JP2008191509A - Near-infrared absorption film and method for manufacturing near-infrared absorption film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a near-infrared absorption film, capable of absorbing near infrared rays irradiated from a light source of a plasma display panel or of a liquid crystal panel and excelling in heat resistance and durability, and to provide a method for manufacturing the near-infrared absorption film. <P>SOLUTION: The near-infrared absorption film contains a heat resistant resin having a ring structure in a main chain and a glass transition temperature of 110-170°C and a phthalocyanine-based dye, the film is thus superior in heat resistance, near-infrared absorption properties and durability. The near-infrared absorption film can be formed by a melt extrusion method due to superior heat resistance. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a near-infrared absorbing film containing a heat-resistant resin having a ring structure in the main chain and a phthalocyanine dye, and a method for producing a near-infrared absorbing film.

  In recent years, flat panel displays such as plasma displays and liquid crystals have attracted attention, and tend to become larger year by year. However, a flat panel display such as a plasma display or a liquid crystal generates near infrared rays when emitting light by plasma discharge from a light source or by emitting light from a cathode tube. And the generation | occurrence | production of the near infrared rays has become remarkable by the enlargement of a display. Problems caused by generating near infrared rays include, for example, inducing a malfunction of a remote control for household appliances. Therefore, it is necessary to remove near infrared rays. Therefore, there is a demand for a near-infrared absorbing film that has a high near-infrared absorptivity and a high visible light transmittance (transparency in the visible region).

  Conventionally, an acrylic resin has been used as a resin contained in a near-infrared absorbing film having a high visible light transmittance. On the other hand, with the recent increase in the size of display panels, the temperature rise in the panel due to the heat generated from the light source during light emission, the photoelastic birefringence in the panel caused by the application of stress such as its own weight, etc. are also problems. It has become to. Therefore, the film itself is required to have high heat resistance, durability, low photoelastic birefringence and the like.

  Further, when a resin having a low glass transition temperature is used for a flat panel display such as a liquid crystal, the durability of the dye is lowered. Furthermore, the use of less durable dyes can contaminate the lines during the manufacturing process, making it very difficult to produce films that can be used for optical applications.

As a conventional infrared absorbing material, for example, Patent Document 1 discloses a liquid crystal display device member including an acrylic resin and a phthalocyanine dye as an infrared absorber. Patent Document 2 discloses an acrylic resin film containing an acrylic resin and a phthalocyanine dye as a near infrared absorber. Patent Document 3 discloses an optical planar thermoplastic resin molded article (optical protective film) in which a heat-resistant acrylic resin film having a lactone ring structure is coated with a layer containing a phthalocyanine dye as a near infrared absorber. It is shown.
JP 2001-305335 A (published October 31, 2001) JP 2004-217773 A (published August 5, 2004) JP 2006-96960 A (published April 13, 2006)

  However, the conventional infrared absorbing material has a problem that it is inferior in heat resistance and durability. Further, the conventional method for producing an infrared absorbing material has a problem that the process is not simplified.

  For example, the liquid crystal display member disclosed in Patent Document 1 does not contain a heat resistant resin. For this reason, the liquid crystal display device member is inferior in heat resistance and durability. Further, the acrylic resin film disclosed in Patent Document 2 does not contain a heat resistant resin. For this reason, the acrylic resin film is also inferior in heat resistance and durability. Further, the optical sheet thermoplastic resin molded article (optical protective film) shown in Patent Document 3 specifically shows that a composition of an acrylic resin and a phthalocyanine dye is formed into a film by melt extrusion. It has not been. For this reason, the optical planar thermoplastic resin molded body (optical protective film) is required to simplify the manufacturing process as the display becomes larger.

  The present invention has been made in view of the above-described conventional problems, and its purpose is heat resistance capable of absorbing near-infrared rays emitted from a light source such as a plasma display and a flat panel display such as a liquid crystal. It is providing the manufacturing method of the near-infrared absorption film excellent in durability, and a near-infrared absorption film.

  In order to solve the above problems, the near-infrared absorbing film of the present invention contains a heat-resistant resin having a ring structure in the main chain and a glass transition temperature of 110 ° C. or higher and 170 ° C. or lower, and a phthalocyanine dye. It is characterized by.

  According to said structure, the near-infrared absorption film of this invention contains the heat resistant resin which has a ring structure in a principal chain and whose glass transition temperature is 110 degreeC or more and 170 degrees C or less. Thereby, since the heat resistant resin does not melt at a temperature lower than 110 ° C., it can be said that the near-infrared absorbing film of the present invention is excellent in heat resistance and durability. Moreover, according to said structure, the near-infrared absorption film of this invention contains the phthalocyanine type pigment | dye. Thereby, since a phthalocyanine type pigment | dye absorbs near infrared rays, it can be said that the near-infrared absorption film of this invention is excellent in near-infrared absorptivity. Moreover, since the phthalocyanine dye has heat resistance, it can be said that the near-infrared absorbing film of the present invention is further excellent in heat resistance and durability.

  Furthermore, according to said structure, since the near-infrared absorption film of this invention is excellent in heat resistance, it can shape | mold by a melt extrusion method, without impairing an external appearance by foaming.

  In the near-infrared absorbing film of the present invention, the heat-resistant resin is preferably a heat-resistant acrylic resin.

  As a result, since the heat-resistant acrylic resin is excellent in optical performance, the near-infrared absorbing film of the present invention is applicable to various optical materials as an optical isotropic material having high light transmittance, low birefringence or low retardation. can do.

  In the near-infrared absorbing film of the present invention, the ring structure is preferably a lactone ring structure.

  Thereby, since the compound which has a lactone ring structure has the transmittance | permeability of visible light, the near-infrared absorption film of this invention can permeate | transmit visible light. Furthermore, since the compound having a lactone ring structure has heat resistance, the near-infrared absorbing film of the present invention can further have heat resistance.

  Moreover, it is preferable to shape | mold the manufacturing method of the near-infrared absorption film of this invention by the melt-extrusion method.

  Thereby, the manufacturing method of the near-infrared absorption film of this invention can make manufacturing cost low and can improve production efficiency rather than the manufacturing method shape | molded by the cast coating method.

  Moreover, it is preferable that the liquid crystal display device of this invention is equipped with the layer which consists of the said near-infrared absorption film at least 1 layer. Moreover, it is preferable that the polarizing plate protective film, retardation film, and diffusion film of this invention consist of the said near-infrared absorption film.

  Obtaining a liquid crystal display device, a polarizing plate protective film, a retardation film and a diffusion film excellent in heat resistance, near-infrared absorptivity, durability by heat resistance, near-infrared absorptivity, and durability included in the near-infrared absorption film Can do.

  As described above, the near-infrared absorbing film of the present invention comprises a heat-resistant resin having a ring structure in the main chain and having a glass transition temperature of 110 ° C. or higher and 170 ° C. or lower, and a phthalocyanine dye.

  Therefore, the near-infrared absorbing film of the present invention includes a heat-resistant resin having a ring structure in the main chain and having a glass transition temperature of 110 ° C. or higher and 170 ° C. or lower, and thus has excellent heat resistance and durability. It can be said that. Moreover, since the near-infrared absorption film of this invention contains the phthalocyanine type pigment | dye, it can be said that it is excellent in near-infrared absorptivity. Furthermore, since the near-infrared absorption film of this invention is excellent in heat resistance, there exists an effect that it can shape | mold by a melt extrusion method.

  Hereinafter, the present invention will be described in detail. However, the scope of the present invention is not limited to these descriptions, and other than the following examples, the present invention can be appropriately modified and implemented without departing from the spirit of the present invention. It is.

  The near-infrared absorbing film according to the present invention includes a heat-resistant resin having a ring structure in the main chain and having a glass transition temperature of 110 ° C. or higher and 170 ° C. or lower, and a phthalocyanine dye.

  The near-infrared absorbing film may be composed of only a heat-resistant resin having a ring structure in the main chain and a glass transition temperature of 110 ° C. or higher and 170 ° C. or lower and a phthalocyanine-based dye. As long as the above is not inhibited, other substances may be contained. It does not specifically limit as a method of including another substance.

<Near infrared and visible light>
Infrared radiation refers to electromagnetic waves in the wavelength region intermediate between visible light and microwaves. The wavelength region of infrared rays is about 0.76 μm or more and 1,000 μm or less. Moreover, near-infrared means a part close | similar to visible light whose wavelength region is 2.5 micrometers or less among infrared rays. Visible light refers to electromagnetic waves having a wavelength range that is perceived as light by human eyes. The wavelength region of visible light is about 0.38 μm or more and 0.78 μm or less. Microwave means a radio wave with a short wavelength. The wavelength region of the microwave is about 300 μm or more and 300,000 μm or less.

<Ring structure>
The ring structure of the heat-resistant resin contained in the near-infrared absorbing film of the present invention includes a lactone ring structure, a glutaric anhydride structure, an N-substituted methacrylimide structure, a maleic anhydride structure, an N-substituted maleimide structure, and a cyclopentane structure. Etc. As a resin having both visible light transmittance and heat resistance, a polymer containing a lactone ring obtained by subjecting a polymer having a hydroxy group and an ester group in a molecular chain to a lactone cyclocondensation reaction ( Hereinafter, the lactone ring structure is preferable as the ring structure.

<Heat resistant resin, glass transition temperature>
Examples of the heat resistant resin contained in the near-infrared absorbing film of the present invention include a heat resistant acrylic resin and a heat resistant norbornene resin.

  Among the heat-resistant resins exemplified above, it is a heat-resistant acrylic resin that has excellent optical performance and is adapted to various optical materials as an optical isotropic material with high light transmittance, low birefringence, and low retardation. Preferably there is.

  The near-infrared absorbing film of the present invention contains a heat resistant resin having a glass transition temperature of 110 ° C. or higher. Moreover, it is preferable that the glass transition temperature of the said heat resistant resin is 120 degreeC or more, and it is more preferable that it is 130 degreeC or more.

  Here, the glass transition temperature is a temperature at which the polymer molecules start micro-Brownian motion. There are various measurement methods for the glass transition temperature. In the present invention, the glass transition temperature is defined as a temperature determined by a midpoint method according to ASTM-D-3418 using a differential scanning calorimeter (DSC). Although a plurality of glass transition temperatures may be observed, in the present invention, a main transition temperature having a larger endothermic amount is adopted.

  The heat-resistant acrylic resin having a glass transition temperature of 110 ° C. or higher refers to a resin having a glass transition temperature of 110 ° C. or higher copolymerized with an acrylate monomer. Specifically, a polymer having a lactone ring structure by intramolecular cyclization reaction of a copolymer of maleic anhydride and acrylate, a copolymer of N-substituted maleimide and acrylate, or an acrylate copolymer (lactone polymer) And polymers having a glutarimide ring structure (glutarimide polymer) by intramolecular cyclization reaction of the acrylate copolymer.

  Moreover, as said acrylate monomer, the (meth) acrylic acid ester which has either a C1-C18 alkyl group, a cyclohexyl group, and a benzyl group is suitable. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) T-butyl acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, Examples include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 3-phenylpropyl (meth) acrylate, 2-hydroxylethyl (meth) acrylate, and the like. Of these, methyl methacrylate is particularly preferred. These (meth) acrylic acid esters may be used alone or in a suitable mixture of two or more.

