JP2007169658A - Near infrared-absorbing coating film and near infrared-absorbing resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a near infrared-absorbing coating film and a near infrared-absorbing resin composition effective for suppressing the deterioration of a near infrared-absorbing pigment and having excellent weather resistance. <P>SOLUTION: The near infrared-absorbing coating film contains a near infrared-absorbing pigment having a peak absorption wavelength at 780-1,200 nm and has a near infrared absorptivity residual ratio of ≥50% after the light irradiation for 48 hours in an accelerated weathering test by an ultraviolet auto fade meter. The near infrared-absorbing coating film is made of a near infrared-absorbing resin composition containing a polymer obtained by polymerizing a monomer component containing a specific monomer, and the near infrared-absorbing pigment is at least one kind of pigment selected from phthalocyanine pigment, naphthalocyanine pigment, anthraquinone pigment and naphthoquinone pigment. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a near-infrared absorbing coating film and a near-infrared absorbing resin composition.

The near-infrared absorbing resin composition can form a film or coating film having the property of absorbing near-infrared rays, which is a heat ray, and such a film or coating film shields the heat ray to prevent a temperature rise. In recent years, it has attracted attention as an absorbent film from the viewpoint of energy saving. For example, a heat ray absorbing film formed from a near-infrared absorbing resin composition is attached to a window glass or the like, sandwiched between two pieces of glass, or a window glass with a near-infrared absorbing resin composition as a coating agent. It is used for buildings, houses, vehicles, arcades, greenhouses, etc.

Such a near-infrared absorbing resin composition is usually prepared by containing a heat ray absorbent and a binder resin, and inorganic fine particles and organic dyes are used as the heat ray absorbent. However, the inorganic fine particles have a problem that the near-infrared absorption performance at a wavelength of 1000 nm or less is low and the temperature rise cannot be sufficiently prevented from the viewpoint of energy saving. In addition, with organic dyes, near-infrared absorption performance is gradually lost due to sunlight in the heat-absorbing film, so the weather resistance of the heat-absorbing film is not sufficient, and research for sustaining near-infrared absorption performance There was room.

Patent Document 1 discloses a laminate including a transparent substrate, an ultraviolet shielding layer, and a heat ray shielding layer containing a heat ray shielding substance. In this laminate, the ultraviolet ray shielding layer is formed closer to the light incident side than the heat ray shielding layer, thereby suppressing deterioration of the heat ray shielding material contained in the heat ray shielding layer. However, by devising the heat ray shielding layer itself, there has been room for research to maintain the heat ray shielding performance more simply and reliably by suppressing the deterioration of the heat ray shielding material.
JP 2000-177064 A

The present invention has been made in view of the above, and a near-infrared-absorbing coating film and a near-infrared-absorbing resin composition that can suppress deterioration of the near-infrared absorbing dye and exhibit excellent weather resistance. The purpose is to provide goods.

The present invention is a near-infrared absorbing coating film containing a near-infrared absorbing dye having a maximum absorption wavelength at 780 nm to 1200 nm, and absorbs near-infrared light after 48 hours of light irradiation in an accelerated weather resistance test using an ultraviolet autofade meter. It is a near-infrared absorptive coating film whose performance remaining rate is 50% or more.

While the inventors have studied various near-infrared absorbing resin compositions that form a near-infrared-absorbing coating film and a heat-absorbing film, the water contained in such a near-infrared-absorbing coating film is near-infrared. Focusing on the fact that it is one of the causes of degrading the absorptive dye, it was found that reducing the water content in the near-infrared absorptive coating can suppress the degradation of the near-infrared absorptive dye, The inventors have come up with the idea that the above problems can be solved brilliantly. As a result, the laminate having near infrared absorption performance can be used for various applications, and the present invention has been achieved. The present invention is described in detail below.

The near-infrared absorbing coating film of the present invention is a coating film containing a near-infrared absorbing pigment having a maximum absorption wavelength at 780 nm to 1200 nm. Such a near-infrared absorptive coating film is formed by the near-infrared absorptive resin composition containing the said near-infrared absorptive pigment | dye and binder resin. The said near-infrared absorptive pigment | dye is a pigment | dye which has a maximum absorption wavelength in 780-1200 nm, and may be used independently and may use 2 or more types together. When two or more types having different near-infrared absorption characteristics are used in combination, the near-infrared absorption effect may be improved. In addition, near-infrared absorptivity is used by the meaning equivalent to heat ray absorptivity. Moreover, the said binder resin makes a polymer essential, is comprised by containing an organic solvent and an unsaturated monomer as needed, may be used independently, and may use 2 or more types together.

