JP2008260899A - Resin composition and laminate containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition excellent in light resistance, heat fastness and warmth fastness and a laminate containing the same. <P>SOLUTION: The resin composition comprises a binder resin and a compound represented by formula (I). The laminate comprises this resin composition. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a resin composition and a laminate including the same.

  A plasma display panel (PDP) displays an image by applying a high voltage to a gas such as xenon and emitting plasma, but near infrared rays are emitted when the excited gas molecules such as xenon become more stable. The For this reason, near infrared rays are generated from the PDP. Near-infrared rays cause harmful effects such as malfunctioning of the remote control device, and therefore it is necessary to take near-infrared shielding measures such as absorbing and removing near-infrared rays. Therefore, a near-infrared absorption filter, for example, a near-infrared absorption film is attached to the front surface of a display using a PDP, that is, a so-called plasma television.

  A near-infrared absorption filter using a dye that absorbs near-infrared rays is known. For example, a filter for an electronic display for PDP or the like, which is obtained by applying a near-infrared absorption layer containing an organic dye such as diimonium salts or a phthalocyanine complex on the front surface of the display is disclosed (for example, Patent Document 1 and 2). However, providing a near-infrared absorption filter by coating has a problem that it is not efficient in terms of productivity.

In recent years, there has been a strong demand for improving the productivity of PDPs. Therefore, in order to solve such problems, there is a demand for further increasing the adhesive layer and the near-infrared absorbing layer by kneading a near-infrared absorbing dye into an adhesive. (See, for example, Patent Document 3).
JP 2001-174627 A JP 2002-249721 A JP 2006-257223 A

  However, conventional dyes such as those mentioned above have problems such as not satisfying the required filter service life due to insufficient dye fastness even when kneaded into an adhesive, and there is a need for more robust dyes. It was.

  In view of the above circumstances, an object of the present invention is to provide a resin composition excellent in light resistance, heat fastness and thermal fastness, and a laminate including the same.

That is, the present invention has the following configuration.
<1> A resin composition comprising a binder resin and at least one selected from the group of compounds represented by the following general formula (I).

In the general formula (I), R ¹¹¹ , R ¹¹² , R ¹²¹ , R ¹²² , R ¹³¹ and R ¹³² each independently represent a hydrogen atom, an aliphatic group or an aromatic group, and R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹³³ , R ¹³⁴ , R ¹³⁵ and R ¹³⁶ each independently represents a hydrogen atom or a substituent, and R ¹¹³ , R ¹¹⁴ , R ¹¹⁴ And R ¹¹¹ , R ¹¹¹ and R ¹¹² , R ¹¹² and R ¹¹⁵ , R ¹¹⁵ and R ¹¹⁶ , R ¹¹⁶ and R ¹²³ , R ¹²³ and R ¹²⁴ , R ¹²⁴ and R ¹²¹ , R ¹²¹ and R ¹²² , R ¹²² and R ¹²⁵ , R ¹²⁵ and R ¹²⁶ , R ¹²⁶ and R ¹³³ , R ¹³³ and R ¹³⁴ , R ¹³⁴ and R ¹³¹ , R ¹³¹ and R ¹³² , R ¹³² and R ^{1 35} , R ¹³⁵ and R ^136, and R ¹³⁶ and R ¹¹³ may be connected to each other to form a ring. X represents a monovalent or divalent anion, n represents 1 or 2, and the product of the valence of X and n is 2. However, R ¹³¹ and R ¹³² are not simultaneously a phenyl group having a group represented by —NR ¹⁴¹ R ¹⁴² at the 4-position. Here, R ¹⁴¹ and R ¹⁴² each independently represent a hydrogen atom, an aliphatic group, or an aromatic group.
<2> The resin composition according to <1>, wherein the transmittance of light having a wavelength of 850 to 1000 nm is 30% or less.
<3> The resin composition according to <1> or <2>, wherein the binder resin has a glass transition temperature of 50 ° C. or lower.
<4> The resin composition according to any one of <1> to <3>, wherein the binder resin has a glass transition temperature of 0 ° C. or lower.
<5> The mass ratio of the compound represented by the general formula (I) to the binder resin is 0.1 to 10%, according to any one of the above <1> to <4>, It is a resin composition.
<6> Any one of the above <1> to <5>, wherein in the general formula (I), at least one of R ¹¹¹ , R ¹¹² , R ¹²¹ , R ¹²² , R ¹³¹ and R ¹³² is different. It is a resin composition as described in one.
<7> In the general formula (I), at least one of R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹³³ , R ¹³⁴ , R ¹³⁵ and R ^136. It is a resin composition as described in any one of said <1>-<6> characterized by the difference in one.
<8> In the general formula (I), X represents a perchlorate ion, a hexafluoroantimonate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, or the following general formulas (II), (III), ( The resin composition according to any one of <1> to <7>, wherein the resin composition is at least one selected from ions represented by any one of IV).

In the general formulas (II) to (IV), R ²¹¹ , R ²¹² , R ³¹¹ , R ³¹² , R ⁴¹¹ , R ⁴¹² and R ⁴¹³ each independently represents an aliphatic group, an aromatic group or a heterocyclic group.
<9> In the general formulas (II) to (IV), R ²¹¹ , R ²¹² , R ³¹¹ , R ³¹² , R ⁴¹¹ , R ⁴¹² and R ⁴¹³ are each independently an aliphatic group having a halogen atom, halogen The resin composition according to <8>, which is an aromatic group having an atom or a heterocyclic group having a halogen atom.
<10> In the general formulas (II to (IV), R ²¹¹ , R ²¹² , R ³¹¹ , R ³¹² , R ⁴¹¹ , R ⁴¹² and R ⁴¹³ are an aliphatic group having a fluorine atom, an aromatic group having a fluorine atom. Or it is a resin composition as described in said <9> which is a heterocyclic group which has a fluorine atom.
<11> A laminate including the resin composition according to any one of <1> to <10>.
<12> The laminate according to <11>, having a structure obtained by sequentially laminating a first ultraviolet absorbing layer, a resin composition layer containing the resin composition, and a second ultraviolet absorbing layer. Is the body.
<13> The resin composition according to any one of <1> to <10>, wherein the resin composition is used for a display face plate mounted on a plasma display.
<14> The laminate according to <11> or <12>, wherein the laminate is used for a display face plate mounted on a plasma display.

  According to the present invention, it is possible to provide a resin composition excellent in light resistance, heat fastness and thermal fastness, and a laminate including the same.

  Hereinafter, the present invention will be described in more detail. In the present specification, “to” is used to mean a lower limit value and an upper limit value of numerical values described before and after.

<Resin composition>
-Compound represented by general formula (I)-
The resin composition of the present invention comprises a binder resin and at least one selected from the group of compounds represented by the following general formula (I).