  In addition, these heat-resistant acrylic resins may be copolymerized with other copolymerizable components as long as the heat resistance is not impaired. Specific examples of other monomer components that can be copolymerized include aromatic vinyl monomers such as styrene and α-methylstyrene, nitrile monomers such as acrylonitrile, vinyl esters such as vinyl acetate, and the like. Is mentioned.

  Furthermore, these heat-resistant acrylic resins preferably have a lactone ring structure represented by the following general formula (1).

^{Wherein, R 1, R 2, R} 3 each independently represent a hydrogen atom or an organic residue having 1 to 20 carbon atoms. The organic residue may contain an oxygen atom.

  Specific examples of the organic residue include an alkyl group having 1 to 20 carbon atoms such as a methyl group, an ethyl group, and a propyl group; an unsaturated aliphatic carbon atom having 1 to 20 carbon atoms such as an ethenyl group and a propenyl group. A hydrogen group; an aromatic hydrocarbon group having 1 to 20 carbon atoms such as a phenyl group or a naphthyl group; one or more hydrogen atoms of the alkyl group, the unsaturated hydrocarbon group, or the aromatic hydrocarbon group are hydroxyl groups; A substituted group; a group in which one or more hydrogen atoms of the alkyl group, the unsaturated hydrocarbon group, or the aromatic hydrocarbon group are substituted with a carboxyl group; the alkyl group, the unsaturated hydrocarbon group, or the aromatic A group in which one or more hydrogen atoms of an aromatic hydrocarbon group are substituted with an ether group; a group in which one or more hydrogen atoms of the alkyl group, the unsaturated hydrocarbon group, or the aromatic hydrocarbon group are substituted with an ester group Preferably . That is, an alkyl group having 1 to 20 carbon atoms, an unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 1 to 20 carbon atoms, or at least one of these groups It is preferable that the hydrogen atom is a group substituted with a hydroxyl group, a carboxyl group, an ether group, or an ester group.

  The upper limit of the content of the polymer having the lactone ring structure represented by the general formula (1) in the heat-resistant acrylic resin is preferably 90% by weight, and the lower limit is preferably 5% by weight. The upper limit is more preferably 70% by weight, and the lower limit is more preferably 10% by weight, and the upper limit is more preferably 60% by weight. If the content of the polymer having the lactone ring structure represented by the general formula (1) in the heat resistant resin is less than 5% by weight, the heat resistance, solvent resistance, and surface hardness may be insufficient. On the other hand, if the content of the polymer having a lactone ring structure represented by the general formula (1) in the heat resistant resin is more than 90% by weight, the moldability may be poor.

  When the lactonized polymer is a chloroform solution having a concentration of 15% by weight, the degree of coloration is preferably 6 or less, more preferably 3 or less, still more preferably 2 or less, and particularly preferably 1 or less. When the coloring degree exceeds 6, transparency may be impaired due to coloring, and may not be used for optical applications. The degree of coloring is obtained by dissolving the lactonized polymer in chloroform and placing it in a quartz cell as 15% by weight, and using a color difference meter (trade name: SZ-Σ90, manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS-K-7103. Measured with transmitted light.

  The mass reduction rate in the range of 150 ° C. or more and 300 ° C. or less in the dynamic TG measurement of the lactonized polymer is preferably 1% or less, more preferably 0.5% or less, further preferably 0.3% or less. It is. The mass reduction rate is obtained by dissolving or diluting the lactonized polymer in tetrahydrofuran, adding it to excess hexane or methanol for reprecipitation, and vacuum-drying the removed precipitate (1 mmHg (1.33 hPa), 80 ° C., Volatile components and the like are removed by conducting the reaction for 3 hours or more, and the obtained white solid resin is analyzed by the following method (dynamic TG method). The above analysis was performed using a thermal analyzer (trade name: Thermo Plus2 TG-8120 Dynamic TG, manufactured by Rigaku Corporation) using 5 to 10 mg of the lactonized polymer as a sample at a rate of temperature increase of 10 ° C./min, 200 ml / min. Measured with a nitrogen flow of min and a step-like isothermal control method (controlled at a mass reduction rate value of 0.005% / sec or less between 60 and 500 ° C.).

  Further, the 5% mass reduction temperature (thermal decomposition temperature) in the thermal mass analysis (TG) of the lactonized polymer is preferably 300 ° C. or higher, more preferably 320 ° C. or higher, and further preferably 330 ° C. or higher. . The 5% mass reduction temperature in thermal mass spectrometry (TG) is an index of thermal stability, and if it is less than 300 ° C., sufficient thermal stability may not be exhibited. The 5% mass reduction temperature is measured by the same method as the mass reduction rate.

  The total amount of residual volatile components contained in the lactonized polymer is preferably 1500 ppm or less, more preferably 1,000 ppm or less. When the total amount of residual volatile components exceeds 1500 ppm, it may be colored due to alteration during molding, foaming, or molding defects such as silver streak. The total amount of the remaining volatile matter is measured by a conventionally known method.

  The lactonized polymer may have a structure other than the lactone ring structure represented by the general formula (1). The structure other than the lactone ring structure represented by the general formula (1) is not particularly limited. For example, a (meth) acrylic acid ester, a hydroxy group-containing monomer, and the following general formula (2) as described later as a method for producing a lactonized polymer

(In the formula, R ⁴ represents a hydrogen atom or a methyl group, and X represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, an —OAc group, a —CN group, a —CO—R ⁵ group, or — Represents a COOH group, an Ac group represents an acetyl group, and R ⁵ represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms.)
It is preferably a polymer structural unit (repeating structural unit) formed by polymerizing at least one monomer selected from the group consisting of monomers represented by formula (1).

  The method for producing the lactonized polymer is not particularly limited. For example, after obtaining a polymer having a hydroxy group and an ester group in a molecular chain by a polymerization step (hereinafter referred to as “polymer (a)”), The obtained polymer (a) is obtained by performing a lactone cyclization condensation step for introducing a lactone ring structure into the polymer by heat treatment.

  In the polymerization step, for example, the following general formula (3)

(In the formula, R ⁷ and R ⁸ each independently represents a hydrogen atom or an organic residue having 1 to 20 carbon atoms). As a result, a polymer (a) having a hydroxy group and an ester group in the molecular chain is obtained.

  Examples of the monomer represented by the general formula (3) include methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate, isopropyl 2- (hydroxymethyl) acrylate, 2- Examples include n-butyl (hydroxymethyl) acrylate, t-butyl 2- (hydroxymethyl) acrylate, and the like. These monomers may be used alone or in combination of two or more. Among these monomers, 2- (hydroxymethyl) methyl acrylate and 2- (hydroxymethyl) ethyl acrylate are preferable, and since the effect of improving heat resistance is high, methyl 2- (hydroxymethyl) acrylate Is particularly preferred.

  The content of the monomer represented by the general formula (3) in the monomer component to be subjected to the polymerization step is preferably 5% by weight to 50% by weight, more preferably 10% by weight to 50% by weight. Hereinafter, it is particularly preferably 10% by weight or more and 40% by weight or less. When the content ratio of the monomer represented by the general formula (3) is less than 5% by weight, heat resistance, solvent resistance, and surface hardness of the obtained polymer may be lowered. Further, if the content of the monomer represented by the general formula (3) exceeds 50% by weight, gelation may occur in the polymerization step or the lactone cyclization condensation step, and the obtained polymer may be molded. May decrease.

  You may mix | blend monomers other than the monomer shown by said general formula (3) with the monomer component provided to the said superposition | polymerization process. Although it does not specifically limit as such a monomer, For example, the monomer etc. which are shown by (meth) acrylic acid ester and said General formula (2) are mentioned. These monomers may be used alone or in combination of two or more.

  The (meth) acrylic acid ester is not particularly limited as long as it is a (meth) acrylic acid ester other than the monomer represented by the general formula (3). For example, methyl acrylate, ethyl acrylate, Acrylic esters such as n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, cyclohexyl acrylate, benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate Methacrylic acid esters such as t-butyl methacrylate, cyclohexyl methacrylate, and benzyl methacrylate; These (meth) acrylic acid esters may be used alone or in combination of two or more. Among these (meth) acrylic acid esters, methyl methacrylate is particularly preferable because the obtained polymer has excellent heat resistance and transparency.

  When a (meth) acrylic acid ester other than the monomer represented by the general formula (3) is used, the content ratio in the monomer component to be subjected to the polymerization step is sufficient to exert the effect of the present invention. And preferably 10% to 95% by weight, more preferably 10% to 90% by weight, still more preferably 40% to 90% by weight, particularly preferably 50% to 90% by weight. .

  When the monomer represented by the general formula (2) is used, examples of the monomer represented by the general formula (2) include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, and methyl vinyl ketone. , Ethylene, propylene, vinyl acetate and the like. These monomers may be used alone or in combination of two or more.

  When the monomer represented by the general formula (2) is used, the content ratio in the monomer component to be subjected to the polymerization step is preferably 30% by weight or less in order to sufficiently exhibit the effects of the present invention. More preferably, it is 20% by weight or less, further preferably 15% by weight or less, and particularly preferably 10% by weight or less.

  The polymerization reaction for obtaining the polymer (a) having a hydroxy group and an ester group in the molecular chain by polymerizing the monomer component is preferably a polymerization form using a solvent, a solution Polymerization is particularly preferred. In addition, living radical polymerization consists only of an initiation reaction and a growth reaction, and does not cause side reactions that deactivate the growth end such as termination or chain transfer. It is particularly suitable for suppressing the generation of foreign matters such as carbides.

  The polymerization temperature and polymerization time in the polymerization step vary depending on the type and ratio of the monomer used, but preferably the polymerization temperature is 0 ° C. or higher and 150 ° C. or lower, and the polymerization time is 0.5 hour or longer and 20 hours or longer. The polymerization temperature is 80 ° C. or more and 140 ° C. or less, and the polymerization time is 1 hour or more and 10 hours or less.

  In the above polymerization step, in the case of a polymerization form using a solvent, the polymerization solvent is not particularly limited, and examples thereof include aromatic hydrocarbon solvents such as toluene, xylene, and ethylbenzene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. An ether solvent such as tetrahydrofuran; These solvents may be used alone or in combination of two or more. Moreover, since the residual volatile matter of the lactonized polymer finally obtained will increase when the boiling point of a solvent is too high, the solvent whose boiling point is 50 to 200 degreeC is preferable.

  In the polymerization step, a polymerization initiator may be added as necessary during the polymerization reaction. The polymerization initiator is not particularly limited as long as it is an initiator having a low ability to extract hydrogen from a polymer molecular chain. For example, t-amylperoxy-2-ethylhexanoate, t-amylperoxyisononano T-amyl type peroxides such as acid, t-amyl peroxyacetate, t-amyl peroxybenzoate, 1,1′-di (t-amylperoxy) cyclohexane; 2,2′-azobis (isobutyrate) Nitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate, etc. Initiator: dichlorotris (triphenylphosphine) ruthenium, aluminum triisopropoxide, 2,2'-dichloroacetopheno Living radical based initiators such like. These polymerization initiators may be used alone or in combination of two or more. The amount of the polymerization initiator used is not particularly limited as long as it is appropriately set according to the combination of monomers and reaction conditions.

