethylene-vinyl acetate, urethane-acrylate, epoxy-acrylate, and the like are preferable. Among these, transparency and colorless epoxy-acrylate and ethylene-vinyl acetate are more preferable. In order to give an antireflection effect to the transparent film in the present invention, silica fine powder, tin oxide, fine powder of titanium oxide are acrylic resin, styrene resin, polyester resin are aromatic hydrocarbons such as toluene, glycol ether, A solution added to a transparent printing ink dissolved in a propylene glycol-based ester organic solvent may be applied to the transparent film. The average particle size of these fine powders is preferably 0.01 to 10 μm, and more preferably, a plurality of types having different particle sizes are mixed. This is to reduce the reflectance of the visual sensation by irregularly reflecting the reflected light by giving the transparent film surface an uneven shape. Next, there is a method of providing a thin layer on a transparent film and utilizing the effects of light reflection and refraction at the interface of the thin layer. That is, when the thickness of the thin layer is λ / 4 (λ: the wavelength of light), the phase of the light of the upper surface reflected light and the lower surface reflected light of the thin layer shifts so as to cancel each other due to interference, and the reflected light. When the refractive index of the thin film is reduced to nf and the refractive index of the transparent film for forming the thin layer is set to nb, nf and nb are raised to the power of 1/2. Apply the principle that the reflection of light is lowest when the values are equal. Therefore, the target of the thickness of the thin layer is ¼ of the wavelength of light that is desired to prevent reflection. That is, the thickness of the thin layer is preferably 0.05 to 0.25 μm. Moreover, when the thin layer 2 is further provided between the transparent film and the thin layer 1, the refractive index of the thin layer 2 is related, and the refractive index of the thin layer 2 is used as nb to prevent reflection by the above calculation method. I can do it. In general, a combination that completely satisfies this condition cannot be obtained, but the refractive index of the thin layer material is required to be as low as possible as that of the transparent film, and the refractive index is 1.28 to 1. It is preferable to use a .45 fluororesin. When the transparent film is polyethylene terephthalate, the refractive index is 1.64, which can be raised as a suitable example. In the case of a cellulose triacetate transparent film, since the refractive index is 1.50, when a fluorine resin is used as a thin layer, a diallyl phthalate resin having a refractive index of 1.59 between the transparent film and the thin layer. It is also possible to provide a layer, a layer of tin oxide having a refractive index of 2.00, or a layer having a refractive index adjusted to 1.59 by mixing tin oxide and an acrylic resin having a refractive index of 1.49. preferable.

In order to give the transparent film antistatic performance, it is preferable to apply or coat a surfactant. A transparent conductive material such as tin oxide, titanium oxide, or ITO may be added to the printing ink and applied to the transparent film, or may be provided as a thin layer by sputtering or the like. If necessary, after providing a layer of transparent conductive agent on the transparent film mentioned above or applying a printing ink of tin oxide, providing a fluororesin, antistatic performance and antireflection performance Both performances can be provided and are more preferred. The surface conductivity is important for imparting antistatic performance, and the surface resistance is preferably 10 ⁶ Ω to 10 ¹² Ω / □.

  Hereinafter, the present invention will be described more specifically with reference to examples. In addition, the material, usage-amount, ratio, processing content, processing procedure, etc. which are shown in the following Examples can be changed suitably unless it deviates from the meaning of this invention. Therefore, the present invention is not limited by the specific examples shown below.

Example 1
<< Preparation of near-infrared absorbing material 106 >>: After subjecting both sides of a transparent biaxially stretched polyethylene terephthalate film having a thickness of 175 μm as a support of the present invention to 100 W / m ² · min corona treatment, the refractive index is 1.55 on both sides. Latex composed of a styrene-butadiene copolymer having an elastic modulus of 100 MPa at 25 ° C. and a glass transition temperature of 37 ° C. (manufactured by Nippon Zeon Co., Ltd., LX407C5) was applied to a thickness of 300 nm to form an undercoat layer. On this undercoat layer, an acrylic latex (HA16, manufactured by Nippon Acrylic Co., Ltd.) having a refractive index of 1.50, an elastic modulus of 120 MPa at 25 ° C., and a glass transition temperature of 50 ° C. is dried to a thickness of 80 nm. This was applied to form a second undercoat layer. The second undercoat layer contains 30 mg / m ² each of tin oxide fine particles (12 nm) doped with 3% indium and zinc oxide fine particles (15 nm) doped with 4% gallium as antistatic agents. Added functionality.