In the present invention, as the near-infrared absorbing dye, it is preferable to use a dye having solubility in an organic solvent, that is, an organic solvent-soluble near-infrared absorbing dye. If the dye is soluble in the organic solvent, it can be easily dissolved in the binder resin solution, so that the coating agent can be easily prepared. On the other hand, if the dye is poorly soluble, it becomes difficult to mix with the binder resin solution, so that it is difficult to prepare a coating agent. As the solubility in an organic solvent, it is preferable to use a near-infrared absorbing dye having a solubility of 0.01% by mass or more based on 100% by mass of the organic solvent. The organic solvent in the organic solvent solubility is not particularly limited, and examples thereof include aromatic solvents such as toluene and xylene; alcohol solvents such as iso-propyl alcohol, n-butyl alcohol, propylene glycol methyl ether, and dipropylene glycol methyl ether. Ester solvents such as butyl acetate, ethyl acetate and cellosolve acetate; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; one or more of dimethylformamide and the like.

Examples of the near-infrared absorbing dye include phthalocyanine dyes, naphthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, etc. Among them, the near-infrared absorbing performance and organic solvent solubility are excellent. Therefore, it is preferable to use a phthalocyanine dye.

As used herein, phthalocyanine-based is a phthalocyanine, phthalocyanine complex, or phthalocyanine and phthalocyanine complex in which one or more substituents of OR, SR, NHR, or NRR ′ are substituted on the benzene ring of the phthalocyanine skeleton. It has more than one. R and R ′ are the same or different and each represents a phenyl group which may have a substituent, an alkyl group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. In addition, it is preferable that one of the substituents is phthalocyanine substituted with NHR.

In the present invention, the near infrared absorbing dye is represented by the following general formula (2);

(In the formula, α is the same or different and represents SR ¹ , OR ² , NHR ³ or a halogen atom, and NHR ³ is essential. R ¹ , R ² and R ³ are the same or different and are each a substituent. Represents a phenyl group, an alkyl group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, β is the same or different and represents SR ¹ , OR ² or a halogen atom, and SR ¹ OR ² is essential, provided that at least one of α and β requires a halogen atom or OR ^2. M represents a metal-free, metal, metal oxide or metal halide). It is preferable that it is a compound represented. Thereby, the effect of this invention can fully be exhibited.

In the general formula (2), examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. N-pentyl group, isopentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group A straight chain or branched alkyl group such as a group, 1,4-dimethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group; cyclohexyl And cyclic alkyl groups such as groups. Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenethyl group. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, It is preferable that it is a fluorine atom.

The phenyl group, the alkyl group having 1 to 20 carbon atoms, or the aralkyl group having 7 to 20 carbon atoms in R ¹ , R ² and R ³ may have one or more substituents. Examples of such substituents include halogen atoms, acyl groups, alkyl groups, alkoxy groups, halogenated alkoxy groups, nitro groups, amino groups, alkylamino groups, alkylcarbonylamino groups, arylamino groups, and arylcarbonylamino groups. , A carbonyl group, an alkoxycarbonyl group, and the like.

In M in the above general formula (2), the metal-free means an atom other than a metal, for example, two hydrogen atoms. Specifically, a structure in which a hydrogen atom is bonded to two opposing nitrogen atoms that may have a substituent, present in the central portion of the phthalocyanine structure. Examples of the metal include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Examples of the metal oxide include titanyl and vanadyl. Examples of the metal halide include aluminum chloride, indium chloride, germanium chloride, tin chloride, and silicon chloride. M is preferably a metal, a metal oxide or a metal halide, and specific examples include nickel, cobalt, copper, zinc, iron, vanadyl, dichlorotin and the like. More preferred are zinc, cobalt, vanadyl and dichlorotin.