  When performing the above polymerization, it is preferable to control the concentration of the polymer produced in the polymerization reaction mixture to be 50% by weight or less in order to suppress gelation of the reaction solution. Specifically, when the concentration of the polymer formed in the polymerization reaction mixture exceeds 50% by weight, it is preferable that the polymerization solvent is appropriately added to the polymerization reaction mixture and controlled to be 50% by weight or less. . The concentration of the polymer formed in the polymerization reaction mixture is more preferably 45% by weight or less, still more preferably 40% by weight or less. In addition, since the productivity is lowered if the concentration of the polymer produced in the polymerization reaction mixture is too low, the concentration of the polymer produced in the polymerization reaction mixture is preferably 10% by weight or more, more preferably 20% by weight. That's it.

  The form in which the polymerization solvent is appropriately added to the polymerization reaction mixture is not particularly limited, and for example, the polymerization solvent may be added continuously or the polymerization solvent may be added intermittently. By controlling the concentration of the polymer formed in the polymerization reaction mixture in this way, the gelation of the reaction solution can be more sufficiently suppressed, and in particular, the heat resistance is improved by increasing the content ratio of the lactone ring. Therefore, even when the ratio of the hydroxy group and the ester group in the molecular chain is increased, gelation can be sufficiently suppressed. The polymerization solvent to be added may be, for example, the same type of solvent used during the initial charging of the polymerization reaction or a different type of solvent, but the solvent used during the initial charging of the polymerization reaction. It is preferable to use the same type of solvent. Moreover, the polymerization solvent to be added may be only one kind of single solvent or two or more kinds of mixed solvents.

  The polymerization reaction mixture obtained when the above polymerization step is completed usually contains a solvent in addition to the obtained polymer, but it is necessary to completely remove the solvent and take out the polymer in a solid state. Rather, it is preferably introduced into the subsequent lactone cyclization condensation step in a state containing a solvent. Further, if necessary, a solvent suitable for the subsequent lactone cyclization condensation step may be added again after the solid is taken out.

  The polymer obtained in the polymerization step is a polymer (a) having a hydroxy group and an ester group in the molecular chain, and the weight average molecular weight of the polymer (a) is preferably 50,000 to 170, 000, more preferably 60,000 to 170,000, still more preferably 70,000 to 170,000. The polymer (a) obtained in the polymerization step is subjected to heat treatment in the subsequent lactone cyclization condensation step, whereby a lactone ring structure is introduced into the polymer to become a lactonized polymer.

  In the reaction for introducing the lactone ring structure into the polymer (a), the hydroxy group and the ester group present in the molecular chain of the polymer (a) are cyclized and condensed to form a lactone ring structure by heating. This is a reaction, and alcohol is by-produced by the cyclocondensation. By forming the lactone ring structure in the molecular chain of the polymer (in the main skeleton of the polymer), high heat resistance is imparted. If the reaction rate of the cyclization condensation reaction leading to the lactone ring structure is insufficient, the heat resistance will not be improved sufficiently, or a condensation reaction will occur during the molding due to the heat treatment during molding, and the resulting alcohol will be contained in the molded product. May exist as bubbles or silver streaks.

  The method for heat-treating the polymer (a) is not particularly limited, and a known method can be used. For example, you may heat-process the polymerization reaction mixture containing the solvent obtained by the superposition | polymerization process as it is. Moreover, you may heat-process using a ring-closing catalyst as needed in presence of a solvent. Further, the heat treatment can be performed using a heating furnace or a reaction apparatus having a vacuum apparatus or a devolatilizing apparatus for removing volatile components, an extruder having a devolatilizing apparatus, or the like.

  When the cyclization condensation reaction is performed, in addition to the polymer (a), another thermoplastic resin may coexist. Further, when performing the cyclization condensation reaction, if necessary, an esterification catalyst or a transesterification catalyst such as p-toluenesulfonic acid generally used as a catalyst for the cyclization condensation reaction may be used. Organic carboxylic acids such as propionic acid, benzoic acid, acrylic acid, and methacrylic acid may be used as a catalyst. When a basic compound, an organic carboxylate, a carbonate, or the like is used, a method disclosed in Japanese Patent Application Laid-Open Nos. 61-254608 and 61-261303 may be used.

  When performing the cyclization condensation reaction, it is preferable to use an organic phosphorus compound as a catalyst. By using an organophosphorus compound as a catalyst, the cyclization condensation reaction rate can be improved, and coloring of the obtained lactonized polymer can be greatly reduced. Furthermore, by using an organophosphorus compound as a catalyst, it is possible to suppress a decrease in molecular weight that can occur when a devolatilization step described later is used in combination, and to impart excellent mechanical strength.

  Examples of the organic phosphorus compound that can be used as a catalyst in the cyclization condensation reaction include alkyl (aryl) phosphonous acids such as methylphosphonous acid, ethylphosphonous acid, and phenylphosphonous acid (however, these are , Which may be tautomeric alkyl (aryl) phosphinic acid) and diesters or monoesters thereof; dimethylphosphinic acid, diethylphosphinic acid, diphenylphosphinic acid, phenylmethylphosphinic acid, phenylethylphosphinic acid, etc. Dialkyl (aryl) phosphinic acids and esters thereof; alkyl (aryl) phosphonic acids such as methylphosphonic acid, ethylphosphonic acid, trifluoromethylphosphonic acid, phenylphosphonic acid and their diesters or monoesters; methylphosphinic acid, Alkyl (aryl) phosphinic acids such as tilphosphinic acid and phenylphosphinic acid and their esters; methyl phosphite, ethyl phosphite, phenyl phosphite, dimethyl phosphite, diethyl phosphite, phosphorus phosphite Phosphorous acid diester, monoester or triester such as diphenyl acid, trimethyl phosphite, triethyl phosphite, triphenyl phosphite; methyl phosphate, ethyl phosphate, 2-ethylhexyl phosphate, octyl phosphate, phosphorus Isodecyl phosphate, lauryl phosphate, stearyl phosphate, isostearyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, di-2-ethylhexyl phosphate, diisodecyl phosphate, dilauryl phosphate, distearyl phosphate, phosphorus Diisostearyl acid, diphenyl phosphate, trimethyl phosphate, lithium Phosphoric acid diesters, monoesters or triesters such as triethyl phosphate, triisodecyl phosphate, trilauryl phosphate, tristearyl phosphate, triisostearyl phosphate, triphenyl phosphate; methylphosphine, ethylphosphine, phenylphosphine, dimethylphosphine, Mono, di or trialkyl (aryl) phosphines such as diethyl phosphine, diphenyl phosphine, trimethyl phosphine, triethyl phosphine, triphenyl phosphine; methyl dichlorophosphine, ethyl dichlorophosphine, phenyl dichlorophosphine, dimethylchlorophosphine, diethylchlorophosphine, diphenylchloro Alkyl (aryl) halogen phosphines such as phosphine; methyl phosphine oxide, ethyl phosphine oxide, phenoxy oxide Mono-, di- or trialkyl (aryl) phosphines such as ruphosphine, dimethylphosphine oxide, diethylphosphine oxide, diphenylphosphine oxide, trimethylphosphine oxide, triethylphosphine oxide, triphenylphosphine oxide; tetramethylphosphonium chloride, tetraethylphosphonium chloride, Halogenated tetraalkyl (aryl) phosphonium such as tetraphenylphosphonium chloride; and the like. Among these, alkyl (aryl) phosphonous acid, phosphorous acid diester or monoester, phosphoric acid diester or monoester, and alkyl (aryl) phosphonic acid are preferable because of high catalytic activity and low colorability. ) Phosphorous acid, phosphorous acid diester or monoester, phosphoric acid diester or monoester are more preferred, and alkyl (aryl) phosphorous acid, phosphoric acid diester or monoester is particularly preferred. These organic phosphorus compounds may use only 1 type and may use 2 or more types together.

  The amount of the catalyst used in the cyclization condensation reaction is not particularly limited, but is preferably 0.001 wt% or more and 5 wt% or less, more preferably 0.01 wt% with respect to the polymer (a). It is not less than 2.5% by weight, more preferably not less than 0.01% by weight and not more than 1% by weight, particularly preferably not less than 0.05% by weight and not more than 0.5% by weight. If the amount of the catalyst used is less than 0.001% by weight, the reaction rate of the cyclization condensation reaction may not be sufficiently improved. On the other hand, if it exceeds 5% by weight, it may cause coloring or heavy load. This is not preferable because it is difficult to melt mold by crosslinking the coalesced. The addition timing of the catalyst is not particularly limited, and it may be added at the beginning of the reaction, during the reaction, or may be added to both of them.

  It is preferable to perform the cyclization condensation reaction in the presence of a solvent and to use a devolatilization step in combination with the cyclization condensation reaction. In this case, a mode in which the devolatilization step is used throughout the cyclization condensation reaction and a mode in which the devolatilization step is not used throughout the entire cyclization condensation reaction and are used only in a part of the process. In the method using the devolatilization step in combination, the alcohol produced as a by-product in the condensation cyclization reaction is forcibly devolatilized and removed, so that the reaction equilibrium is advantageous for the lactone polymer production side.

  The devolatilization step refers to a step of removing volatile components such as a solvent and residual monomer and alcohol produced as a by-product by a cyclocondensation reaction leading to a lactone ring structure, if necessary under reduced pressure heating conditions. If this removal treatment is insufficient, the residual volatile components in the produced resin increase, resulting in problems such as coloration due to alteration during molding, and molding defects such as bubbles and silver streaks.

  In the case of using a devolatilization step throughout the cyclization condensation reaction, the apparatus to be used is not particularly limited. In order to carry out the present invention more effectively, it is preferable to use a devolatilizer comprising a heat exchanger and a devolatilization tank, an extruder with a vent, a devolatilizer and an extruder arranged in series, etc. It is more preferable to use a devolatilizer or an extruder with a vent comprising an exchanger and a devolatilization tank.

  In the devolatilization step, the reaction treatment temperature in the case of using a devolatilizer comprising a heat exchanger and a devolatilization tank is preferably in the range of 150 ° C to 350 ° C, and more preferably in the range of 200 ° C to 300 ° C. . If the reaction treatment temperature is less than 150 ° C., the cyclization condensation reaction may be insufficient and the residual volatile matter may increase. On the other hand, if the reaction treatment temperature exceeds 350 ° C., the obtained polymer may be colored or decomposed.

  In the above devolatilization step, the pressure during the reaction treatment when using a devolatilizer comprising a heat exchanger and a devolatilization tank is preferably within a range of 931 hPa or less and 1.33 hPa or more (700 mmHg or less and 1 mmHg or more), and 798 hPa or less. The range of 66.5 hPa or more (600 mmHg or less and 50 mmHg or more) is more preferable. When the said pressure exceeds 931 hPa, there exists a problem that the volatile matter containing alcohol will remain easily. Conversely, if it is less than 1.33 hPa, there is a problem that industrial implementation becomes difficult.