Furthermore, a near-infrared absorbing dye (adjusted so that S-7 and I-6 are each equimolar) (attachment amount: 5 × 10 ⁻⁴ mol / m ² ) and an ultraviolet absorber (on the second undercoat layer) U-1) (attached amount: 5 × 10 ⁻⁴ mol / m ² ), water dispersible resin (VB) 2.7 g / m ² , gelatin 0.9 g / m ² , dihydroxybenzene derivative (H-10) ( 1 × 10 ⁻³ mol / m ² ), pyrazolidone derivative (4)) (5 × 10 ⁻⁴ mol / m ² ), alkali agent (NaOH) (3 × 10 ⁻³ mol / m ² ) First, a coating solution for forming an infrared absorbing layer (details of the dispersion of the near infrared absorbing dye are shown below) and a coating solution for forming a gelatin protective layer described below were prepared.

(Preparation of coating solution for forming near-infrared absorbing layer)
The dispersion of the near-infrared absorbing dye is obtained by dissolving 10 ^-2 mol of dye in 5 ml of chloroform, and adding 0.1 g each of a condensate of lauryl alcohol and a polyethylene glycol having a polymerization degree of 10 and sodium dodecylbenzenesulfonate, In addition to 100 ml of a 4% gelatin aqueous solution in which the resin was dispersed (resin to gelatin ratio 3: 1), the mixture was dispersed with a high-speed stirrer of 30000 rps for 30 minutes while removing the organic solvent with a vacuum pump. The particle diameter was measured using a Coulter Counter Multisizer II type manufactured by Coulter Co., Ltd., and confirmed to be dispersed so that the average particle diameter was 100 nm. The amount of resin and gelatin applied during coating was adjusted while adding resin or gelatin to the coating solution.

  The crosslinking agent added to the coating solution was 0.1 mmol of glyoxal, bis-1,3- (vinylsulfone) -2-hydroxypropane, epichlorohydrin and bisphenol A condensate, diethylaminoethyltriethoxy, respectively, per gram of gelatin. Silane and 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium were added.

(Preparation of coating solution for forming gelatin protective layer)
The protective layer of the near-infrared absorbing layer was prepared by adding 1 L of a 10% aqueous solution of alkali-treated gelatin and 6- (2-benzotriazolyl) -4-t-octyl-6′-t-butyl-4 ′ as an ultraviolet absorber. -3 g of methyl-2,2'-methylenebisphenol, 2 mmol of 1,3-bis (vinylsulfonamido) -2-hydroxypropane as a cross-linking agent per 1 g of gelatin, a matting agent (average particle size of 3 μm), and gelatin It was prepared so that the attached amount of was 0.7 g / m ² .

Further, the coating solution for the gelatin protective layer is such that diperfluorohexyl sulfosuccinate as a fluorine surfactant is added to the coating solution so that the surface tension becomes 0.036 N / m ² (36 ± ² dyn / cm). Prepared.

(Application)
The coating is performed by using a slide coater, and the near-infrared absorbing layer forming coating solution and the gelatin protective layer forming coating solution are applied simultaneously at a coating speed of 200 m / min. did. The wind speed on the coating film surface was set to 2 m / s over a period of ½ or less of the time from immediately after coating to the end of the constant rate drying period.

  In application, the coating solution was filtered by three-stage filtration in which 3 μm, 10 μm, and 30 μm filtration filters manufactured by Millipore were connected in series. The sample was applied, dried, cut, and packaged in an environment where the cleanliness was US Federal Standard 209d class 10,000 or less.

  An antireflection film and a hard coat film were applied to the opposite side of the near infrared absorption layer with respect to the support. Details of the application of these functional films will be described below, but the antireflection film and the hard coat film did not impair the performance of near-infrared absorption on the opposite side.