In the general formula (I), R ¹¹¹ , R ¹¹² , R ¹²¹ , R ¹²² , R ¹³¹ and R ¹³² each independently represent a hydrogen atom, an aliphatic group or an aromatic group, and R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹³³ , R ¹³⁴ , R ¹³⁵ and R ¹³⁶ each independently represents a hydrogen atom or a substituent, and R ¹¹³ , R ¹¹⁴ , R ¹¹⁴ And R ¹¹¹ , R ¹¹¹ and R ¹¹² , R ¹¹² and R ¹¹⁵ , R ¹¹⁵ and R ¹¹⁶ , R ¹¹⁶ and R ¹²³ , R ¹²³ and R ¹²⁴ , R ¹²⁴ and R ¹²¹ , R ¹²¹ and R ¹²² , R ¹²² and R ¹²⁵ , R ¹²⁵ and R ¹²⁶ , R ¹²⁶ and R ¹³³ , R ¹³³ and R ¹³⁴ , R ¹³⁴ and R ¹³¹ , R ¹³¹ and R ¹³² , R ¹³² and R ^{1 35} , R ¹³⁵ and R ^136, and R ¹³⁶ and R ¹¹³ may be connected to each other to form a ring. X represents a monovalent or divalent anion, n represents 1 or 2, and the product of the valence of X and n is 2. However, R ¹³¹ and R ¹³² are not simultaneously a phenyl group having a group represented by —NR ¹⁴¹ R ¹⁴² at the 4-position. Here, R ¹⁴¹ and R ¹⁴² each independently represent a hydrogen atom, an aliphatic group, or an aromatic group.

  The compound represented by the general formula (I) is a near-infrared absorbing dye, and includes the compound represented by the general formula (I) in the resin composition of the present invention to absorb and block near-infrared rays. It can be used as a blocking material. For example, when used for a display surface plate of a plasma display panel (PDP), near infrared rays emitted from the PDP can be blocked. In addition, since the compound is excellent in light fastness, heat fastness and wet heat fastness, even when the PDP is exposed to ultraviolet rays / visible light as external light and placed in a high temperature environment (for example, 80 ° C.). Can be used.

  In order to block near-infrared rays to a level where there is no practical problem, the transmittance of the resin composition of the present invention with respect to light in the wavelength region of 850 to 1000 nm is 30% or less, preferably 20% or less, more preferably 10 % Or less is preferable.

In the general formula (I), the “aliphatic group” represented by R ¹¹¹ , R ¹¹² , R ¹²¹ , R ¹²² , R ¹³¹ or R ¹³² is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, An alkynyl group, a substituted alkynyl group, an aralkyl group or a substituted aralkyl group is meant.
The alkyl group may have a branch or may form a ring. The alkyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 18 carbon atoms. For example, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl, bicyclo [1.2 .2] heptan-2-yl, bicyclo [2.2.2] octane-3-yl, and the like.
The alkyl part of the substituted alkyl group has the same meaning as the alkyl group, and the preferred range is also the same.
The alkenyl group may have a branch or may form a ring. The alkenyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 18 carbon atoms. For example, vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, bicyclo [2.2.1] hept-2-en-1-yl, bicyclo [2. 2.2] Oct-2-en-4-yl and the like.
The alkenyl part of the substituted alkenyl group has the same meaning as the alkenyl group, and the preferred range is also the same.
The alkynyl group may have a branch or may form a ring. The alkynyl group preferably has 2 to 20 carbon atoms, and more preferably 2 to 18 carbon atoms. For example, ethynyl, propargyl, trimethylsilylethynyl and the like can be mentioned.
The alkynyl part of the substituted alkynyl group has the same meaning as the alkynyl group, and the preferred range is also the same.
The alkyl part of the aralkyl group and the substituted aralkyl group has the same meaning as the alkyl group. Examples of the aralkyl group include a benzyl group and a phenylethyl group. The aryl part of the aralkyl group and the substituted aralkyl group has the same meaning as the following aryl group.

  Examples of the substituent of the alkyl part of the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group and the substituted aralkyl group include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [Represents a linear, branched, or cyclic substituted or unsubstituted alkyl group. The “alkyl group” includes an alkyl group (preferably an alkyl group having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl. 2-ethylhexyl), a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably A substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms (a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms), for example, bicyclo [1.2.2] heptane-2 -Yl, bicyclo [2.2.2] octane-3-yl), and tricyclo structures with more ring structures Also includes an alkyl group. In addition, an alkyl group (for example, an alkyl group of an alkylthio group) as a substituent to be described later has the same meaning and a preferable range is also the same. ],

Alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. The “alkenyl group” includes an alkenyl group (preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably having 3 carbon atoms). -30 substituted or unsubstituted cycloalkenyl groups (monovalent groups in which one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms has been removed), for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl ), A bicycloalkenyl group (substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms (monovalent with one hydrogen atom of a bicycloalkene having one double bond removed) Group), for example, bicyclo [2.2.1] hept-2-en-1-yl, bicyclo [2.2.2] Transfected-2-en-4-yl) are intended to encompass. ],

An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms such as ethynyl, propargyl, trimethylsilylethynyl), an aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as Phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably a 5- or 6-membered, substituted or unsubstituted, aromatic or non-aromatic heterocyclic compound A monovalent group in which one hydrogen atom is removed from, a 5- to 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl, 2-thienyl, 2 -Pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro group, carboxy group, alkoxy group (preferably A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as methoxy, ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), an aryloxy group (preferably having 6 to 6 carbon atoms) 30 substituted or unsubstituted aryloxy groups such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy groups (preferably having 3 carbon atoms) To 20 silyloxy groups such as trimethylsilyloxy and t-butyldimethylsilyloxy), heterocyclic oxy groups (preferably substituted or unsubstituted heterocyclic oxy groups having 2 to 30 carbon atoms such as 1-phenyltetrazole- 5-oxy, 2-tetrahydropyranyloxy), reed An oxy group (preferably a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy , Benzoyloxy, p-methoxyphenylcarbonyloxy),

A carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di- n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t -Butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy, -Methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), amino group (preferably amino group, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms, or An unsubstituted anilino group such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), an acylamino group (preferably a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, C6-C30 substituted or unsubstituted arylcarbonylamino group such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), amino Carbonylamino group Preferably, it is a substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group ( Preferably, a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms (for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino),

An aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino), Sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino ), An alkylsulfonylamino group and an arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, such as methyl Nylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio group (preferably substituted or unsubstituted alkylthio having 1 to 30 carbon atoms) Group, such as methylthio, ethylthio, n-hexadecylthio), arylthio group (preferably substituted or unsubstituted arylthio having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), heterocyclic thio A group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably having a carbon number of 0 to 30 replacements or no placement Sulfamoyl groups such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl, N- ( N′-phenylcarbamoyl) sulfamoyl), sulfo group,