  When using the extruder with a vent, one or a plurality of vents may be used, but it is preferable to have a plurality of vents.

  In the case of using the vented extruder, the reaction treatment temperature is preferably in the range of 150 ° C to 350 ° C, more preferably in the range of 200 ° C to 300 ° C. If the reaction treatment temperature is less than 150 ° C., the cyclization condensation reaction may be insufficient and the residual volatile matter may increase. On the other hand, if the reaction treatment temperature exceeds 350 ° C., the obtained polymer may be colored or decomposed.

  In the case of using the vented extruder, the reaction treatment pressure is preferably in the range of 931 hPa or less and 1.33 hPa or more (700 mmHg or less and 1 mmHg or more), and more preferably in the range of 798 hPa or less and 13.3 hPa or more (600 mmHg or less and 10 mmHg or more). When the reaction treatment pressure is higher than 931 hPa, there is a problem that volatile components including alcohol easily remain, and when it is lower than 1.33 hPa, there is a problem that industrial implementation becomes difficult.

  In the case where the devolatilization step is used throughout the cyclization condensation reaction, the physical properties of the lactonized polymer obtained under severe heat treatment conditions may deteriorate as described later. It is preferable to use a reaction catalyst and use a vented extruder or the like under the mildest conditions possible.

  In the case of using the devolatilization step throughout the entire cyclization condensation reaction, preferably, the polymer (a) obtained in the polymerization step is introduced into the cyclization condensation reactor system together with the solvent. If necessary, it may be passed through the reactor system such as a vented extruder once again. You may perform the form used together only in a part of process, without using a devolatilization process over the whole process of cyclization condensation reaction. For example, the apparatus for producing the polymer (a) is further heated, and if necessary, a part of the devolatilization step is used together to advance the cyclization condensation reaction to some extent in advance, followed by the devolatilization step. Is used to complete the reaction.

  In the form of using a devolatilization step throughout the cyclization condensation reaction, for example, when the polymer (a) is heat-treated at a high temperature of nearly 250 ° C. or higher using a twin-screw extruder, Due to the difference in thermal history, partial decomposition or the like may occur before the cyclization condensation reaction occurs, and the physical properties of the obtained lactonized polymer may be deteriorated. Therefore, if the cyclization condensation reaction is allowed to proceed to some extent before performing the cyclization condensation reaction combined with the devolatilization step, the latter reaction conditions can be relaxed, and deterioration of the physical properties of the resulting lactonized polymer can be suppressed. Therefore, it is preferable. As a particularly preferred mode, a mode in which the devolatilization step is started after a lapse of time from the start of the cyclization condensation reaction, that is, a hydroxy group and an ester group present in the molecular chain of the polymer (a) obtained in the polymerization step. In which the cyclization condensation reaction rate is increased to some extent and then the cyclization condensation reaction is used in combination with the devolatilization step. Specifically, for example, a cyclization condensation reaction is allowed to proceed to a certain reaction rate in the presence of a solvent in advance using a kettle-type reactor, and then a reactor equipped with a devolatilizer, for example, a heat Preferred is a mode in which the cyclization condensation reaction is completed with a devolatilizer comprising an exchanger and a devolatilization tank, an extruder with a vent, or the like. Particularly in this form, it is more preferable that a catalyst for the cyclization condensation reaction is present.

  As described above, the hydroxy group and the ester group present in the molecular chain of the polymer (a) obtained in the polymerization step are preliminarily subjected to a cyclization condensation reaction to increase the cyclization condensation reaction rate to some extent. The method of carrying out the cyclization condensation reaction using the volatilization process is a preferred form for obtaining a lactonized polymer in the present invention. With this form, a lactonized polymer having a higher glass transition temperature, a higher cyclization condensation reaction rate, and excellent heat resistance can be obtained. In this case, as a measure of the cyclization condensation reaction rate, the mass reduction rate within the range of 150 ° C. or more and 300 ° C. or less in dynamic TG measurement is preferably 2% or less, more preferably 1.5% or less. More preferably, it is 1% or less.

  The reactor that can be employed in the case of the cyclization condensation reaction performed in advance before the cyclization condensation reaction combined with the devolatilization step is not particularly limited, but preferably an autoclave, a kettle reactor, a heat exchanger, and a devolatilization tank And the like. Furthermore, an extruder with a vent suitable for a cyclization condensation reaction using a devolatilization step can also be used, and an autoclave and a kettle reactor are preferable. However, even when using a reactor such as an extruder with a vent, by adjusting the temperature condition, barrel condition, screw shape, screw operating condition, etc. It is possible to carry out the cyclization condensation reaction in the same state as the reaction state in the kettle reactor.

  In the case of the cyclization condensation reaction performed in advance before the cyclization condensation reaction combined with the devolatilization step, preferably, a mixture containing the polymer (a) and the solvent obtained in the polymerization step is used as (i). Examples include a method in which a catalyst is added and subjected to a heat reaction, (ii) a method in which a heat reaction is performed without a catalyst, and a method in which the above (i) or (ii) is performed under pressure. The “mixture containing the polymer (a) and the solvent” introduced into the cyclization condensation reaction in the lactone cyclization condensation step may be the polymerization reaction mixture obtained in the polymerization step as it is, or once After removing the solvent, a solvent suitable for the cyclization condensation reaction may be added again.

  The solvent that can be re-added in the cyclization condensation reaction performed in advance before the cyclization condensation reaction combined with the devolatilization step is not particularly limited, for example, aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; chloroform, dimethyl sulfoxide (DMSO), tetrahydrofuran; These solvents may be used alone or in combination of two or more. Moreover, it is preferable to use the same kind of solvent as the solvent used in the polymerization step.

  Examples of the catalyst to be added in the above method (i) include esterification catalysts or transesterification catalysts such as p-toluenesulfonic acid, basic compounds, organic carboxylates, and carbonates that are generally used. Is preferably the above-described organophosphorus compound. The addition timing of the catalyst is not particularly limited, and it may be added at the beginning of the reaction, during the reaction, or both. The amount of the catalyst to be added is not particularly limited, but is preferably 0.001% by weight to 5% by weight, more preferably 0.01% by weight to 2.5% by weight, based on the weight of the polymer (a). More preferably, they are 0.01 weight% or more and 0.1 weight% or less, Especially preferably, they are 0.05 weight% or more and 0.5 weight% or less. The heating temperature and heating time in method (i) are not particularly limited, but the heating temperature is preferably room temperature to 180 ° C., more preferably 50 ° C. to 150 ° C., and the heating time is preferably 1 hour. It is 20 hours or less, more preferably 2 hours or more and 10 hours or less. When the heating temperature is low or the heating time is short, the cyclization condensation reaction rate is lowered, which is not preferable. Further, if the heating time is too long, the resin may be colored or decomposed, which is not preferable.

  Examples of the method (ii) include a method of heating the polymerization reaction mixture obtained in the polymerization step as it is using a pressure-resistant kettle or the like. Although the heating temperature and heating time of method (ii) are not particularly limited, for example, the heating temperature is preferably 100 ° C. or higher and 180 ° C. or lower, more preferably 100 ° C. or higher and 150 ° C. or lower. The heating time is preferably 1 hour or more and 20 hours or less, more preferably 2 hours or more and 10 hours or less. When the heating temperature is low or the heating time is short, the cyclization condensation reaction rate is lowered, which is not preferable. Further, if the heating time is too long, the resin may be colored or decomposed, which is not preferable.

  Both the above methods (i) and (ii) have no problem even under pressure depending on conditions. In the case of the cyclization condensation reaction performed in advance before the cyclization condensation reaction using the devolatilization step, there is no problem even if a part of the solvent volatilizes naturally during the reaction.

  Mass reduction rate in the range of 150 ° C. or more and 300 ° C. or less in dynamic TG measurement at the end of the cyclization condensation reaction performed in advance before the cyclization condensation reaction combined with the devolatilization step, that is, immediately before the start of the devolatilization step. Is preferably 2% or less, more preferably 1.5% or less, and still more preferably 1% or less. When the mass reduction rate is higher than 2%, the cyclization condensation reaction rate does not rise to a sufficiently high level even if the cyclization condensation reaction is performed together with the devolatilization step, and the physical properties of the obtained lactonized polymer are lowered. There is a fear. In addition, when performing said cyclization condensation reaction, in addition to a polymer (a), you may coexist other thermoplastic resins.

  In the above methods (i) and (ii), the hydroxy group and the ester group present in the molecular chain of the polymer (a) obtained in the polymerization step are subjected to a cyclization condensation reaction in advance to increase the cyclization condensation reaction rate to some extent. It may be carried out in a form in which the cyclization condensation reaction using the devolatilization step is performed. For example, a polymer obtained by a cyclization condensation reaction performed in advance (a polymer in which at least a part of a hydroxyl group and an ester group present in a molecular chain is subjected to a cyclization condensation reaction) and a solvent are used in combination with a devolatilization step. You may introduce | transduce into a cyclocondensation reaction. In addition, if necessary, other treatment such as re-adding the solvent after isolating the above polymer (polymer in which at least a part of the hydroxyl group and ester group present in the molecular chain has undergone cyclization condensation reaction) is performed. It may be introduced into the cyclization condensation reaction using the devolatilization step after passing through. The devolatilization step is not limited to being completed at the same time as the cyclization condensation reaction, and may be completed after a lapse of time from the completion of the cyclization condensation reaction.

  The lactonized polymer is not only excellent in transparency and heat resistance, but also has desired properties such as low colorability, mechanical strength, molding processability, etc. It is particularly suitable for optical applications.

<Phthalocyanine dye>
The phthalocyanine dye contained in the near-infrared absorbing film of the present invention is not particularly limited as long as it has an excellent near-infrared absorbing ability, and a known phthalocyanine dye can be used. Among these, the compounds represented by the following general formula (4) and general formula (5) are preferable.

In the general formula ^{(4), A} 1 ^{~A 16} represents a functional group. In the general formula (4), A ^{1 to} A ¹⁶ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxysulfonyl group, a carboxyl group, a thiol group, or an optionally substituted carbon atom having 1 to 20 carbon atoms. Alkyl group, optionally substituted alkoxy group having 1 to 20 carbon atoms, optionally substituted aryl group having 6 to 20 carbon atoms, optionally substituted 6 to 6 carbon atoms 20 aryloxy groups, an optionally substituted aralkyl group having 7 to 20 carbon atoms, an optionally substituted aralkyloxy group having 7 to 20 carbon atoms, and an optionally substituted carbon atom An alkylthio group having 1 to 20 carbon atoms, an arylthio group having 6 to 20 carbon atoms which may be substituted, an aralkylthio group having 7 to 20 carbon atoms which may be substituted, An optionally substituted alkylsulfonyl group having 1 to 20 carbon atoms, an optionally substituted arylsulfonyl group having 6 to 20 carbon atoms, and an optionally substituted aralkyl having 7 to 20 carbon atoms A sulfonyl group, an optionally substituted acyl group having 1 to 20 carbon atoms, an optionally substituted alkoxycarbonyl group having 2 to 20 carbon atoms, and an optionally substituted carbon atom having 6 to 20 carbon atoms Aryloxycarbonyl group, optionally substituted aralkyloxycarbonyl group having 2 to 20 carbon atoms, optionally substituted alkylcarbonyloxy group having 2 to 20 carbon atoms, optionally substituted A good arylcarbonyloxy group having 6 to 20 carbon atoms, an optionally substituted aralkylcarbonyloxy group having 8 to 20 carbon atoms, Are carbon atoms which may have 2-20 heterocyclic group, a substituted amino group which may be, optionally substituted aminosulfonyl group or an optionally substituted aminocarbonyl group.