A preferred form of the compound represented by the general formula (2) is that 4 to 8 of 8 βs are the same or different and represent SR ¹ or OR ² . More preferably, all eight βs are the same or different and represent SR ¹ or OR ² . Examples of such near-infrared absorbing dyes include ZnPc (PhS) ₈ (PhNH) ₃ F ₅ , ZnPc (PhS) ₈ (PhNH) ₄ F ₄ , ZnPc (PhS) ₈ (PhNH) ₅ F ₃ , ZnPc (PhS) ₈ (PhCH ₂ NH) ₄ F ₄ , ZnPc (PhS) ₈ (PhCH ₂ NH) ₅ F ₃ , ZnPc (PhS) ₈ (PhCH ₂ NH) ₆ F ₂ , CuPc (PhS) ₈ (PhNH) ₇ F, CuPc (PhS) ₈ (PhNH) ₆ F ₂ , CuPc (PhS) ₈ (PhNH) ₅ F ₃ , VOPc (PhO) ₈ (PhCH ₂ NH) ₅ F ₃ , VOPc (PhO) ₈ (PhCH ₂ NH) ₆ F ₂ , VOPc (PhO) ₈ (PhCH ₂ NH) ₈ , VOPc (PhS) ₈ (PhCH ₂ NH) ₈ , VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO } ₄ { _{h (CH 3) CHNH} 3} F, VOPc (2,5-Cl 2 PhO) 8 {2,6- (CH 3) 2 PhO} 4 {Ph (CH 2 NH) 4, CuPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {Ph (CH ₂ NH) ₄ , CuPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ , VOPc (4-CNPhO) ₈ {2,6-Br ₂ -4- (CH ₃ ) PhO} ₄ {Ph (CH ₃ ) CHNH} ₄ , ZnPc (2,6-Cl ₂ PhO) ₈ {2,6 A phthalocyanine compound represented by an abbreviation of —Br ₂ -4- (CH ₃ ) PhO} ₄ {Ph (CH ₃ ) CHNH} ₃ F; Among these compounds, 4 of 8 α's are the same or different and represent OR ² or a halogen atom. For example, ZnPc (PhS) ₈ (PhNH) ₃ F ₅ , ZnPc (PhS) ₈ ( PhNH) ₄ F ₄ , ZnPc (PhS) ₈ (PhCH ₂ NH) ₄ F ₄ , VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {Ph (CH ₃ ) CHNH} ₃ F, VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {Ph (CH ₂ NH) ₄ , CuPc (2,5-Cl ₂ PhO) ₈ { 2,6- (CH ₃ ) ₂ PhO} ₄ {Ph (CH ₂ NH) ₄ , CuPc (PhS) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ , VOPc (4- CNPhO) ₈ {2,6-Br ₂ -4- (CH ₃ ) PhO} ₄ {Ph (CH ₃ ) CHNH} ₄ , ZnPc (2,6-Cl ₂ PhO) ₈ {2,6-Br ₂ -4- (CH ₃ ) PhO} ₄ {Ph (CH ₃ ) CHNH} ₃ F And compounds represented by the formula.

As the usage-amount of the said near-infrared absorptive pigment | dye, it is preferable to set it as 0.0005-20 weight part with respect to 100 weight part of binder resins, for example. If the amount is less than 0.0005 parts by weight, the near-infrared absorbing coating film formed from the near-infrared absorbing resin composition may not exhibit sufficient near-infrared absorbing performance. There exists a possibility that the physical property of an absorptive coating film may fall. More preferably, it is 0.0015-10 weight part, More preferably, it is 0.002-7 weight part. Moreover, it is preferable to set suitably according to the thickness of a near-infrared absorptive coating film, for example, in thickness 10 micrometers, it is preferable to set it as 0.5-20 weight part, and setting it as 1.0-10 weight part. More preferred. When it is set as the near-infrared absorptive coating film of thickness 3mm, it is preferable to set it as 0.002-0.06 weight part, and it is more preferable to set it as 0.005-0.03 weight part. In thickness 10mm, it is preferable to set it as 0.0005-0.02 weight part, and it is more preferable to set it as 0.0010-0.01 weight part. Furthermore, as a weight contained per unit area of a near-infrared absorptive coating film, it is preferable to set it as 0.01-2.4 g / m < ² >, for example. If it is less than 0.01 g / m ² , the action of the near-infrared absorbing dye may not be sufficiently exerted, and if it exceeds 2.4 g / m ² , the production cost of the near-infrared absorbing coating film may increase. There is. More preferably 0.05 to 1.0 g / m ^2.

In this invention, it is preferable that the water absorption rate of a coating film is 2 mass% or less. Moreover, it is so preferable that the water absorption rate of a coating film is close to 0 mass%. When the water absorption rate of the coating film exceeds 2% by mass, the content of water in the near-infrared absorbing film cannot be reduced so that deterioration of the near-infrared absorbing dye can be sufficiently suppressed. The effect of the present invention may not be exhibited. More preferably, it is 1 mass% or less, More preferably, it is 0.8 mass% or less. The water absorption rate of the coating film refers to a coating film (coating film) formed from a near-infrared absorbing resin composition containing a near-infrared absorbing dye, a curing agent, and various additives as required in addition to the binder resin. The weight ratio (mass%) which increases by containing water with progress of time is shown. The water absorption rate of the coating film is calculated using the following formula by the following measurement method.