Alkylsulfinyl group and arylsulfinyl group (preferably substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenyl Sulfinyl, p-methylphenylsulfinyl), an alkylsulfonyl group and an arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, for example, Methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), an acyl group (preferably a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted aryl group having 7 to 30 carbon atoms). Bonyl group, heterocyclic carbonyl group bonded to a carbonyl group with a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxy Phenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m -Nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycar Cycloalkenyl, n- octadecyloxycarbonyl),

A carbamoyl group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methyl Sulfonyl) carbamoyl), arylazo groups and heterocyclic azo groups (preferably substituted or unsubstituted arylazo groups having 6 to 30 carbon atoms, substituted or unsubstituted heterocyclic azo groups having 3 to 30 carbon atoms, such as phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide group (preferably N-succinimide, N-phthalimide), phosphino group (preferably substituted with 2 to 30 carbon atoms) Or an unsubstituted phosphino group such as dimethylphosphino, diphenylphospho Fino, methylphenoxyphosphino), phosphinyl group (preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyloxy group (Preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino group (preferably having 2 carbon atoms) -30 substituted or unsubstituted phosphinylamino groups such as dimethoxyphosphinylamino and dimethylaminophosphinylamino, silyl groups (preferably substituted or unsubstituted silyl groups having 3 to 30 carbon atoms, For example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethyl Representing the Rushiriru).

  Among the above substituents, those having a hydrogen atom may be those further substituted with the above substituents. Examples of such a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. Examples thereof include methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, and benzoylaminosulfonyl groups.

  The substituent of the aryl part of the substituted aralkyl group in the aliphatic group is the same as the substituent of the substituted aryl group described later, and the preferred range is also the same.

In the general formula (I), the “aromatic group” represented by R ¹¹¹ , R ¹¹² , R ¹²¹ , R ¹²² , R ¹³¹ or R ¹³² means an aryl group or a substituted aryl group. The aromatic group may be condensed with an aliphatic ring, another aromatic ring or a heterocyclic ring. 6-40 are preferable, as for the carbon atom number of an aryl group, 6-30 are more preferable, and 6-20 are more preferable. Among them, the aryl group is preferably phenyl or naphthyl, and particularly preferably phenyl.

  The aryl part of the substituted aryl group has the same meaning as the aryl group, and the preferred range is also the same. The substituent of the substituted aryl group is synonymous with the substituent described as the substituent of the alkyl part of the above substituted alkyl group, substituted alkenyl group, substituted alkynyl group and substituted aralkyl group, and the preferred range is also the same.

In the general formula (I), a “substituent” represented by R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹³³ , R ¹³⁴ , R ^135, or R ¹³⁶ "Is synonymous with the substituent described as the substituent of the alkyl moiety of the above substituted alkyl group, substituted alkenyl group, substituted alkynyl group and substituted aralkyl group, and the preferred range is also the same.

In the general formula (I), R ¹¹¹ , R ¹¹² , R ¹²¹ , R ¹²² , R ¹³¹ or R ¹³² is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, substituted or unsubstituted, from the viewpoint of productivity. A substituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, more preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted group having 2 to 20 carbon atoms. Or an unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, and a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, more preferably a substituted or unsubstituted group having 1 to 10 carbon atoms. An alkyl group, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms and a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, More preferred is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 8 carbon atoms.
Among these, from the viewpoint of productivity, a substituted or unsubstituted alkyl group having 2 to 6 carbon atoms is most preferable.
In terms of productivity, at least one of R ¹¹¹ , R ¹¹² , R ¹²¹ , R ¹²² , R ¹³¹ and R ¹³² is preferably represented by a different functional group. That is, it is preferable in terms of hue that one of the three phenyl groups bonded to the central nitrogen atom of the structure represented by the general formula (I) is different or all are different, and bonded to the central nitrogen atom. More preferably, one of the three phenyl groups is different.

In the general formula (I), R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹³³ , R ¹³⁴ , R ¹³⁵ or R ¹³⁶ are in terms of productivity. , Preferably hydrogen atom, halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, cyano group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyl Oxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, A Lillethio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, imide group, phosphino group, phosphinyl group, phosphinyloxy group Phosphinylamino group, silyl group, more preferably hydrogen atom, halogen atom, alkyl group, alkenyl group, aryl group, cyano group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, amino group Group, alkylthio group, arylthio group, imide group, silyl group, more preferably hydrogen atom, halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, silyloxy group, amino group, most preferred. Is a hydrogen atom, an alkyl group.
Further, it is preferable that at least one of R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹³³ , R ¹³⁴ , R ¹³⁵ and R ¹³⁶ is a different functional group. . That is, it is preferable in terms of hue that one of the three phenyl groups bonded to the central nitrogen atom of the structure represented by the general formula (I) is different or all different, and bonded to the central nitrogen atom. More preferably, one of the three phenyl groups is different.

In the general formula (I), R ¹³¹ and R ¹³² are not simultaneously a phenyl group having a group represented by —NR ¹⁴¹ R ¹⁴² at the 4-position. Here, R ¹⁴¹ and R ¹⁴² each independently represent a hydrogen atom, an aliphatic group, or an aromatic group. The aliphatic group and aromatic group represented by R ¹⁴¹ and R ¹⁴² have the same meaning as the aliphatic group and aromatic group described in the description of R ¹¹¹ , R ¹¹² , R ¹²¹ , R ¹²² , R ^131, or R ^132. The preferred ranges thereof are also the same.

Furthermore, in said general formula (I), ^R113 and ^R114 , ^R114 and ^R111 , ^R111 and ^R112 , ^R112 and ^R115 , ^R115 and ^R116 , ^R116 and ^R123 , ^R123 and R ¹²⁴ , ^R124 and ^R121 , ^R121 and ^R122 , ^R122 and ^R125 , ^R125 and ^R126 , ^R126 and ^R133 , ^R133 and ^R134 , ^R134 and ^R131 , ^R131 and ^R132 , R ¹³² and R ¹³⁵ , R ¹³⁵ and R ¹³⁶ , and R ¹³⁶ and R ¹¹³ may be connected to each other to form a ring.

In the general formula (I), X represents a monovalent or divalent anion, and n represents 1 or 2. The product of the valence of X and n has a relationship of 2.
X is a monovalent anion such as perchlorate ion (ClO ₄ ⁻ ), hexafluoroantimonate ion (SbF ₆ ⁻ ), hexafluorophosphate ion (PF ₆ ⁻ ), tetrafluoroborate ion ( BF ₄ ⁻ ) and ions represented by any one of the following general formulas (II) to (IV), and divalent anions, sulfate ions (SO ₄ ²⁻ ) are included.
Among them, in terms of productivity, perchlorate ion, hexafluoroantimonate ion, hexafluorophosphate ion, tetrafluoroborate ion, and ions represented by any of the following general formulas (II) to (IV) It is preferable that it is 1 type selected from.