The functional groups of A ^{1 to} A ¹⁶ may be the same type or different types, and may be the same or different in the same type, and the functional groups may be connected via a linking group. M ¹ represents two hydrogen atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or an oxy metal. In the present specification, an “acyl group” is a group in which a hydroxyl group has been removed from an organic acid (the definition described on page 17 of the third edition of the Dictionary of Science and Technology Terms published by Nikkan Kogyo Shimbun Co., Ltd.). Specifically, it is a group represented by RCO— (where R is an aliphatic group, an alicyclic group or an aromatic group).

When the terminal is a functional group other than an amino group, in the general formula (4), examples of the halogen atom of the functional groups A ^{1 to} A ¹⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the optionally substituted alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, Examples thereof include linear, branched or cyclic alkyl groups such as t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group. However, it is not limited to these. Examples of the optionally substituted alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butyloxy group, iso-butyloxy group, sec-butyloxy Group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, etc., linear, branched or cyclic An alkoxy group is mentioned. However, it is not limited to these. Examples of the aryl group having 6 to 20 carbon atoms which may be substituted include a phenyl group and a naphthyl group. However, it is not limited to these. Examples of the optionally substituted aryloxy group having 6 to 20 carbon atoms include phenoxy group and naphthoxy group. However, it is not limited to these. Examples of the aralkyl group having 7 to 20 carbon atoms which may be substituted include a benzyl group, a phenethyl group and a diphenylmethyl group. However, it is not limited to these. Examples of the aralkyloxy group having 7 to 20 carbon atoms which may be substituted include a benzyloxy group, a phenethyloxy group and a diphenylmethyloxy group. However, it is not limited to these. Examples of the optionally substituted alkylthio group having 1 to 20 carbon atoms include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, Examples thereof include linear, branched or cyclic alkylthio groups such as t-butylthio group, n-pentylthio group, n-hexylthio group, cyclohexylthio group, n-heptylthio group, n-octylthio group and 2-ethylhexylthio group. However, it is not limited to these. Examples of the optionally substituted arylthio group having 6 to 20 carbon atoms include a phenylthio group and a naphthylthio group. However, it is not limited to these. Examples of the aralkylthio group having 7 to 20 carbon atoms which may be substituted include benzylthio group, phenethylthio group, diphenylmethylthio group and the like. However, it is not limited to these. Examples of the optionally substituted alkylsulfonyl group having 1 to 20 carbon atoms include methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, iso-propylsulfonyl group, n-butylsulfonyl group, iso-butylsulfonyl. Group, sec-butylsulfonyl group, t-butylsulfonyl group, n-pentylsulfonyl group, n-hexylsulfonyl group, cyclohexylsulfonyl group, n-heptylsulfonyl group, n-octylsulfonyl group, 2-ethylhexylsulfonyl group, etc. A linear, branched or cyclic alkylsulfonyl group is mentioned. However, it is not limited to these. Examples of the arylsulfonyl group having 6 to 20 carbon atoms which may be substituted include a phenylsulfonyl group and a naphthylsulfonyl group. However, it is not limited to these. Examples of the aralkylsulfonyl group which may be substituted include a benzylsulfonyl group, a phenethylsulfonyl group, a diphenylmethylsulfonyl group and the like. However, it is not limited to these. Examples of the optionally substituted acyl group having 1 to 20 carbon atoms include methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl group, straight chain such as sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, n-hexylcarbonyl group, cyclohexylcarbonyl group, n-heptylcarbonyl group, n-octylcarbonyl group, 2-ethylhexylcarbonyl group, Examples include branched or cyclic alkylcarbonyl groups, arylcarbonyl groups such as benzylcarbonyl groups and phenylcarbonyl groups, and aralkylcarbonyl groups such as benzoyl groups. However, it is not limited to these. Examples of the optionally substituted alkoxycarbonyl group having 2 to 20 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, iso-propyloxycarbonyl group, n-butyloxycarbonyl group, iso -Butyloxycarbonyl group, sec-butyloxycarbonyl group, t-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxy A carbonyl group, 2-ethylhexyloxycarbonyl group, etc. are mentioned. However, it is not limited to these. Examples of the optionally substituted aryloxycarbonyl group having 7 to 20 carbon atoms include phenoxycarbonyl group and naphthylcarbonyl group. However, it is not limited to these. Examples of the aralkyloxycarbonyl group having 8 to 20 carbon atoms which may be substituted include a benzyloxycarbonyl group, a phenethyloxycarbonyl group, and a diphenylmethyloxycarbonyl group. However, it is not limited to these. Examples of the optionally substituted alkylcarbonyloxy group having 2 to 20 carbon atoms include acetyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxy group, and n-butylcarbonyloxy group. , Iso-butylcarbonyloxy group, sec-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, n-hexylcarbonyloxy group, cyclohexylcarbonyloxy group, n-heptylcarbonyloxy group, 3- A heptyl carbonyloxy group, n-octyl carbonyloxy group, etc. are mentioned. However, it is not limited to these. Examples of the optionally substituted arylcarbonyloxy group having 7 to 20 carbon atoms include a benzoyloxy group. However, it is not limited to these. Examples of the optionally substituted aralkylcarbonyloxy group having 8 to 20 carbon atoms include a benzylcarbonyloxy group. However, it is not limited to these. Examples of the optionally substituted heterocyclic group having 2 to 20 carbon atoms include a pyrrole group, an imidazole group, a piperidine group, and a morpholine group. However, it is not limited to these.

In the general formula (4), the alkyl group, alkoxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group, alkylthio group, arylthio group, aralkylthio group, alkylsulfonyl of the functional groups A ^{1 to} A ¹⁶ Group, arylsulfonyl group, aralkylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, aralkylcarbonyloxy group or heterocyclic group are substituted In this case, examples of the substituents present in these functional groups A ^{1 to} A ¹⁶ include, for example, a halogen atom, an acyl group, an alkyl group, a phenyl group, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group, a nitro group, and an amino group. , Al Ruamino group, alkylcarbonylamino group, arylamino group, arylcarbonylamino group, carbonyl group, alkoxycarbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, alkylthio group, carbamoyl group, aryloxycarbonyl group, cyano group, heterocyclic group Etc. However, it is not limited to these. A plurality of these substituents may be present. When a plurality of substituents are present, they may be the same or different, and even in the same case, they may be the same or different. Moreover, substituents may be connected through a linking group.

In the case of a functional group whose terminal is an amino group, in the above general formula (4), the functional groups A ^{1 to} A ¹⁶ may be substituted amino groups, may be substituted aminosulfonyl groups, The substituents on the aminocarbonyl group may be a hydrogen atom; methyl group, ethyl group, n-propyl group, n-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group. Linear, branched or cyclic alkyl groups such as cyclohexyl group; aryl groups such as phenyl group and naphthyl group; aralkyl groups such as benzyl group and phenethyl group; acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso- Propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl group, sec-butylcarbonyl group, t-butylcarbonyl group, -Linear, branched or cyclic alkylcarbonyl groups such as pentylcarbonyl group, n-hexylcarbonyl group, cyclohexylcarbonyl group, n-heptylcarbonyl group, 3-heptylcarbonyl group, n-octylcarbonyl group; benzoyl group, naphthylcarbonyl An arylcarbonyl group such as a group; and an aralkylcarbonyl group such as a benzylcarbonyl group. However, the substituent is not limited thereto, and these substituents may be further substituted with a substituent. These substituents may be present in the number of 0, 1 or 2, and when 2 are present, they may be the same or different from each other, and even in the same type, they may be the same or different. Also good. Moreover, when there are two substituents, the substituents may be connected via a linking group.

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

Examples of the divalent metal as the metal M ¹ include Cu (II), Co (II), Zn (II), Fe (II), Ni (II), Ru (II), and Rh (II). , Pd (II), Pt (II), Mn (II), Mg (II), Ti (II), Be (II), Ca (II), Ba (II), Cd (II), Hg (II) , Pb (II), Sn (II) and the like. However, it is not limited to these. Examples of trivalent substituted metal atoms include Al-F, Al-Cl, Al-Br, Al-I, Fe-Cl, Ga-F, Ga-Cl, Ga-I, Ga-Br, In-F. , In-Cl, In-Br , In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Al-C 6 H 5, Al-C 6 H 4 (CH 3), In-C _{6 H 5, In-C 6} H 4 (CH 3), In-C 6 H 5, Mn (OH), Mn (OC 6 H 5), Mn [OSi _{(CH 3)} 3], Ru-Cl, etc. is Can be mentioned. However, it is not limited to these. Examples of tetravalent substituted metal atoms include CrCl ₂ , SiF ₂ , SiCl ₂ , SiBr ₂ , SiI ₂ , ZrCl ₂ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ , SnF ₂ , SnCl ₂ , SnBr ₂ , TiF ₂ , TiCl ₂ , TiBr ₂ , Ge (OH) ₂ , Mn (OH) ₂ , Si (OH) ₂ , Sn (OH) ₂ , Zr (OH) ₂ , Cr (R ₁ ) ₂ , Ge (R ₁ ) ₂ , Si (R ₁ ) ₂ , Sn (R ₁ ) ₂ , Ti (R ₁ ) ₂ {R ₁ represents an alkyl group, a phenyl group, a naphthyl group, or a derivative thereof} Cr (OR ₂ ) ₂ , _{Ge (OR 2) 2, Si} (OR 2) 2, Sn (OR 2) 2, Ti (OR 2) 2, {R 2 is an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group, a dialkyl Alkoxysilyl represents a group or a derivative _{thereof}, Sn (SR 3) 2} , Ge (SR 3) 2 {R 3 is an alkyl group, a phenyl group, a naphthyl group or a derivative thereof}, and the like. However, it is not limited to these. Examples of the oxymetal include VO, MnO, TiO and the like. However, it is not limited to these.