Method for measuring water absorption rate of coating film About 3 cm x 3 cm of coating film with a thickness of 1 mm is dried at 80 ° C for 12 hours under reduced pressure condition of 30 mPa or less, and then the weight (W ₀ ) is measured. Value. Next, it is immersed in water and stored at room temperature (25 ° C.) for 20 days, then taken out and measured for weight (W ₁ ). The water absorption rate of the coating film is calculated using the following formula.
Water absorption rate of coating film (mass%) = {(W ₁ −W ₀ ) / W ₀ } × 100

In the present invention, for measuring the water absorption rate of the coating film, for example, after coating the prepared near-infrared absorbing resin composition on a glass substrate so that the dry film thickness is 1 mm, the conditions shown below are applied. By using a coating film that is dried and peeled off from the substrate, the water absorption rate of the coating film can be measured under certain conditions. In the present invention, the curing agent has two embodiments, a case where a cured coating film is obtained by crosslinking a resin and a curing agent, and a case where a drying coating film is formed without a curing agent. When a cured coating film is formed by crosslinking, a near-infrared absorbing resin composition is prepared by blending a curing agent as shown below, and the coating film is prepared under the following conditions and used for measuring the water absorption rate. This makes it possible to measure the water absorption rate of the coating film under certain conditions. The conditions for preparing a coating film (coating film) for measuring the water absorption rate are specifically shown below.
(1) No curing agent (lacquer)
Drying conditions: 3 minutes at 80 ° C. and 7 days at 50 ° C. (2) Curing agent: Type of isocyanate compound curing agent: “Sumijour N3200” (trade name) manufactured by Sumitomo Bayer Urethane Co., Ltd.
Curing agent blending amount: isocyanate group of curing agent / hydroxyl group of binder resin = 1/1 (molar ratio) Curing condition: 3 minutes at 80 ° C., 7 days at 50 ° C. (3) Curing agent: aminoplast resin curing agent Type: “Cymel 325” (trade name), manufactured by Mitsui Cytech
Curing catalyst: “Catalyst 296-9” (trade name), manufactured by Mitsui Cytec
Curing agent content: binder resin / curing agent / curing catalyst = 80/19/1 (solid content weight ratio)
Curing conditions: 30 minutes at 110 ° C

In the present invention, the binder resin preferably has a glass transition temperature (Tg) of −80 to 160 ° C. As a result, the weather resistance of the binder resin itself is improved, and in combination with the suppression of the water content in the near infrared absorbing coating film, the near infrared absorbing performance of the near infrared absorbing coating film is sustained. The weather resistance and physical properties of the near-infrared absorbing coating film itself are further improved. Preferably, it is -50-130 degreeC, More preferably, it is 20-110 degreeC, More preferably, it is 40-100 degreeC.

Examples of the binder resin include (meth) acrylic resin, (meth) acrylic urethane resin, polyvinyl chloride resin, polyvinylidene chloride resin, melamine resin, urethane resin, styrene resin, and alkyd resin. Modification of resins, phenolic resins, epoxy resins, polyester resins, (meth) acrylic silicone resins, alkylpolysiloxane resins, silicone resins, silicone alkyd resins, silicone urethane resins, silicone polyester resins, silicone acrylic resins, etc. Examples include fluororesins such as silicone resins, polyvinylidene fluoride, and fluoroolefin vinyl ether polymers. Thermoplastic resins may be used, and thermosetting resins, moisture curable resins, UV curable resins, electron beam curable resins, etc. Resin may be usedAlso, organic binder resins such as synthetic rubber such as ethylene-propylene copolymer rubber, polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber or natural rubber; silica sol, alkali silicate, silicon alkoxide and their (hydrolysis) Conventionally known binder resins such as inorganic binders such as condensates and phosphates may be mentioned. These may be used alone or in combination of two or more. Among these, (meth) acrylic resins, (meth) acrylic urethanes can be formed by drying at a relatively low temperature to form a near-infrared absorbing coating film and having excellent weather resistance of the binder resin itself. Resin, (meth) acrylic silicone resins, silicone resins, silicone alkyd resins, silicone urethane resins, silicone polyester resins, modified silicone resins such as silicone acrylic resins, and fluorine resins such as polyvinylidene fluoride and fluoroolefin vinyl ether polymers Is preferred. More preferred is a (meth) acrylic resin. Note that acrylic resins and methacrylic resins are also referred to as acrylic resins.