(Hard coat film formation)
UV curable acrylic resin (Aronix UV-3700: Toagosei Co., Ltd.) 25.0 parts by mass, tin oxide doped with indium (particle diameter: 0.2 to 2.0 μm) 8.0 parts by mass, methyl ethyl ketone 24 A hard coat layer coating comprising 0.0 part by mass and 33.0 parts by mass of toluene was applied with a Mayer bar, and irradiated with ultraviolet rays for 1 second to 2 seconds with a high pressure mercury lamp to obtain a hard coat film.

(Formation of antireflection film)
On the hard coat layer, the coating liquid for the low refractive index layer described below was further applied so that the film thickness after drying was 100 μm, and heat treatment was performed at 120 ° C. for 1 hour. An antireflection film was obtained (refractive index of the low refractive index layer = 1.42). The resulting antireflection film had a total light transmittance of 94.0%, a haze value of 0.5, and a minimum reflectance of 0.5 in the visible light wavelength region, and was excellent in antireflection properties.

<< Preparation of coating solution for forming low refractive index layer >>
Tetraethoxysilane hydrolyzate A (preparation method is shown below) 103 parts by mass γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM503) 1 part by mass linear dimethyl silicone-EO block copolymer (manufactured by Nihon Unicar) FZ-2207) 0.1 part by mass Hollow silica-based fine particles (P-4 manufactured by Catalyst Chemical Industry Co., Ltd.) 50 parts by mass Propylene glycol monomethyl ether 270 parts by mass Isopropyl alcohol 270 parts by mass <Preparation of tetraethoxysilane hydrolyzate A >
The mixture was prepared by mixing 25 g of tetraethoxysilane and 222 g of ethanol, adding 54 g of a 1.5% aqueous solution of citric acid monohydrate, and then stirring at room temperature for 3 hours.

<< Preparation of near-infrared absorbing materials 100-105, 107-122 >>
In the production of the near-infrared absorbing material 106, a near-infrared absorbing dye, a dihydroxybenzene derivative (described as DHB in Table 1) or a pyrazolidone derivative (described as PZN in Table 1), an alkali agent, an ultraviolet absorber, and a resin dispersion Except having changed the kind as described in Table 1, it carried out similarly and produced near-infrared absorption materials 100-105 and 107-122, respectively.

  The resin dispersion was prepared as follows.

<< Preparation of resin dispersion >>
(Preparation of acrylic resin aqueous dispersion (symbol AL))
To a 0.5 L three-necked flask, add 300 g of deionized water, 25 g of methyl methacrylate (MMA), 25 g of styrene, 45 g of ethyl acrylate (EA), 5 g of hydroxyethyl methacrylate (HEMA), 250 mg of ammonium persulfate, and bubbling with nitrogen. The mixture was stirred at 100 ° C. for 3 hours and returned to room temperature to prepare an acrylic resin aqueous dispersion (AL).

(Preparation of styrene-butadiene resin aqueous dispersion (symbol SB))
Polymerization was conducted in the same manner as the above acrylic resin aqueous dispersion. Specifically, 300 g of deionized water, 48 g of butadiene, 40 g of styrene, 12 g of itaconic acid, 2 g of acrylic acid, 1 g of anionic emulsifier and 6 g of potassium persulfate are added to a 0.5 L three-necked flask and stirred at 25 ° C. for 30 minutes. The mixture was then heated to 60 ° C. and 2 g of sodium bisulfite was added and polymerized for 3 hours.

(Preparation of styrene-isoprene resin aqueous dispersion (symbol SI))
Polymerization was conducted in the same manner as the above acrylic resin aqueous dispersion. Specifically, 300 g of deionized water, 40 g of isoprene, 48 g of styrene, 12 g of itaconic acid, 2 g of acrylic acid, 1 g of an anionic emulsifier, and 6 g of potassium persulfate are added to a 1 L three-necked flask and stirred at 25 ° C. for 30 minutes. The mixture was then heated to 60 ° C. and 2 g of sodium bisulfite was added and polymerized for 3 hours.