In the general formula ^{(5), B} 1 ^{~B 24} represents a functional group. B ^{1 to} B ²⁴ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxysulfonyl group, a carboxyl group, a thiol group, an optionally substituted alkyl group having 1 to 20 carbon atoms, or a substituted group. An optionally substituted alkoxy group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, an optionally substituted aryloxy group having 6 to 20 carbon atoms, and substitution An aralkyl group having 7 to 20 carbon atoms which may be substituted, an aralkyloxy group having 7 to 20 carbon atoms which may be substituted, and an alkylthio group having 1 to 20 carbon atoms which may be substituted , An optionally substituted arylthio group having 6 to 20 carbon atoms, an optionally substituted aralkylthio group having 7 to 20 carbon atoms, and an optionally substituted carbon atom 1-20 alkylsulfonyl groups, optionally substituted arylsulfonyl groups having 6-20 carbon atoms, optionally substituted aralkylsulfonyl groups having 7-20 carbon atoms, optionally substituted Good acyl group having 1 to 20 carbon atoms, optionally substituted alkoxycarbonyl group having 2 to 20 carbon atoms, optionally substituted aryloxycarbonyl group having 6 to 20 carbon atoms, substitution An aralkyloxycarbonyl group having 2 to 20 carbon atoms which may be substituted, an alkylcarbonyloxy group having 2 to 20 carbon atoms which may be substituted, and 6 to 20 carbon atoms which may be substituted Arylcarbonyloxy group, optionally substituted aralkylcarbonyloxy group having 8 to 20 carbon atoms, optionally substituted carbon atom 2-20 heterocyclic group, a substituted amino group which may be, optionally substituted aminosulfonyl group or an optionally substituted aminocarbonyl group.

The functional groups of B ^{1 to} B ²⁴ may be the same or different, and may be the same or different in the same type, and the functional groups may be linked via a linking group. M ² represents two hydrogen atoms, a divalent metal atom, a trivalent substituted metal atom, a tetravalent substituted metal atom, or an oxy metal.

When the terminal is a functional group other than an amino group, in the general formula (5), examples of the halogen atom of the functional groups B ^{1 to} B ²⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the optionally substituted alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, Examples thereof include linear, branched or cyclic alkyl groups such as t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group and 2-ethylhexyl group. However, it is not limited to these. Examples of the optionally substituted alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propyloxy group, iso-propyloxy group, n-butyloxy group, iso-butyloxy group, sec-butyloxy Group, t-butyloxy group, n-pentyloxy group, n-hexyloxy group, cyclohexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, etc., linear, branched or cyclic An alkoxy group is mentioned. However, it is not limited to these. Examples of the aryl group having 6 to 20 carbon atoms which may be substituted include a phenyl group and a naphthyl group. However, it is not limited to these. Examples of the optionally substituted aryloxy group having 6 to 20 carbon atoms include phenoxy group and naphthoxy group. However, it is not limited to these. Examples of the aralkyl group having 7 to 20 carbon atoms which may be substituted include a benzyl group, a phenethyl group and a diphenylmethyl group. However, it is not limited to these. Examples of the aralkyloxy group having 7 to 20 carbon atoms which may be substituted include a benzyloxy group, a phenethyloxy group and a diphenylmethyloxy group. However, it is not limited to these. Examples of the optionally substituted alkylthio group having 1 to 20 carbon atoms include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, iso-butylthio group, sec-butylthio group, Examples thereof include linear, branched or cyclic alkylthio groups such as t-butylthio group, n-pentylthio group, n-hexylthio group, cyclohexylthio group, n-heptylthio group, n-octylthio group and 2-ethylhexylthio group. However, it is not limited to these. Examples of the optionally substituted arylthio group having 6 to 20 carbon atoms include a phenylthio group and a naphthylthio group. However, it is not limited to these. Examples of the aralkylthio group having 7 to 20 carbon atoms which may be substituted include benzylthio group, phenethylthio group, diphenylmethylthio group and the like. However, it is not limited to these. Examples of the optionally substituted alkylsulfonyl group having 1 to 20 carbon atoms include methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, iso-propylsulfonyl group, n-butylsulfonyl group, iso-butylsulfonyl. Group, sec-butylsulfonyl group, t-butylsulfonyl group, n-pentylsulfonyl group, n-hexylsulfonyl group, cyclohexylsulfonyl group, n-heptylsulfonyl group, n-octylsulfonyl group, 2-ethylhexylsulfonyl group, etc. A linear, branched or cyclic alkylsulfonyl group is mentioned. However, it is not limited to these. Examples of the arylsulfonyl group having 6 to 20 carbon atoms which may be substituted include a phenylsulfonyl group and a naphthylsulfonyl group. However, it is not limited to these. Examples of the aralkylsulfonyl group which may be substituted include a benzylsulfonyl group, a phenethylsulfonyl group, a diphenylmethylsulfonyl group and the like. However, it is not limited to these. Examples of the optionally substituted acyl group having 1 to 20 carbon atoms include methylcarbonyl group, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl group, straight chain such as sec-butylcarbonyl group, t-butylcarbonyl group, n-pentylcarbonyl group, n-hexylcarbonyl group, cyclohexylcarbonyl group, n-heptylcarbonyl group, n-octylcarbonyl group, 2-ethylhexylcarbonyl group, Examples include branched or cyclic alkylcarbonyl groups, arylcarbonyl groups such as benzylcarbonyl groups and phenylcarbonyl groups, and aralkylcarbonyl groups such as benzoyl groups. However, it is not limited to these. Examples of the optionally substituted alkoxycarbonyl group having 2 to 20 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, n-propyloxycarbonyl group, iso-propyloxycarbonyl group, n-butyloxycarbonyl group, iso -Butyloxycarbonyl group, sec-butyloxycarbonyl group, t-butyloxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, cyclohexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxy A carbonyl group, 2-ethylhexyloxycarbonyl group, etc. are mentioned. However, it is not limited to these. Examples of the optionally substituted aryloxycarbonyl group having 7 to 20 carbon atoms include phenoxycarbonyl and naphthylcarbonyl groups. However, it is not limited to these. Examples of the aralkyloxycarbonyl group having 8 to 20 carbon atoms which may be substituted include a benzyloxycarbonyl group, a phenethyloxycarbonyl group, and a diphenylmethyloxycarbonyl group. However, it is not limited to these. Examples of the optionally substituted alkylcarbonyloxy group having 2 to 20 carbon atoms include acetyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, iso-propylcarbonyloxy group, and n-butylcarbonyloxy group. , Iso-butylcarbonyloxy group, sec-butylcarbonyloxy group, t-butylcarbonyloxy group, n-pentylcarbonyloxy group, n-hexylcarbonyloxy group, cyclohexylcarbonyloxy group, n-heptylcarbonyloxy group, 3- A heptyl carbonyloxy group, n-octyl carbonyloxy group, etc. are mentioned. However, it is not limited to these. Examples of the optionally substituted arylcarbonyloxy group having 7 to 20 carbon atoms include a benzoyloxy group. However, it is not limited to these. Examples of the optionally substituted aralkylcarbonyloxy group having 8 to 20 carbon atoms include a benzylcarbonyloxy group. However, it is not limited to these. Examples of the optionally substituted heterocyclic group having 2 to 20 carbon atoms include a pyrrole group, an imidazole group, a piperidine group, and a morpholine group. However, it is not limited to these.

In the general formula (5), an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, an alkylthio group, an arylthio group, an aralkylthio group, an alkylsulfonyl group of the functional groups B ^{1 to} B ²⁴ , When an arylsulfonyl group, aralkylsulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, aralkylcarbonyloxy group or heterocyclic group is substituted, as substituents present in these functional groups B ¹ .about.B ^24, for example, a halogen atom, an acyl group, an alkyl group, a phenyl group, an alkoxy group, a halogenated alkyl group, halogenated alkoxy group, a nitro group, an amino group, alkylamino Group, alkylcarbonylamino group, arylamino group, arylcarbonylamino group, carbonyl group, alkoxycarbonyl group, alkylaminocarbonyl group, alkoxysulfonyl group, alkylthio group, carbamoyl group, aryloxycarbonyl group, cyano group, heterocyclic group, etc. Is mentioned. However, it is not limited to these. A plurality of these substituents may be present. When a plurality of substituents are present, they may be the same or different, and even in the same case, they may be the same or different. Moreover, substituents may be connected through a linking group.

In the case of a functional group whose terminal is an amino group, in the above general formula (5), the functional group B ^{1 to} B ²⁴ may be substituted with an amino group, an optionally substituted aminosulfonyl group, The substituents on the aminocarbonyl group may be a hydrogen atom; methyl group, ethyl group, n-propyl group, n-butyl group, sec-butyl group, n-pentyl group, n-hexyl group, 2-ethylhexyl group. Linear, branched or cyclic alkyl groups such as cyclohexyl group; aryl groups such as phenyl group and naphthyl group; aralkyl groups such as benzyl group and phenethyl group; acetyl group, ethylcarbonyl group, n-propylcarbonyl group, iso- Propylcarbonyl group, n-butylcarbonyl group, iso-butylcarbonyl group, sec-butylcarbonyl group, t-butylcarbonyl group, -Linear, branched or cyclic alkylcarbonyl groups such as pentylcarbonyl group, n-hexylcarbonyl group, cyclohexylcarbonyl group, n-heptylcarbonyl group, 3-heptylcarbonyl group, n-octylcarbonyl group; benzoyl group, naphthylcarbonyl An arylcarbonyl group such as a group; and an aralkylcarbonyl group such as a benzylcarbonyl group. However, the substituent is not limited thereto, and these substituents may be further substituted with a substituent. These substituents may be present in the number of 0, 1 or 2, and when 2 are present, they may be the same or different from each other, and even in the same type, they may be the same or different. Also good. Moreover, when there are two substituents, the substituents may be connected via a linking group.

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

Examples of the divalent metal as the metal M ² include Cu (II), Co (II), Zn (II), Fe (II), Ni (II), Ru (II), and Rh (II). , Pd (II), Pt (II), Mn (II), Mg (II), Ti (II), Be (II), Ca (II), Ba (II), Cd (II), Hg (II) , Pb (II), Sn (II) and the like. However, it is not limited to these. Examples of trivalent substituted metal atoms include Al-F, Al-Cl, Al-Br, Al-I, Fe-Cl, Ga-F, Ga-Cl, Ga-I, Ga-Br, In-F. , In-Cl, In-Br , In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Al-C 6 H 5, Al-C 6 H 4 (CH 3), In-C _{6 H 5, In-C 6} H 4 (CH 3), In-C 6 H 5, Mn (OH), Mn (OC 6 H 5), Mn [OSi _{(CH 3)} 3], Ru-Cl, etc. is Can be mentioned. However, it is not limited to these. Examples of tetravalent substituted metal atoms include CrCl ₂ , SiF ₂ , SiCl ₂ , SiBr ₂ , SiI ₂ , ZrCl ₂ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ , SnF ₂ , SnCl ₂ , SnBr ₂ , _{TiF 2, TiCl 2, TiBr 2} , Ge (OH) 2, Mn (OH) 2, Si (OH) 2, Sn (OH) 2, Zr (OH) 2, Cr (R1) 2, Ge (R 1) ₂ , Si (R ₁ ) ₂ , Sn (R ₁ ) ₂ , Ti (R ₁ ) ₂ {R ₁ represents an alkyl group, a phenyl group, a naphthyl group, or a derivative thereof}, Cr (OR ₂ ) ₂ , Ge (OR ₂ ) ₂ , Si (OR ₂ ) ₂ , Sn (OR ₂ ) ₂ , Ti (OR ₂ ) ₂ {R ₂ is an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group, a dialkyl group. Represents a alkoxysilyl group or a derivative thereof}, Sn (SR ₃ ) ₂ , Ge (SR ₃ ) ₂ {R ₃ represents an alkyl group, a phenyl group, a naphthyl group, or a derivative thereof}. However, it is not limited to these. Examples of the oxymetal include VO, MnO, TiO and the like. However, it is not limited to these. Specifically, trade names EEX COLOR IR-10A, EEX COLOR IR-12, EEX COLOR IR-14, TX-EX-906B, TX-EX-910B, TX-EX-902K (all Nippon Shokubai).