Among the (meth) acrylic resins, in the present invention, the binder resin is represented by the following general formula (1);

(Wherein R ⁴ represents a hydrogen atom or a methyl group; Z represents a hydrocarbon group having 4 to 25 carbon atoms). It is preferable to use a polymer obtained as a binder resin. One type of monomer represented by the general formula (1) may be used, or two or more types may be used in combination. Thereby, in addition to improving the durability of the near-infrared absorbing pigment, the weather resistance of the binder resin itself is also excellent, so that the weather resistance of the near-infrared absorbing coating film can be further improved. In this case, from the near-infrared absorbing resin composition containing a polymer obtained by polymerizing the monomer component containing the monomer represented by the general formula (1). It will be formed.

In the general formula (1), examples of the hydrocarbon group having 4 to 25 carbon atoms represented by Z include alicyclic hydrocarbon groups such as cyclohexyl group, methylcyclohexyl group, and cyclododecyl group; butyl group, isobutyl A linear or branched alkyl group such as a group, tert-butyl group, 2-ethylhexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, pentadecyl group, octadecyl group; Examples include polycyclic hydrocarbon groups such as isobornyl group. Among these, an alicyclic hydrocarbon group, a branched alkyl group, and a linear alkyl group having 6 or more carbon atoms are preferable. More preferably, it is an alicyclic hydrocarbon group having 6 or more carbon atoms.

Examples of the monomer represented by the general formula (1) include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, isobutyl (meth) ) Acrylate, tert-butyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.

As the usage-amount of the monomer represented by the said General formula (1), when all the monomer components are 100 mass%, it is preferable to set it as 30 mass% or more, for example. If it is less than 30% by mass, the weather resistance of the binder resin itself may not be sufficiently improved. More preferably, it is 40 mass% or more, More preferably, it is 60 mass% or more, Most preferably, it is 80 mass% or more. The other copolymerizable unsaturated monomer that can be used for the monomer component is not particularly limited, and examples thereof include the following monomers. These may be used alone or in combination of two or more.

Unsaturated monomers having a carboxyl group such as (meth) acrylic acid, itaconic acid, maleic anhydride; acidic phosphate ester unsaturated monomers such as 2- (meth) acryloyloxyethyl acid phosphate; Has active hydrogen such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate (for example, trade name “PLAXEL FM” manufactured by Daicel Chemical Industries, Ltd.) Unsaturated monomers having a group; (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate; glycidyl (meta ) Epoxy such as acrylate Unsaturated monomer having a.

Unsaturated monomers having nitrogen atoms such as (meth) acrylamide, N, N′-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, imide (meth) acrylate; ethylene glycol di ( Two or more polymerizable double bonds such as (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and pentaerythritol tetra (meth) acrylate Unsaturated monomers having halogen atoms such as vinyl chloride; aromatic unsaturated monomers such as styrene and α-methylstyrene; vinyl esters such as vinyl acetate; vinyl ethers.

The present invention also provides a polymer obtained by polymerizing a near-infrared absorbing dye having a maximum absorption wavelength at 780 nm to 1200 nm and a monomer component containing 30% by mass or more of the monomer represented by the general formula (1). It is also a near-infrared absorbing resin composition comprising a coalescence. Such a near-infrared absorptive resin composition will be used suitably as a resin composition which forms the near-infrared absorptive coating film of this invention.

In the present invention, in order to improve the weather resistance of the near-infrared absorbing coating film, a polymerizable UV-absorbing monomer and a polymerizable UV-stable monomer are used as the unsaturated monomer copolymerized with the binder resin. can do. In particular, when the near-infrared absorbing coating film of the present invention requires further ultraviolet blocking ability, an unsaturated monomer having an ultraviolet absorbing group such as benzotriazole, benzophenone or triazine may be used. Specifically, “RUVA93” (trade name, manufactured by Otsuka Chemical Co., Ltd.), “BP-1A” (trade name, manufactured by Osaka Organic Chemical Co., Ltd.) and the like can be used. You may use it combining the above suitably. When further improvement of the weather resistance of the binder resin is required, an unsaturated monomer having an ultraviolet stable group having a sterically hindered piperidine group may be used. Specifically, “ADK STAB LA-82”, “ADK STAB LA-87” (both trade names, manufactured by Asahi Denka Kogyo Co., Ltd.) and the like can be mentioned. You may use it in combination.

As a polymerization method for producing the binder resin, for example, a polymerization initiator can be used by a conventionally known polymerization method such as solution polymerization, dispersion polymerization, suspension polymerization or emulsion polymerization. The solvent for performing the solution polymerization is not particularly limited, and for example, one or more organic solvents as described above can be used. What is necessary is just to set suitably as the usage-amount of a solvent by polymerization conditions, the weight ratio of the polymer in binder resin, etc.