In the general formulas (II) to (IV), R ²¹¹ , R ²¹² , R ³¹¹ , R ³¹² , R ⁴¹¹ , R ⁴¹² and R ⁴¹³ each independently represents an aliphatic group, an aromatic group or a heterocyclic group. To express. Here, the aliphatic group and the aromatic group represented by R ²¹¹ , R ²¹² , R ³¹¹ , R ³¹² , R ⁴¹¹ , R ⁴¹² , or R ⁴¹³ are R ¹¹¹ , R ¹¹² , R ¹²¹ , R ¹²² , R ¹³¹ or respectively the same meaning as aliphatic and aromatic groups as described in the description of R ^132, preferred ranges are also the same. In addition, the heterocyclic group represented by R ²¹¹ , R ²¹² , R ³¹¹ , R ³¹² , R ⁴¹¹ , R ⁴¹² , or R ⁴¹³ includes the substituted alkyl group, the substituted alkenyl group, the substituted alkynyl group, and the substituted aralkyl. It is synonymous with the heterocyclic group described by description of the substituent of the alkyl part of group, and its preferable range is also the same.

In the general formulas (II) to (IV), R ²¹¹ , R ²¹² , R ³¹¹ , R ³¹² , R ⁴¹¹ , R ⁴¹² and R ⁴¹³ are each independently an aliphatic group, an aromatic group or a halogen atom. It is preferably a heterocyclic group, more preferably an aliphatic group having a fluorine atom, an aromatic group or a heterocyclic group.

In the general formulas (II) to (IV), R ²¹¹ , R ²¹² , R ³¹¹ , R ³¹² , R ⁴¹¹ , R ⁴¹² , and R ⁴¹³ are preferably each independently an alkyl group having a halogen atom, halogen An alkenyl group having an atom, an alkynyl group having a halogen atom, an aryl group having a halogen atom, or a heterocyclic group having a halogen atom, more preferably each independently an alkyl having 1 to 20 carbon atoms. Group, an alkenyl group having a halogen atom having 2 to 20 carbon atoms, an alkynyl group having a halogen atom having 2 to 20 carbon atoms, or an aryl group having a halogen atom having 6 to 20 carbon atoms, and more preferably each independently. And an alkyl group having a halogen atom having 1 to 10 carbon atoms and an alkene having a halogen atom having 2 to 10 carbon atoms. Or an aryl group having a halogen atom having 6 to 10 carbon atoms, particularly preferably each independently an alkyl group having 1 to 8 carbon atoms or a halogen atom having 6 to 8 carbon atoms. And most preferably each independently an alkyl group having a halogen atom having 1 to 4 carbon atoms.
Among these, a perfluoroalkyl group represented by C _n F _{2n + 1} (n = 1 to 4) is preferable.

X is preferably hexafluoroantimonate ion, hexafluorophosphate ion, or R ²¹¹ , R ²¹² , R ³¹¹ , R ³¹² , R ⁴¹¹ , R ⁴¹² and general formulas (II) to (IV) R ⁴¹³ each independently represents an alkyl group having a halogen atom represented by 2 to 6 carbon atoms, an alkenyl group having a halogen atom, an alkynyl group having a halogen atom, an aryl group having a halogen atom, or a complex having a halogen atom. is an anion represented by any one of formulas (II) when a Hajime Tamaki ~ (IV), more preferably, in a hexafluoroantimonate ion or the general formula (II) ~ (IV), R 211 , Pa ^{R 212, R 311, R 312} , R 411, R 412 and ^{R 413} are to be _{independently} represented by C _{n F 2n + 1} An anion represented by any one of the general formulas (II) to (IV) in the case of a fluoroalkyl group, more preferably a hexafluoroantimonate ion or a general formula (II) to (IV) An anion represented by any one of the general formulas (II) to (IV) in the case where R ²¹¹ , R ²¹² , R ³¹¹ , R ³¹² , R ⁴¹¹ , R ⁴¹² and R ⁴¹³ are CF ₃ , particularly preferred Is a hexafluoroantimonate ion or an anion represented by the general formula (II) when R ²¹¹ and R ²¹² are CF ₃ in the general formula (II). Of the above, hexafluoroantimonate ions are most preferable.

From the viewpoint of heat resistance and solubility, the compound represented by the general formula (I) in the present invention is such that R ¹¹¹ , R ¹¹² , R ¹²¹ , R ¹²² , R ¹³¹ and R ¹³² are a hydrogen atom, an alkyl group, or an aryl. R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹³³ , R ¹³⁴ , R ¹³⁵ and R ¹³⁶ are hydrogen atoms, alkyl groups or alkoxy groups R ²¹¹ , R ²¹² , R ³¹¹ , R ³¹² , R ⁴¹¹ , R ⁴¹² and R ⁴¹³ are preferably alkyl groups or aryl groups, and R ¹¹¹ , R ¹¹² , R ¹²¹ , R ¹²² , R ¹³¹ and R ¹³² is an alkyl group having 2 to 6 carbon ^{atoms, R 113, R 114, R} 115, R 116, R 123, R 124 ^{R 125, R 126, R 133} , R 134, R 135 and ^{R 136} is a hydrogen ^{atom, R 211, R 212, R} 311, R 312, R 411, R 412 and ^{R 413} are carbon atoms 1 to 6 The perfluoroalkyl group is more preferable.

In the present invention, all of R ¹¹¹ , R ¹¹² , R ¹²¹ , R ¹²² , R ¹³¹ and R ¹³² are branched alkyl groups having 2 to 6 carbon atoms, and R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹³³ , R ¹³⁴ , R ^135, and R ¹³⁶ are hydrogen atoms, and R ²¹¹ , R ²¹² , R ³¹¹ , R ³¹² , R ⁴¹¹ , R ^412, and R ⁴¹³ Is preferably a C 1-6 perfluoroalkyl group.
In addition, at least one of R ¹¹¹ , R ¹¹² , R ¹²¹ , R ¹²² , R ^131, and R ¹³² is an alkyl group having a cyano group having 2 to 6 carbon atoms, and R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹³³ , R ¹³⁴ , R ¹³⁵ and R ¹³⁶ are hydrogen atoms, and R ²¹¹ , R ²¹² , R ³¹¹ , R ³¹² , R ⁴¹¹ , R ⁴¹² and R It is also preferable that ⁴¹³ is a C1-C6 perfluoroalkyl group, and it is more preferable that a halogen atom is a fluorine atom.

  The compound represented by the general formula (I) can take a tautomer depending on the structure and the environment in which the compound is placed. One typical form is described in this specification, but tautomers having structures different from those described herein are also included in the compounds used in the present invention.