  These phthalocyanine dyes may be used alone or in a suitable mixture of two or more.

  Further, as phthalocyanine dyes that can absorb near infrared rays in the region of 900 nm to 920 nm and 1,000 nm to 1,020 nm, trade names include EEXCOLOR IR-10A, EEXCOLOR IR-12, and EEX. Color IR-14, TX-EX-906B, TX-EX-910B, TX-EX-902K, TX-EX-806B, TX-EX-802K (all manufactured by Nippon Shokubai Co., Ltd.) are preferable.

  You may add another near-infrared absorption pigment | dye to the near-infrared absorption film of this invention. Other near infrared absorbing dyes that can be used in combination include known cyanine dyes, polymethine dyes, squarylium dyes, porphyrin dyes, metal dithiol complex dyes, phthalocyanine dyes, diimonium dyes, inorganic oxide particles, etc. Can be mentioned.

  Furthermore, you may add the pigment | dye which absorbs visible light as needed. Examples of dyes that absorb visible light include cyanine, phthalocyanine, naphthalocyanine, porphyrin, tetraazaporphyrin, metal dithiol complex, squarylium, azurenium, diphenylmethane, triphenylmethane, oxazine, and azine. , Thiopyrylium, viologen, azo, azo metal complex, bisazo, anthraquinone, perylene, indanthrone, nitroso, indico, azomethine, xanthene, oxanol, indoaniline, quinoline Known dyes such as diketopyrrolopyrrole series and the like can be widely added.

  Moreover, in order to adjust the color tone of the thin film which consists of a near-infrared absorption film, you may add the visible light absorption pigment | dye for toning. The type of visible light absorbing dye for toning is not particularly limited. For example, 1: 2 chromium complex, 1: 2 cobalt complex, copper phthalocyanine, anthraquinone, diketopyrrolopyrrole and the like can be mentioned. Specifically, Orazole Blue GN, Orazole Blue BL, Orazole Red 2B, Orazole Red G, Orazole Black CN, Orazole Yellow 2GLN, Orazole Yellow 2RLN, Microlith DPP Red BK (all Ciba Specialty Chemicals Co., Ltd.).

<Additives other than heat-resistant resins and phthalocyanine dyes, water>
Although the near-infrared absorption film of this invention may consist only of a heat resistant resin and a phthalocyanine type pigment | dye, it may contain various additives further. Examples of additives include hindered phenol-based, phosphorus-based and sulfur-based antioxidants; light-resistant stabilizers, weather-resistant stabilizers, heat stabilizers and other stabilizers; reinforcing materials such as glass fibers and carbon fibers; phenyl UV absorbers such as salicylate, (2,2′-hydroxy-5-methylphenyl) benzotriazole, 2-hydroxybenzophenone; near infrared absorbers; tris (dibromopropyl) phosphate, triallyl phosphate, antimony oxide, etc. Flame retardants; Antistatic agents such as anionic, cationic and nonionic surfactants; Colorants such as inorganic pigments, organic pigments and dyes; Organic fillers and inorganic fillers; Resin modifiers; Organic fillers and inorganic fillers Agents, plasticizers, lubricants, antistatic agents, flame retardants, and the like. Moreover, after pre-blending the molded product raw material with a conventionally known mixer such as an omni mixer, the resulting mixture may be added. In this case, a mixer is not specifically limited, For example, you may use conventionally well-known mixers, such as extruders, such as a single screw extruder and a twin screw extruder, and a pressure kneader.

  The content of the additive in the near-infrared absorbing film is preferably 5% by weight or less, more preferably 2% by weight or less, and further preferably 0.5% by weight or less.

  The near-infrared absorbing film of the present invention may further contain water. The water content in the near-infrared absorbing film is preferably 5,000 ppm or less, more preferably 1,000 ppm or less, and even more preferably 500 ppm or less. If the water content is 5,000 ppm or more, side effects such as hydrolysis involving water may occur.

<Molding method>
The method for producing the near-infrared absorbing film of the present invention is not particularly limited as long as the heat-resistant resin and the phthalocyanine dye are sufficiently mixed, and the conditions, order, etc. when mixing them are not particularly limited.

<Melt extrusion method>
Moreover, it is preferable that the near-infrared absorption film which concerns on this invention shape | molds a heat resistant resin and a phthalocyanine type pigment | dye by the melt extrusion method. If a near-infrared absorption film is shape | molded by the melt-extrusion method, a manufacturing cost will be low and production efficiency is good rather than the case where it shape | molds by the cast coating method.

  Below, the method of shape | molding the near-infrared absorption film containing a heat resistant acrylic resin by a melt extrusion method is demonstrated in detail. In addition, about a near-infrared absorption sheet, it can shape | mold by the shaping | molding method similar to a near-infrared absorption film.

  Examples of the melt extrusion method include a T-die method and an inflation method. The molding temperature at that time may be appropriately adjusted according to the glass transition temperature of the film raw material, and is not particularly limited. For example, the temperature is preferably 150 ° C. or higher and 350 ° C. or lower, and more preferably 200 ° C. or higher and 300 ° C. or lower.

  When forming a film by the T-die method, a roll-shaped film is obtained by attaching a T-die to the tip of a known single-screw extruder or twin-screw extruder and winding the film extruded into a film shape. Can do. Under the present circumstances, it is also possible to carry out uniaxial stretching by adjusting the temperature of a winding roll suitably, and extending | stretching in an extrusion direction. Also, simultaneous biaxial stretching, sequential biaxial stretching, and the like can be performed by stretching the film in a direction perpendicular to the extrusion direction.

  In order to produce a film from the above heat-resistant acrylic resin, for example, a film raw material is pre-blended with a conventionally known mixer such as an omni mixer, and then the obtained mixture is extruded and kneaded. In this case, the mixer used for extrusion kneading is not particularly limited. For example, a conventionally known mixer such as a single screw extruder, an extruder such as a twin screw extruder, or a pressure kneader can be used.

  The near-infrared absorbing film of the present invention may be either an unstretched film or a stretched film. In the case of a stretched film, either a uniaxially stretched film or a biaxially stretched film may be used. In the case of a biaxially stretched film, either a simultaneous biaxially stretched film or a sequential biaxially stretched film may be used. In the case of biaxial stretching, the mechanical strength is improved and the film performance is improved. When the lactonized polymer is mixed with another thermoplastic resin, an increase in retardation can be suppressed even when stretched, and a film having optical isotropy can be obtained.

  In the manufacturing method of the near-infrared absorption film of this invention, it is preferable that extending | stretching temperature is the glass transition temperature vicinity of the lactonization polymer which is a film raw material. Specifically, it is preferably in the range of (glass transition temperature−30 ° C.) or more and (glass transition temperature + 100 ° C.), and in the range of (glass transition temperature−20 ° C.) to (glass transition temperature + 80 ° C.). More preferably, it is within. If the stretching temperature is less than (glass transition temperature-30 ° C.), a sufficient stretching ratio may not be obtained. On the contrary, when the stretching temperature exceeds (glass transition temperature + 100 ° C.), the polymer flows, and stable stretching may not be performed.

  In the manufacturing method of the near-infrared absorbing film of the present invention, the draw ratio defined by the area ratio is preferably in the range of 1.1 to 25 times, and in the range of 1.3 to 10 times. More preferably. If the draw ratio is less than 1.1 times, the toughness accompanying the drawing may not be improved. On the other hand, when the draw ratio exceeds 25 times, the effect of increasing the draw ratio may not be recognized.

  In the method for producing a near-infrared absorbing film of the present invention, the stretching speed is preferably in the range of 10% / min to 20,000% / min in one direction, preferably 100% / min to 10,000%. More preferably, it is within the range of / min or less. When the stretching speed is less than 10% / min, it takes time to obtain a sufficient stretching ratio, and the production cost may increase. On the other hand, when the stretching speed exceeds 20,000% / min, the stretched film may be broken.

  The near-infrared absorbing film of the present invention can be subjected to heat treatment (annealing) or the like after the stretching treatment in order to stabilize its optical isotropy and mechanical properties. The conditions for the heat treatment may be appropriately selected similarly to the conditions for the heat treatment performed on a conventionally known stretched film, and are not particularly limited. In addition, about the said near-infrared absorption sheet, the heat processing similar to a near-infrared absorption film can be performed.

<Properties of near-infrared absorbing film>
The thickness of the near-infrared absorbing film is preferably 5 μm or more and 200 μm or less, and more preferably 10 μm or more and 100 μm or less. When the thickness is less than 5 μm, not only the strength of the film is lowered, but also when the durability test is performed by sticking to other parts, the crimp may be increased. The thickness of the near-infrared absorbing sheet is preferably more than 200 μm and 5 mm or less, and more preferably 500 μm or more and 3 mm or less. If it exceeds 5 mm, the transparency of the sheet may be lowered.

  The surface tension of the near-infrared absorbing film is preferably 40 mN / m or more, more preferably 50 mN / m or more, and further preferably 55 mN / m or more. When the surface wetting tension is at least 40 mN / m or more, the adhesive strength between the film made of the lactonized polymer and other parts is further improved. In order to adjust the surface wetting tension, for example, corona discharge treatment, ozone spraying, ultraviolet irradiation, flame treatment, chemical treatment, and other conventionally known surface treatments can be performed. The sheet preferably has the same surface wetting tension as the film.

  The near-infrared absorbing film preferably has a content of foreign matter such as polymer gel or polymer carbide having an average particle diameter of 50 μm or more with respect to 100 g of the near-infrared absorbing film. Thereby, the near-infrared absorption film of this invention turns into an optical film which has the outstanding optical characteristic. For example, when an acrylic resin having a lactone ring structure is used as a molding material in an optical application, if the content of foreign matter exceeds 100 with respect to 100 g of the near infrared absorbing film, it may not be suitable for an optical application. The content of foreign matter is most preferably 0 with respect to 100 g of the near-infrared absorbing film.

<Liquid crystal display device>
In addition, the liquid crystal display device of the present invention includes at least one layer made of the near-infrared absorbing film.

  The near-infrared absorbing film can be suitably used as a member for a liquid crystal display device, and is particularly useful as a polarizing plate protective film, a retardation film, a diffusion film, etc., which will be described later.

<Polarizing plate protective film>
Moreover, the polarizing plate protective film of this invention consists of the said near-infrared absorption film.

  Since the polarizing plate is closest to the light source in the liquid crystal display device, light emitted from the light source is directly incident on the polarizing plate. Therefore, the polarizing plate protective film is easily deteriorated. However, when the polarizing plate protective film is made of the near infrared absorbing film, the polarizing plate protective film is hardly deteriorated due to the durability of the near infrared absorbing film.