The polymerization initiator is not particularly limited. For example, 2,2′-azobis- (2-methylbutyronitrile), tert-butylperoxy-2-ethylhexanoate, 2,2′-azobisiso Examples include usual radical polymerization initiators such as butyronitrile, benzoyl peroxide, and di-tert-butyl peroxide. These may be used alone or in combination of two or more. The amount used may be set as appropriate from the desired characteristic value of the polymer. For example, when the monomer component is 100% by mass, it is preferably 0.01 to 50% by mass. More preferably, it is 0.05-20 mass%.

The polymerization conditions in the polymerization method may be appropriately set depending on the polymerization method, and are not particularly limited. For example, the polymerization temperature is preferably room temperature to 200 ° C. More preferably, it is 40-140 degreeC. What is necessary is just to set suitably as reaction time so that a polymerization reaction may be completed according to the composition of a monomer component, the kind of polymerization initiator, etc.

As a number average molecular weight of the polymer which comprises the said binder resin, it is preferable that it is 1000-100,000, for example. More preferably, it is 2000-80000, More preferably, it is 4000-60000. The weight average molecular weight is a value measured with polystyrene standard GPC.

As a usage-amount of the said binder resin, when it is set as 100 mass% of near-infrared absorptive resin compositions, it is preferable to set it as 50-99.9995 mass%, for example. If it is less than 50% by mass, the near-infrared absorbing coating film formed from the near-infrared absorbing resin composition may have insufficient physical properties. If it exceeds 99.9995% by mass, the near-infrared absorbing dye Since the weight ratio decreases, the near infrared absorbing performance of the near infrared absorbing coating film may not be sufficient. More preferably, it is 60-99.9985 mass%, More preferably, it is 70-99.998 mass%.

The near-infrared absorbing coating film of the present invention preferably further contains a dehydrating agent. Thereby, content of the water in a near-infrared absorptive coating film can be effectively suppressed with binder resin. As the dehydrating agent, there are various inorganic compounds or organic compounds. However, when used in the present invention, it is preferable that it is volatilized at the time of forming the coating film and does not remain after the formation because there is no deterioration in the performance of the coating film. . In this respect, it is preferable to use an organic dehydrating agent that is relatively volatile. Examples of such dehydrating agents include trimethyl orthoformate, triethyl orthoformate, trimethyl orthoacetate, triethyl orthoacetate, methyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, methyl silicate, ethyl silicate, etc. 1 type or 2 types or more can be used. A preferable form of the chemical structure of such a dehydrating agent is, for example, the following general formula (3);

(Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and represent an organic group having 1 to 8 carbon atoms, preferably an organic group having 1 to 3 carbon atoms). Is done. Moreover, as the usage-amount of a dehydrating agent, it is preferable to set it as 1-20 weight part with respect to 100 weight part of binder resin, for example. If the amount is less than 1 part by weight, the effect of the dehydrating agent may not be sufficiently exhibited. If the amount exceeds 20 parts by weight, the physical properties of the near-infrared absorbing coating film may be deteriorated. More preferably, it is 2-10 weight part, More preferably, it is 3-7 weight part.

The near-infrared absorbing coating film of the present invention can be used either cross-linked or non-cross-linked, but a cross-linked film is preferable from the viewpoint of improving the durability of the dye. It is preferable to mix to form a cured coating film. The near-infrared-absorbing resin composition that forms the near-infrared-absorbing coating film of the present invention can be cured under various curing conditions depending on the use in which it is used and the type of crosslinking agent. It can be used as a curable type, a heat curable type, an ultraviolet ray or an electron beam curable type, and the like. In addition, the amount of the crosslinking agent used, the addition and dispersion method, etc. are not particularly limited. For example, when the binder resin is composed of a polyol having a plurality of hydroxyl groups in one molecule, the amount used normally for the polyol, An addition and dispersion method may be used.

Examples of the crosslinking agent include a (block) polyisocyanate compound and an aminoplast resin when the binder resin is composed of a polyol. These may be used alone or in combination of two or more.

The (block) polyisocyanate compound means a polyisocyanate compound and / or a block polyisocyanate compound. The polyisocyanate compound is not particularly limited as long as it is a compound having at least two isocyanate groups in the molecule. For example, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, Polyisocyanates such as 4,4'-methylenebis (cyclohexyl isocyanate), lysine diisocyanate, trimethylhexamethylene diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate; Polyisocyanate derivatives (modified products) such as isocyanate adducts, burettes, isocyanurates, etc. That.