  Specific examples (I-1) to (I-62) of the compound represented by the general formula (I) of the present invention are shown below, but the present invention is not limited thereto.

  Compounds represented by the above general formula (I) (including the case where X in the general formula (I) is represented by the general formulas (II) to (IV). Hereinafter, they may be collectively referred to as “compound (I)”. Can be synthesized by a conventional method, for example, by the method described in Der Deutschen Chemischen Gesellshaft, Vol. 92, pages 245-251 (1959), or JP-A-2006-143673. is there.

Here, as an example, a synthesis example of the specific example (I-11) is shown.
5 g of tris (4-di (n-butyl) aminophenyl) amine was completely dissolved in 40 ml of DMF, and the mixture was heated and stirred at 60 ° C. Thereto was added 15 g of bis (trifluoromethanesulfonyl) imide silver salt, and the mixture was heated and stirred at 60 ° C. for 3 hours. After the reaction solution was filtered to remove insoluble components, 200 ml of water was added to the reaction solution, and the precipitated crystals were filtered. The obtained crystals were washed with water and dried to obtain 8.6 g (91%) of the target compound 5.
When the mass spectrum was measured, it was M ⁺ = 627. When the absorption spectrum was measured, the maximum absorption wavelength was λmax = 916 nm (dichloromethane).

  In the resin composition of the present invention, the near infrared absorbing dye may be used alone as the compound (I), or a plurality of compounds (I) may be used in combination. Furthermore, other near infrared ray absorbing dyes other than the compound (I) can be used in combination with the compound (I).

One or more near infrared absorbing dyes that can be used in combination with compound (I) may be used at the same time, for example, cyanine compounds, merocyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, squarylium compounds, croconium Compounds, oxonol compounds, triarylmethane compounds, naphthoquinone compounds, anthraquinone compounds, thiol nickel complex compounds, oxonol compounds, or R ¹³¹ and R ¹³² in the general formula (I) are simultaneously placed in the 4-position -NR ¹⁴¹ R ¹⁴² (R ¹⁴¹ R ¹⁴² represents a hydrogen atom, an aliphatic group or an aromatic group), and a compound represented by a phenyl group having a group represented by ¹⁴¹ R ¹⁴² .
Among them, a phthalocyanine compound, a naphthalocyanine compound, or R ¹³¹ and R ¹³² in the general formula (I) are simultaneously —NR ¹⁴¹ R ¹⁴² (where R ¹⁴¹ R ¹⁴² is a hydrogen atom, an aliphatic group or an aromatic group). The compound represented by the phenyl group which has the group represented by this is preferable, More preferably, they are a phthalocyanine type compound and a naphthalocyanine type compound.

  As the near-infrared absorbing dye used in the resin composition of the present invention, it is most preferable to use one compound (I).

  In the resin composition of the present invention, the mass ratio of the compound (I) to a binder resin (including a binder resin copolymerized with a monomer having a crosslinkable functional group) described later is 0.1 to 10%. Is preferred.

-Binder resin-
The resin composition of the present invention contains at least one binder resin.
There is no restriction | limiting in particular in the kind of said binder resin, For example, polystyrene compounds, such as polyolefin, such as polyethylene and a polypropylene, polystyrene, poly ((alpha) -methylstyrene); Styrene-butadiene copolymer, styrene-isoprene copolymer, styrene -Styrene copolymers such as maleic acid copolymer and styrene-maleic acid ester copolymer; polyvinyl compounds such as polyvinyl chloride, polyvinyl alcohol and polyvinyl acetate; poly (meth) acrylate methyl, poly (meta ) Poly (meth) acrylates such as ethyl acrylate, poly (meth) acrylate, butyl poly (meth) acrylate; polyethers such as polyoxymethylene and polyethylene oxide; polyethylene succinate, polybutylene adipate, poly Lactic acid Polyesters such as glycolic acid, polycaprolactone and polyethylene terephthalate; natural polymers such as cellulose, starch and rubber; polyamides such as 6-nylon and 6,6-nylon; polyurethane, epoxy resin, polyacrylic acid resin, rosin and modified rosin Terpene resins, phenol resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, halogen-modified products thereof, and the like. These can be used alone or in combination of two or more. . Particularly preferred are acrylic and polyester binders.

  The binder resin used in the present invention preferably has a glass transition temperature of 50 ° C, preferably 0 ° C or less. Examples of binder resins having such a glass transition temperature include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, (meth ) Hexyl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, myristyl (meth) acrylate, ( Examples thereof include palmityl acrylate and stearyl (meth) acrylate. These may be used alone or in combination of two or more.

-Monomer-
The resin composition of the present invention can further contain a monomer. The monomer is preferably a monomer having a crosslinkable functional group capable of forming a copolymer with the binder resin (crosslinkable functional group-containing monomer). Examples of monomers having a crosslinkable functional group include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth) acrylic acid 2 -(Meth) acrylic acid hydroxyalkyl esters such as hydroxybutyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, Acrylamides such as N-methylolacrylamide and N-methylolmethacrylamide; monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, monoethylamino (meth) acrylate (Meth) acrylic acid monoalkyl aminoalkyl such as propyl and the like. These monomers may be used independently and may be used in combination of 2 or more type.

  Further, if desired, monomers other than those described above can be further used, for example, vinyl esters such as vinyl acetate and vinyl propionate; olefins such as ethylene, propylene and isobutylene; halogens such as vinyl chloride and vinylidene chloride. Olefins; styrene monomers such as styrene and α-methylstyrene; diene monomers such as butadiene, isoprene and chloroprene; nitrile monomers such as acrylonitrile and methacrylonitrile; N, N-dimethylacrylamide N, N-dialkyl-substituted acrylamides such as N, N-dimethylmethacrylamide and the like. These may be used alone or in combination of two or more.

The content of the structural unit derived from the crosslinkable functional group-containing monomer in the copolymer varies depending on the type, but is usually about 0.1 to 20% by mass, preferably 1 to 10% by mass. is there.
The copolymer is not particularly limited as to the form of copolymerization, and may be any of random, block, and graft copolymers.
The molecular weight is preferably within the range of 300,000 to 2.5 million in terms of weight average molecular weight. If this weight average molecular weight is 300,000 or more, when forming a laminate to be described later, it is excellent in adhesion and adhesion durability with the adherend, and within 2.5 million, the resin composition of the present invention, Good suitability for application to a support described later. In view of adhesion, adhesion durability, coating suitability, etc., the weight average molecular weight is preferably 300,000 to 2,000,000, particularly 500,000 to 1,800,000.
In addition, the said weight average molecular weight is the value of polystyrene conversion measured by the gel permeation chromatography (GPC) method.
In this invention, the said copolymer may be used individually by 1 type, and may be used in combination of 2 or more type. If desired, the high molecular weight copolymer can be used in combination with a homopolymer or copolymer having a low molecular weight, for example, a weight average molecular weight of 100,000 or less.