  In addition to high transparency and high optical isotropy, optical protective films such as polarizing plates have low optical elastic modulus, heat resistance, light resistance, high surface hardness, high mechanical strength, and wavelength dependence of retardation. Characteristics such as a small phase difference and a small dependence of the phase difference on the incident angle are required.

<Phase difference film>
Moreover, the retardation film of the present invention is composed of the above-mentioned near-infrared absorbing film.

  In addition to high transparency and high optical isotropy, the retardation film has low optical elastic modulus, heat resistance, light resistance, high surface hardness, high mechanical strength, large retardation, and wavelength dependence of retardation. Characteristics such as a small size and a small dependency of the phase difference on the incident angle are required.

<Diffusion film>
Moreover, the diffusion film of the present invention is composed of the above-mentioned near-infrared absorbing film.

  In addition to high transparency and high optical isotropy, the diffusion film is required to have properties such as low optical elastic modulus, heat resistance, light resistance, high surface hardness, and high mechanical strength. In particular, the diffusion film has a higher heat resistance than the polymethyl methacrylate (PMMA) contained in the current optical film in the resin contained therein, thereby reducing the optical characteristics due to molding distortion. It is hoped to suppress it.

  Thus, the near-infrared absorbing film according to the present invention includes, for example, a heat-resistant resin having a glass transition temperature of 110 ° C. or more and a phthalocyanine-based dye having a maximum absorption wavelength value of 900 to 1050 nm in the near-infrared region. If it has the structure of including, the specific structure will not be specifically limited.

  In addition, the near-infrared absorbing film according to the present invention may have, for example, a structure including a heat-resistant acrylic resin having a ring structure in the main chain and a glass transition temperature of 110 ° C. or higher, and a phthalocyanine dye.

  In addition, the near-infrared absorbing film according to the present invention may have a structure in which a main chain has a lactone ring structure, for example.

  Moreover, the structure of shape | molding by the melt extrusion method may be sufficient as the near-infrared absorption film which concerns on this invention, for example.

  In addition, the liquid crystal display panel according to the present invention may have a configuration in which, for example, a near-infrared absorbing film is used in at least one layer.

  Moreover, the structure which uses a near-infrared absorption film may be sufficient as the polarizer protective film which concerns on this invention, for example.

  Moreover, the structure which uses a near-infrared absorption film may be sufficient as the phase difference film which concerns on this invention, for example.

  Moreover, the structure which uses a near-infrared absorption film may be sufficient as the diffusion film which concerns on this invention, for example.

  In addition, this invention is not limited to embodiment mentioned above, A various change is possible in the range shown to the claim. That is, embodiments obtained by combining technical means appropriately changed within the scope of the claims are also included in the technical scope of the present invention.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these. Hereinafter, for convenience, “parts by weight” will be simply referred to as “parts”, and “liters” will be simply referred to as “L”.

[Method for producing pellets made of polymer of heat-resistant resin]
A 30 L reaction kettle equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing pipe was charged with 20 parts of methyl 2- (hydroxymethyl) acrylate, 80 parts of methyl methacrylate, and 100 parts of toluene while passing nitrogen. The temperature was raised to ° C and refluxed. Thereafter, 0.1 part of t-amylperoxyisonononate (trade name: Lupazole 570, manufactured by Atofina Yoshitomi Co., Ltd.) was added as a polymerization initiator, and at the same time, 0.2 part of t-amylperoxyisonononate and toluene were added. Solution polymerization was performed at 105 to 110 ° C. while dropping a solution consisting of 1 part over 2 hours. The solution was aged over 4 hours. To the obtained solution, 0.1 part of a mixture of stearyl phosphate and distearyl phosphate (trade name: Phoslex A-18, manufactured by Sakai Chemical Industry Co., Ltd.) is added, and the mixture is circulated at 100 to 110 ° C. for 5 hours under reflux. A polycondensation reaction was performed. Next, the obtained solution was converted into a bent type screw twin screw extruder having a barrel temperature of 260 ° C., a rotation speed of 100 rpm, a degree of vacuum of 13.3 to 400 hPa (10 to 300 mmHg), a rear vent number of 1 and a forevent number of 4 ( A transparent pellet of a lactonized polymer was obtained by introducing it into a resin having a processing rate of 2.0 kg / h in terms of resin amount into Φ = 30 mm, L / D = 42).

  And the weight average molecular weight of the said lactonized polymer and the glass transition temperature were measured on condition of the following.

<Measurement method of weight average molecular weight>
The weight average molecular weight of the lactonized polymer was obtained by polystyrene conversion of GPC (GPC system manufactured by Tosoh Corporation). As a result, the weight average molecular weight was 150,000.

<Measuring method of glass transition temperature>
The thermal analysis of the resin was performed using DSC (trade name: DSC-8230, manufactured by Rigaku Corporation) under the conditions of about 10 mg of sample, a heating rate of 10 ° C./min, and a nitrogen flow of 50 cc / min. The glass transition temperature (Tg) of the polymer of the heat resistant resin was determined by the midpoint method according to ASTM-D-3418. As a result, the glass transition temperature (Tg) was 130 ° C.

[Example 1]
A mixture produced by kneading 100 parts of the above pellets and 0.1 part of a phthalocyanine dye (trade name: EX-806B, manufactured by Nippon Shokubai Co., Ltd.) was used as follows, using an extruder having a cylinder diameter of 20 mm. Extrusion was performed under the conditions described above to produce a film having a thickness of 100 μm.
Die: temperature 260 ° C, width 1,000mm
Temperature of three rolls with gloss: first roll 125 ° C., second roll 142 ° C., third roll 118 ° C.
Take-off speed: 1.5 m / min The near-infrared transmittance, visible light transmittance, and photoelastic coefficient of the film were measured under the following conditions. Moreover, the durability (heat resistance, heat and moisture resistance) of the film was measured under the following conditions.

<Near-infrared transmittance>
The near-infrared transmittance of the film is a minimum at wavelengths of 800 to 1,100 nm by measuring a transmission spectrum of 350 to 1,100 nm using a spectrophotometer (trade name: UV-3100, manufactured by Shimadzu Corporation). The transmittance was obtained.

<Visible light transmittance>
The visible light transmittance of the above film was measured using a spectrophotometer (trade name: UV-3100, manufactured by Shimadzu Corporation), measured for a transmission spectrum of 350 to 1,100 nm, and average transmission at a wavelength of 450 to 700 nm. Obtained by rate.

<Photoelastic coefficient>
The photoelastic coefficient of the film was determined from the slope of the photoelastic modulus at 400 nm at various tensile strengths using an ellipsometer (manufactured by JEOL Ltd.).

<Heat resistance>
The film was allowed to stand in a dryer at 100 ° C. for 20 hours, and near-infrared transmittance, visible light transmittance, and rate of change in photoelasticity before and after the drying were determined. Moreover, the said film was made into the size of 10 cm x 10 cm, and the change rate of the size before and after the drying was calculated | required. Here, the rate of change (%) was obtained by the following equation.
Rate of change (%) = (value before drying / value after drying) × 100
<Heat and heat resistance>
The film was allowed to stand in a constant temperature and humidity chamber at 80 ° C. and 95% RH for 20 hours, and the near infrared transmittance, the visible light transmittance, and the rate of change in photoelasticity before and after the treatment were determined. Moreover, the said film was made into the size of 10 cm x 10 cm, and the change rate of the size before and after the process was calculated | required.

[Example 2]
The same operation as in Example 1 was performed except that 0.1 part of phthalocyanine dye (trade name: EX-806B, manufactured by Nippon Shokubai Co., Ltd.) was changed to 0.3 part.

Example 3
Example 1 except that 0.1 part of phthalocyanine dye (trade name: EX-806B) was changed to 0.1 part of phthalocyanine dye (trade name: EX-802K, manufactured by Nippon Shokubai Co., Ltd.) Was performed.

Example 4
Example 1 except that 0.1 part of phthalocyanine dye (trade name: EX-806B) was changed to 0.3 part of phthalocyanine dye (trade name: EX-802K, manufactured by Nippon Shokubai Co., Ltd.) Was performed.

Example 5
0.1 part of phthalocyanine dye (trade name: EX-806B), 0.3 part of phthalocyanine dye (trade name: EX-802K) and 0.2 part of phthalocyanine dye (trade name: EX-806B) The same operation as in Example 1 was performed except that the mixture was changed to a mixture.

[Comparative Example 1]
Example 1 except that 0.1 part of phthalocyanine dye (trade name: EX-806B) was changed to 0.3 part of diimonium dye (trade name: EX-991K, manufactured by Nippon Shokubai Co., Ltd.) Was performed.

  Table 1 summarizes the near-infrared transmittance, visible light transmittance, and photoelastic modulus of the films measured in Examples 1 to 5 and Comparative Example 1.

  As shown in Table 1, when Examples 1 to 5 and Comparative Example 1 are compared, the near-infrared transmittance of Examples 1 to 5 mixed with a phthalocyanine dye is that of Comparative Example 1 mixed with a diimonium dye. The result was smaller than near infrared transmittance. That is, it has been clarified that the near-infrared absorbing film according to the present invention hardly transmits near-infrared light by absorbing near-infrared light.

  Tables 2 and 3 summarize the durability (heat resistance and heat and moisture resistance) of the films measured in Examples 1 to 5.

  As shown in Table 2, the near-infrared transmittance and visible light transmittance of Examples 1 to 5 after being left in a drier at 100 ° C. for 20 hours did not change. On the other hand, the near-infrared transmittance of Comparative Example 1 increased and the visible light transmittance decreased. Moreover, as shown in Table 3, the near-infrared transmittances of Examples 1 to 5 after standing for 20 hours in a constant temperature and humidity chamber at 80 ° C. and 95% RH increased by 0 to 5%, and visible light The transmittance decreased by 0 to 5%. On the other hand, the near-infrared transmittance of Comparative Example 1 increased by 10%, and the visible light transmittance decreased by 20%. That is, it was revealed that the near-infrared absorbing film according to the present invention is excellent in heat resistance and durability.

  As described above, the present invention provides a near-infrared absorbing film excellent in heat resistance and durability that can absorb near-infrared rays emitted from light sources of plasma display panels and liquid crystal panels, and a method for producing a near-infrared absorbing film. It becomes possible to provide. Therefore, the present invention can be widely used in the fields of plasma display, flat panel display such as liquid crystal.

Claims (8)

  A near-infrared absorbing film comprising a heat-resistant resin having a ring structure in a main chain and a glass transition temperature of 110 ° C. or higher and 170 ° C. or lower and a phthalocyanine dye.   The near-infrared absorbing film according to claim 1, wherein the heat-resistant resin is a heat-resistant acrylic resin.   The near-infrared absorbing film according to claim 1 or 2, wherein the ring structure is a lactone ring structure.   The near-infrared absorption film of any one of Claims 1-3 is shape | molded by the melt extrusion method, The manufacturing method of the near-infrared absorption film characterized by the above-mentioned.   A liquid crystal display device comprising at least one layer comprising the near-infrared absorbing film according to claim 1.   A polarizing plate protective film comprising the near-infrared absorbing film according to claim 1.   A retardation film comprising the near-infrared absorbing film according to claim 1.   A diffusion film comprising the near-infrared absorbing film according to claim 1.