The above-mentioned blocked polyisocyanate compound is usually a crosslinking agent for the isocyanate group of the polyisocyanate compound in order to crosslink the near infrared absorbing resin composition when heated and dried and to improve the storage stability at room temperature. Blocked with The blocking agent is not particularly limited, and examples thereof include compounds such as ε-caprolactam, phenol, cresol, oxime and alcohol. Commercially available products of the above (block) polyisocyanate compounds include, for example, Sumidur N3200, Sumidur N3300, Sumidur BL3175, Death Module N3400, Death Module N3600, Death Module VPLS2102 (trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.), Duranate E-402-90T (trade name, manufactured by Asahi Kasei Kogyo Co., Ltd.) and the like. Moreover, in order to prevent yellowing of the near-infrared absorptive coating film formed from a near-infrared absorptive resin composition, the non-yellowing polyisocyanate compound which does not have the isocyanate group directly couple | bonded with the aromatic ring is preferable.

Although it does not specifically limit as the usage-amount of the said (block) polyisocyanate compound, For example, the isocyanate group in a (block) polyisocyanate compound will be 0.6-1.4 mol with respect to 1 mol of hydroxyl groups in binder resin. It is preferable to do so. If the amount is less than 0.6 mol, a large amount of residual hydroxyl groups remain in the near-infrared absorbing resin composition, so the near-infrared absorbing coating film formed using the obtained near-infrared absorbing resin composition Weather resistance may decrease. When the amount exceeds 1.4 mol, a large amount of unreacted isocyanate groups remain in the near-infrared absorbing coating film, which reacts with moisture in the air when the coating film is cured, causing the coating film to foam or whiten. is there. More preferably, it is 0.8-1.2 mol.

The aminoplast resin is an addition condensate of a compound having an amino group such as melamine or guanamine with formaldehyde, and is also called an amino resin. The aminoplast resin is not particularly limited. For example, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, fully alkyl methylated melamine, fully alkyl butylated melamine, fully alkyl type. Melamine resins such as isobutylated melamine, fully alkyl type mixed etherified melamine, methylol group methylated melamine, imino group type methylated melamine, methylol group type mixed etherified melamine, imino group type mixed etherified melamine; butylated benzoguanamine, Examples thereof include guanamine resins such as methyl / ethyl mixed alkylated benzoguanamine, methyl / butyl mixed alkylated benzoguanamine and butylated glycoluril.

Examples of commercially available aminoplast resins include Cymel 1128, Cymel 303, My Coat 506, Cymel 232, Cymel 235, Cymel 771, Cymel 325, Cymel 272, Cymel 254, Cymel 1170 (all trade names are Mitsui Cytec). Etc.).

It does not specifically limit as the usage-amount of the said aminoplast resin, For example, it is preferable to mix | blend so that solid content weight ratio of binder resin and aminoplast resin may be 9/1-6/4. When the binder resin is less than 6/4, the obtained near-infrared absorbing coating film becomes too hard and the performance of the coating film may be deteriorated. When the binder resin is more than 9/1, the crosslinking does not proceed sufficiently, so that the obtained near-infrared absorbing coating film may be inferior in water resistance and solvent resistance.

The said near-infrared absorptive resin composition may also contain the 1 type (s) or 2 or more types of curing catalyst for accelerating the crosslinking reaction of binder resin and a crosslinking agent as needed. Although it does not specifically limit as such a curing catalyst, For example, when using the said (block) polyisocyanate compound, it is preferable to use catalysts, such as a dibutyl tin dilaurate and a tertiary amine, When using an aminoplast resin, it is preferable to use an acidic or basic curing catalyst.

The near-infrared-absorbing resin composition that forms the near-infrared-absorbing coating film of the present invention contains, for example, one or more solvents, additives, and the like as a composition other than those described above. Also good. Examples of such solvents include the same organic solvents as described above, and examples of additives include conventionally known additives that are generally used in resin compositions that form films and coating films. Can be used, for example, leveling agent; inorganic fine particles such as colloidal silica and alumina sol, antifoaming agent, anti-sagging agent, silane coupling agent, titanium white, complex oxide pigment, carbon black, organic pigment, intermediate pigment Pigment such as body; Pigment dispersant; Antioxidant; Viscosity modifier; UV stabilizer; Metal deactivator; Peroxide decomposer; Filler; Reinforcer; Plasticizer; Lubricant; Examples include rusting agents; fluorescent whitening agents; organic and inorganic ultraviolet absorbers, inorganic heat ray absorbers; organic / inorganic flameproofing agents; and antistatic agents.

As a usage form of the near-infrared absorbing coating film of the present invention, for example, a laminated body provided on a transparent substrate with a near-infrared absorbing coating film formed from a near-infrared absorbing resin composition as a near-infrared absorbing layer. Or a laminate sandwiched between two transparent substrates. The transparent substrate is not particularly limited. For example, an organic substrate such as polycarbonate resin, acrylic resin, polyethylene resin, polyester resin, polypropylene resin, polystyrene resin, or polyvinyl chloride resin; inorganic group such as glass Materials. In addition, the transparent base material may be colored or various designs may be printed.