(Preparation of polyvinyl butyral resin aqueous dispersion (symbol VB))
A 1 L stainless steel flask was charged with 80 g of polyvinyl alcohol particles having a polymerization degree of 1500 and a saponification degree of 99.5 mol% and 300 g of pure water, and the dispersion was heated to 95 ° C. and dissolved and then cooled to 75 ° C. 3 g of 10% by mass hydrochloric acid and 20 g of butyraldehyde were added to the aqueous solution to proceed the reaction. During the reaction, reflux was performed to prevent volatilization and outflow of aldehyde out of the system. 90 g of 10% strength hydrochloric acid was added as an additional catalyst and the temperature was kept at 82 ° C. for 4 hours. After completion of the reaction, the liquid was cooled to 40 ° C., neutralized with sodium bicarbonate at room temperature, and the resulting resin was washed with water and dried. 100 g of this resin was dispersed in 300 g of a 15% aqueous solution of isopropanol.

(Preparation of aqueous dispersion of vinyl acetate resin (symbol VA))
A 1L stainless steel flask was charged with 300 g of water, 100 g of vinyl acetate, and 1 g of an anionic emulsifier, and this dispersion was heated to 85. After 30 minutes, 3 g of potassium persulfate was added, and emulsion polymerization was performed at 85 ° C. for 3 hours. It was.

  Urethane resin aqueous dispersion (symbol UN): 1 L reaction vessel was charged with 70 g of polytetramethylene ether glycol having a number average molecular weight of 2000, cooled to 85 ° C. at 100 ° C. for 1 hour under a nitrogen stream, and then isophorone diisocyanate 32 g. Was reacted at 85 ° C. for 3 hours to obtain 102 g of a urethane polymer. An isopropyl alcohol solution of urethane polymer was used. Subsequently, 300 g of water was added with stirring at 40 ° C., and after dispersion, an aqueous dispersion of polyurethane resin was obtained.

<< Evaluation of deterioration over time >>
Each of the obtained near-infrared absorbing materials 100 to 122 is allowed to stand for 200 hours under conditions of a temperature of 70 ° C. and 90% RH (relative humidity), and has an average transmittance absorption of a visible portion of 400 nm to 750 nm, 800 nm to 1000 nm. The average absorption ratio% in the near infrared part was displayed. Table 1 shows the contents of the fabricated samples and the evaluated performance results. The light resistance deterioration test was obtained by using a Super Xenon Weather Meter SX75 manufactured by Suga Test Instruments Co., Ltd., and evaluating the rate of absorption deterioration after a 110-hour test at 55% RH (relative humidity), irradiation intensity 50 W / m ² . The results are shown in Table 2.

  From Table 2, compared with the comparison, the sample of the present invention maintains a high transmittance for visible light of 450 nm to 750 nm before and after irradiation with ultraviolet light, and has a high absorptivity for near infrared light of 800 nm to 1000 nm. It can be seen that

  From this, it is clear that the sample of the present invention is a near-infrared-absorbing material in which the near-infrared absorptivity does not decrease and the light resistance does not deteriorate even under high temperature and high humidity conditions.

Claims (7)

The support has at least one near-infrared absorbing layer, and the near-infrared absorbing layer contains a compound having a maximum wavelength in the range of 750 nm to 1100 nm, and the near-infrared absorbing layer or the near-infrared absorbing layer A near-infrared absorbing material, wherein a layer adjacent to the layer contains a dihydroxybenzene derivative or a pyrazolidone derivative. The near-infrared absorbing material according to claim 1, wherein the dihydroxybenzene derivative is a 1,4-dihydroxybenzene derivative. The near-infrared absorbing material according to claim 1, wherein the pyrazolidone derivative is a 1-phenyl-3-pyrrolidone derivative. The near-infrared absorbing material according to any one of claims 1 to 3, wherein the near-infrared absorbing layer or the adjacent layer contains an alkali agent. The near-infrared absorbing material according to claim 4, wherein the alkali agent is a metal salt selected from a metal group selected from alkali metals and alkaline earth metals. 6. The near-infrared absorption according to claim 1, wherein the compound is at least one selected from the group consisting of a phthalocyanine derivative, a nickel dithiol complex compound, a diimonium derivative, and a squalium derivative. material. The structure layer has at least one layer selected from a functional layer group consisting of an antireflection layer, a high hardness layer, an adhesive layer, and an electromagnetic wave absorption layer. The near-infrared absorbing material described.