-Crosslinking agent-
A crosslinking agent can be used in the resin composition of the present invention. There is no restriction | limiting in particular as this crosslinking agent, Arbitrary things can be suitably selected and used from what was conventionally used as a crosslinking agent in an acrylic adhesive. Examples of such cross-linking agents include polyisocyanate compounds, epoxy resins, melamine resins, urea resins, dialdehydes, methylol polymers, and the like. In the present invention, polyisocyanate compounds are preferably used.
Examples of the polyisocyanate compound include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated diphenylmethane diisocyanate. Polyisocyanates, etc., and biurets, isocyanurates, and adducts that are a reaction product with low molecular active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, castor oil, etc. Can be mentioned.
In this invention, this crosslinking agent may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, although the usage-amount is based also on the kind of crosslinking agent, it is 0.001-50 mass parts normally with respect to 100 mass parts of resin compositions of this invention, Preferably, 0.01-10 mass parts is preferable. Selected by range.

-Various additives-
In the resin composition of the present invention, various known additives such as a plasticizer, a silane coupling agent, an antioxidant, an ultraviolet absorber, and the like may be used, as long as the object of the present invention is not impaired. It is possible to add a dye or a pigment for correcting the color tone of the display device.
Of these various additives, when a silane coupling agent is added to the resin composition, the adhesiveness to the glass plate under wet heat conditions is improved, and floating and peeling are less likely to occur. The silane coupling agent is an organosilicon compound having at least one alkoxysilyl group in the molecule, having good compatibility with the binder resin component, and having light transparency, for example, substantially transparent Is preferred. Examples of such a silane coupling agent include vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and the like, and the addition amount is based on 100 parts by mass of the solid content of the resin composition. The range of 0.001 to 10 parts by mass is preferable, and the range of 0.005 to 5 parts by mass is particularly preferable.

  From the viewpoint of improving the productivity of an electronic display device such as a plasma display panel (PDP), in the resin composition of the present invention, the near-infrared absorbing dye is preferably contained in a state kneaded in the resin composition.

<Laminated body>
The laminate of the present invention contains the resin composition of the present invention. That is, the resin composition of the present invention contains the binder resin and the compound (I) as described above.
The laminate of the present invention preferably has a structure in which a first ultraviolet absorbing layer, a resin composition layer containing the resin composition, and a second ultraviolet absorbing layer are sequentially laminated.
The resin composition layer is preferably applied as an adhesive layer for adhering each layer of a laminate constituting a display face plate of an electronic display device such as a plasma display panel (PDP). In this case, the resin composition layer may be applied as one of the pressure-sensitive adhesive layers, or may be applied as two or more pressure-sensitive adhesive layers.

  A front panel for a conventional PDP panel is obtained by kneading a near-infrared absorbing dye into a resin composition, and applying a resin composition layer using the resin composition as the adhesive layer. The near-infrared absorbing film or the near-infrared absorbing layer, which is one of the layer configurations, can be eliminated, and the layer configuration can be simplified.

  When a resin composition layer is formed as an adhesive layer on an adherend using a resin composition in which a near-infrared absorbing dye is kneaded, the thickness is usually 5 to 200 μm, preferably 10 to 150 μm. It is. Moreover, a peeling film can be provided on a resin composition layer as needed. Examples of the release film include paper such as glassine paper, coated paper, and laminated paper, and various plastic films coated with a release agent such as silicone resin. Although there is no restriction | limiting in particular about the thickness of this peeling film, Usually, it is about 20-150 micrometers.

  The resin composition layer in the laminate of the present invention is made of a polyethylene terephthalate (PET) solution containing a near-infrared absorbing dye, a solvent, a binder resin, and the like in addition to kneading the near-infrared absorbing dye into the resin composition. It can also be produced by coating on a transparent film such as The layer thickness of the resin composition layer is preferably 0.1 μm or more at the time of drying in order to effectively obtain the near infrared shielding effect, the solvent at the time of film formation hardly remains, and the operability of film formation is easy. From this point, it is more preferably 20 μm or less. Especially preferably, it is 0.3-10 micrometers.

The concentration and coating amount of the near infrared absorbing dye used in the laminate of the present invention are the absorption wavelength and absorption coefficient of the dye, the transmission characteristics and transmittance required for the laminate, and the medium in which the near infrared absorbing dye is dispersed or Although it is determined by the kind and thickness of the coating film and is not particularly limited, the total application amount of the near infrared absorbing dye is 0.01 g / m ^{2 because it} is necessary to obtain near infrared absorbing ability while maintaining transparency. ˜2 g / m ² is preferable, and 0.05 to 1 g / m ² is more preferable.
Further, the mass ratio of the binder resin and the near-infrared absorbing dye is preferably 0.01 to 15%, more preferably 0.1 to 10%, still more preferably 0.5 to 3%, still more preferably 1 to 2. .5%.

For example, when the temperature of the environment in which the PDP is used is high, the temperature of the laminate used for the front plate of the PDP also rises. Therefore, the near-infrared absorbing dye used in the laminate of the present invention is, for example, at 80 ° C. It is preferable to have heat resistance that does not significantly deteriorate due to decomposition or the like. For the same reason, it is preferable that the near-infrared absorbing dye used in the laminate of the present invention has moisture and heat resistance that does not significantly deteriorate even under high temperature and high humidity. In addition, when light resistance may be required and deterioration of display light emission or external light due to ultraviolet rays or visible rays becomes a problem, the laminate of the present invention does not transmit a member containing an ultraviolet absorber or ultraviolet rays. By using a member or containing an ultraviolet absorber together with a near-infrared absorbing dye, the deterioration of the near-infrared absorbing dye used in the laminate of the present invention by ultraviolet rays is reduced, and there is no significant deterioration due to ultraviolet rays or visible light. It is important to use near infrared absorbing dyes.
The same applies to humidity and a combined environment in addition to heat and light. When the near-infrared absorbing dye used in the laminate of the present invention is deteriorated, the transmission characteristics of the laminate of the present invention are changed, and there is a possibility that the color tone changes or the near-infrared cutting ability is lowered. Furthermore, in order to disperse in a medium or a coating film, solubility and dispersibility in an appropriate solvent are also important.

  Further, in the present invention, two or more kinds of near infrared absorbing dyes having different absorption wavelengths may be contained in one medium or coating film, or two or more media and coating films containing near infrared absorbing dyes are provided. May be.

-UV absorbing layer-
The laminate of the present invention is preferably imparted with an ultraviolet-cutting property for the purpose of preventing deterioration of the near-infrared absorbing dye. As the ultraviolet ray cutting ability necessary for protecting the dye, the transmittance in the ultraviolet region shorter than the wavelength of 380 nm is 20% or less, preferably 10% or less, more preferably 5% or less. The ultraviolet cut property can be obtained by forming a layer (ultraviolet absorption layer) containing an ultraviolet absorber or an inorganic compound that reflects or absorbs ultraviolet rays on a transparent substrate. The ultraviolet absorbing layer may be the same layer as the near infrared absorbing agent or may be a different layer, but is preferably a different layer. From the viewpoint of preventing deterioration of the near-infrared absorbing dye, it is more preferable to have a structure in which an ultraviolet absorbing layer, a layer containing a near infrared absorbing agent, and an ultraviolet absorbing layer are sequentially laminated.

  It is also preferable to contain an ultraviolet absorber or an inorganic compound that reflects or absorbs ultraviolet rays in the aqueous dispersion of the polymer.

  Conventionally known UV absorbers such as benzotriazoles and benzophenones can be used, and their types and concentrations are dispersibility / solubility in the medium to be dispersed or dissolved, absorption wavelength / absorption coefficient, thickness of the medium. It is determined from the above and is not particularly limited.

  In addition, it is preferable that the functional film which has ultraviolet cut-off property has little absorption of visible light region, and does not show visible light transmittance | permeability remarkably or exhibit colors, such as yellow. Examples of such a film include “Teijin (registered trademark) Tetron (registered trademark) film PET HB” manufactured by Teijin DuPont Films, Inc.

  As ultraviolet absorbers that can be preferably used in the laminate of the present invention, JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-97075, and JP-A-9-34057 are disclosed. Benzotriazole compounds described in JP-A No. 46-2784, JP-A No. 5-194443, U.S. Pat. No. 3,214,463, etc., JP-B No. 48-30492, Cinnamic acid compounds described in JP-A Nos. 56-21141, 10-88106, etc., JP-A-4-298503, 8-53427, 8-239368, 10-182621. No. 8, JP-A-8-501291, etc., triazine compounds, Research Disclosure No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based compounds and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used.

-Other additives-
In the present invention, it is preferable to use an antioxidant in order to improve the stability of the dye. As the antioxidant, various organic and metal complex anti-fading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, No. VII, I to J, ibid. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544 at page 527, ibid. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of the representative compounds described in pages 127 to 137 of JP-A-62-215272 can be used.

-Support-
In the laminate of the present invention, various known transparent plastic films can be used as a support, but polyethylene terephthalate (PET) is preferably used from the viewpoints of transparency, cost, and handleability. It is done.
The thickness of the film is preferably 50 μm or more and 200 μm or less.
The surface of the tack film to which the coating solution is applied may be subjected to surface treatment such as ultraviolet irradiation treatment, corona discharge treatment, glow discharge treatment, saponification or the like in advance.

  As a method for applying the resin composition layer to the transparent support (film), for example, a dip coating method, a roller coating method, a spray coating method, a gravure coating method, a die coating method, a bar coating method and the like can be selected. These coating methods can perform continuous processing, and are more productive than batch-type vapor deposition methods. Also, a spin coating method that can form a thin and uniform coating film can be employed.

  The coating solution for the resin composition layer in the laminate of the present invention must be a solvent that dissolves the near-infrared absorbing dye and the binder resin. For example, an aromatic solvent such as toluene or xylene; iso-propyl alcohol Alcohol solvents such as n-butyl alcohol, propylene glycol methyl ether and dipropylene glycol methyl ether; ester solvents such as butyl acetate, ethyl acetate and cellosolve acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone One or more of dimethylformamide and the like may be mentioned.

  In this invention, you may provide another functionality to a resin composition layer as needed. Alternatively, a functional layer having functionality may be provided separately from the resin composition layer. This functional layer can have various specifications for each application. For example, an antireflection layer with an antireflection function that adjusts the refractive index and film thickness, a non-glare layer or an antiglare layer (both have a glare prevention function), and a color tone adjustment function that absorbs visible light in a specific wavelength range Provide an anti-fouling layer that has a function that easily removes dirt such as fingerprints, an antistatic layer, a hard-coat layer that is not easily damaged, a glass scattering prevention function when a glass is broken, and a layer that has a gas barrier layer. Can do.

  The features of the present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not construed as being limited by the specific examples shown below.

Example 1
[Production of near-infrared absorbing laminate (near-infrared absorbing film)]
Acrylic ester copolymer (binder resin) was produced by polymerizing butyl acrylate, ethyl acrylate, and 2-hydroxyethyl acrylate at a mass ratio of 77: 15: 8 by a conventional method (weight). Average molecular weight: 800,000).
Next, 4 parts by mass (solid content) of an isocyanate-based crosslinking agent [trade name “Coronate L” manufactured by Nippon Polyurethane Co., Ltd.] was added to 100 parts by mass (solid content) of the acrylate copolymer. Furthermore, the near-infrared absorbing dye of sample number 101 in Table 1 below was added so that the mass ratio was 1.5% with respect to the solid content of the entire resin composition, and this was diluted with methyl ethyl ketone. Prepared. This resin composition was placed on a 150 μm thick polyethylene terephthalate (PET) film [manufactured by Teijin DuPont Films, Teijin (registered trademark) Tetron (registered trademark) film PET HB] (first ultraviolet absorbing layer). The resin composition layer was formed by coating and drying so that the film thickness after drying was 20 μm.

  Further, on the surface of the resin composition layer opposite to the surface on which the PET film is provided, a PET film having a thickness of 100 μm [manufactured by Teijin DuPont Films, Teijin (registered trademark) Tetron (registered trademark) film] PET HB] (second ultraviolet absorption layer) was placed and pressure-bonded to produce a near infrared absorbing laminate (near infrared absorbing film) of sample number 101.

Further, in the production process of the laminate of sample number 101, the laminate of sample number 101 was replaced by replacing the near-infrared absorbing dye of sample number 101 with the near-infrared absorbing dyes of sample numbers 102 to 122 in Table 1 below. In the same manner, laminates (near infrared absorbing films) of sample numbers 102 to 121 were produced.
The near-infrared absorbing dyes I-1 and the like in sample numbers 101 to 121 in Table 1 below correspond to the specific examples (I-1) to (I-62) of the compound (I), and sample numbers 122 and 123. Comparative compound-1 and Comparative compound-2 in are each a compound represented by the following structural formula.

(Example 2)
[Preparation of near-infrared absorbing film]
A resin composition obtained by adding 100 ml of methyl ethyl ketone to 10 g of methyl methacrylate polymer and 0.12 g of near-infrared absorbing dye shown in Sample No. 201 of Table 2 below, stirring and dissolving at 40 ° C. for 15 minutes, The thickness of the resin composition layer after drying on a 100 μm PET film (Teijin DuPont Films Co., Ltd., Teijin (registered trademark) Tetron (registered trademark) film PET HB) (first ultraviolet absorbing layer) is 20 μm. Was applied and dried. To this resin composition layer, an adhesive resin (adhesive; manufactured by Toagosei Co., Ltd., S-1601) was applied and dried to a thickness of 25 μm.
Further, a PET film having a thickness of 100 μm [manufactured by Teijin DuPont Films, Teijin (registered trademark) Tetron (registered trademark) film PET is provided on the surface of the pressure-sensitive adhesive layer opposite to the surface on which the PET film is provided. HB] (second ultraviolet absorbing layer) was pressure-bonded to prepare a near infrared absorbing laminate (near infrared absorbing film) of sample number 201.

In the production process of the laminate of sample number 201, the near-infrared absorbing dye of sample number 201 was replaced with the near-infrared absorbing dyes shown in sample numbers 202 to 223 of Table 2 below. Similarly, laminates (near infrared absorption films) of sample numbers 202 to 223 were produced.
The near-infrared absorbing dyes I-1 and the like in sample numbers 201 to 221 in Table 2 below correspond to the specific examples (I-1) to (I-62) of the compound (I), and sample numbers 222 and 223. Comparative compound-1 and Comparative compound-2 in are the same as the comparative compounds in Table 1.

[Evaluation]
-Light resistance-
The laminates obtained in Example 1 and Example 2 were irradiated with 950,000 lux for 3 days with a xenon lamp, and the residual ratio was measured by measuring the concentration of the spectral absorption maximum wavelength of compound (I) with respect to that before irradiation. The light resistance was determined.

-Heat fastness-
Under the condition of 80 ° C., the laminate of Example 1 is allowed to stand for 200 hours, the laminate of Example 2 is allowed to stand for 500 hours, and the concentration of the spectral absorption maximum wavelength of Compound (I) before being left is measured. The residual ratio was obtained from the above, and the heat fastness was obtained.

-Moist heat fastness-
Under the conditions of 60 ° C. and 90% relative humidity (RH), the laminate of Example 1 is allowed to stand for 200 hours, the laminate of Example 2 is allowed to stand for 500 hours, and the spectral absorption of Compound (I) before standing The residual ratio was determined by measuring the concentration at the maximum wavelength, and was defined as fastness to wet heat.

  The evaluation results of the light resistance, heat fastness and wet heat fastness are shown in Table 1 for Example 1 and in Table 2 for Example 2, respectively.

  As shown in Tables 1 and 2, the compounds represented by the general formula (I) of the present invention had good light resistance, heat fastness, and wet heat fastness.

Claims (14)

The resin composition containing binder resin and at least 1 sort (s) selected from the compound group represented by the following general formula (I).

[In General Formula (I), R ¹¹¹ , R ¹¹² , R ¹²¹ , R ¹²² , R ¹³¹ and R ¹³² each independently represents a hydrogen atom, an aliphatic group or an aromatic group, and R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹³³ , R ¹³⁴ , R ¹³⁵ and R ¹³⁶ each independently represent a hydrogen atom or a substituent, and R ¹¹³ , R ¹¹⁴ , R ¹¹⁴ and R ¹¹¹ , R ¹¹¹ and R ¹¹² , R ¹¹² and R ¹¹⁵ , R ¹¹⁵ and R ¹¹⁶ , R ¹¹⁶ and R ¹²³ , R ¹²³ and R ¹²⁴ , R ¹²⁴ and R ¹²¹ , R ¹²¹ and R ¹²² , R ¹²² and R ¹²⁵ , R ¹²⁵ and R ¹²⁶ , R ¹²⁶ and R ¹³³ , R ¹³³ and R ¹³⁴ , R ¹³⁴ and R ¹³¹ , R ¹³¹ and R ¹³² , R ¹³² and R ¹³⁵ , R ¹³⁵ and R ^136, and R ¹³⁶ and R ¹¹³ may be linked to each other to form a ring. X represents a monovalent or divalent anion, n represents 1 or 2, and the product of the valence of X and n is 2. However, R ¹³¹ and R ¹³² are not simultaneously a phenyl group having a group represented by —NR ¹⁴¹ R ¹⁴² at the 4-position. Here, R ¹⁴¹ and R ¹⁴² each independently represent a hydrogen atom, an aliphatic group, or an aromatic group. ]   The resin composition according to claim 1, wherein the transmittance of light having a wavelength of 850 to 1000 nm is 30% or less.   The resin composition according to claim 1 or 2, wherein the binder resin has a glass transition temperature of 50 ° C or lower.   The resin composition according to any one of claims 1 to 3, wherein a glass transition temperature of the binder resin is 0 ° C or lower.   The resin composition according to any one of claims 1 to 4, wherein a mass ratio of the compound represented by the general formula (I) to the binder resin is 0.1 to 10%. . 6. The device according to claim 1, wherein at least one of R ¹¹¹ , R ¹¹² , R ¹²¹ , R ¹²² , R ^131, and R ¹³² is different in the general formula (I). Resin composition. In the general formula (I), at least one of R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , R ¹¹⁶ , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹³³ , R ¹³⁴ , R ^135, and R ¹³⁶ is different. The resin composition according to any one of claims 1 to 6, wherein: In the general formula (I), X is a perchlorate ion, hexafluoroantimonate ion, hexafluorophosphate ion, tetrafluoroborate ion, or any one of the following general formulas (II) to (IV). The resin composition according to claim 1, wherein the resin composition is at least one selected from ions to be formed.

[In the general formulas (II) to (IV), R ²¹¹ , R ²¹² , R ³¹¹ , R ³¹² , R ⁴¹¹ , R ⁴¹² and R ⁴¹³ are each independently an aliphatic group, an aromatic group or a heterocyclic group. Represents. ] In the general formulas (II) to (IV), R ²¹¹ , R ²¹² , R ³¹¹ , R ³¹² , R ⁴¹¹ , R ⁴¹² and R ⁴¹³ each independently have an aliphatic group having a halogen atom and a halogen atom. The resin composition according to claim 8, which is an aromatic group or a heterocyclic group having a halogen atom. In the general formulas (II) to (IV), R ²¹¹ , R ²¹² , R ³¹¹ , R ³¹² , R ⁴¹¹ , R ⁴¹² and R ⁴¹³ each independently have an aliphatic group having a fluorine atom or a fluorine atom. The resin composition according to claim 9, wherein the resin composition is an aromatic group or a heterocyclic group having a fluorine atom.   The laminated body containing the resin composition of any one of Claims 1-10.   The laminate according to claim 11, wherein the laminate has a structure in which a first ultraviolet absorbing layer, a resin composition layer containing the resin composition, and a second ultraviolet absorbing layer are sequentially laminated.   It is used for the display surface board with which a plasma display is mounted | worn, The resin composition of any one of Claims 1-10 characterized by the above-mentioned.   It is used for the display surface board with which a plasma display is mounted | worn, The laminated body of Claim 11 or Claim 12 characterized by the above-mentioned.