As a method for forming the near infrared absorbing layer, for example, (1) a near infrared absorbing resin composition is applied on a transparent substrate, and then the applied near infrared absorbing resin composition is cured to obtain a near infrared absorbing layer. (2) A method of forming a film by forming a near-infrared absorbing resin composition and attaching it to a transparent substrate to form a laminate, and the method (1) is simple To preferred.

In the method for forming the near-infrared absorbing layer, as a method for applying the near-infrared absorbing resin composition on the transparent substrate, for example, dipping, spraying, brush coating, curtain flow coating, gravure coating, roll coating, spin coating , Blade coating, bar coating, reverse coating, die coating, spray coating, electrostatic coating, and the like. In these cases, the organic solvent described above can be appropriately mixed and applied to the near-infrared absorbing resin composition. Moreover, what is necessary is just to set suitably according to the kind etc. of binder resin as a method of hardening a near-infrared absorptive resin composition, For example, the method of heating, the method of irradiating an ultraviolet-ray or an electron beam, etc. are mentioned.

The thickness of the near-infrared absorbing layer is not particularly limited as long as it is appropriately set depending on the intended use. For example, it is preferable to set the thickness at the time of drying to 0.5 to 1000 μm. More preferably, it is 1-100 micrometers. More preferably, it is 1-50 micrometers, Most preferably, it is 1-20 micrometers.

In the said laminated body, it is preferable to provide an ultraviolet absorption layer in the light-incidence side of a near-infrared absorption layer. Thereby, deterioration of the near-infrared absorptive pigment | dye by sunlight can be suppressed more effectively. The laminated structure of such a laminated body is not particularly limited. For example, (1) a form in which an ultraviolet absorbing layer, a near infrared absorbing layer, and a substrate are laminated in this order from the light incident side, and (2) an ultraviolet ray from the light incident side. The form laminated | stacked in order of the absorption layer, the base material, the near-infrared absorption layer, etc. are mentioned. In addition, in order to improve scratch resistance and stain resistance, a surface protective layer such as a silicon-based or organic hard coat layer or a photocatalytic functional layer may be further provided on the surface of the laminate, and if necessary, laminated with a substrate. A primer layer may be provided between the body and each layer of the laminate. There are no particular restrictions on the composition or thickness of such an ultraviolet absorbing layer, surface protective layer, or primer layer.

The near-infrared absorbing coating film of the present invention is also characterized in that there is little deterioration in near-infrared absorbing performance, and as a physical property of the coating film, the near-infrared absorbing performance of the near-infrared absorbing dye after the accelerated weather resistance test The decrease is small, that is, the absorption capacity remaining rate is high, and the near-infrared absorption capacity remaining rate after light irradiation at 63 ° C. and 48 hours in the accelerated weather resistance test with an ultraviolet autofade meter is 50% or more. Specifically, an accelerated weathering test using an ultraviolet fade meter is performed using a coating film formed using a near-infrared absorbing resin composition, and the residual capacity of absorption required by the following evaluation method is 50% or more. It is. Preferably, it is 60% or more, more preferably 70% or more, still more preferably 80% or more. In addition, the actual measurement of the near-infrared absorption performance remaining rate is performed with a coating film coated on a base material that does not absorb in the near-infrared region such as glass and PET film.

Method for evaluating near-infrared absorptive residual rate A near-infrared-absorbing coating film is formed on a substrate, and the transmittance of light at the maximum absorption wavelength in the near-infrared region of the obtained laminate is Measure with a spectrophotometer ( _Ti initial value). Further, the transmittance of the substrate at the wavelength is measured (T ₀ ). Using this laminate, an irradiation test with an ultraviolet autofade meter (trade name “FAL-AU-B”, manufactured by Suga Test Instruments Co., Ltd.) was continuously irradiated at 63 ° C. for 48 hours to make an accelerated weathering test, and after the test The transmittance at the maximum absorption wavelength in the near infrared region is measured (T). From these measured values, the remaining capacity R (%) is obtained by the following equation.
R (%) = (T ₀ −T) / (T ₀ −T _i )

The near-infrared-absorbing coating film of the present invention and the laminate comprising the near-infrared-absorbing coating film as the near-infrared-absorbing layer preferably have high transparency. For example, the haze (cloudiness value) is 3.0. % Or less is preferable. More preferably, it is 2.0% or less, More preferably, it is 1.0% or less. Such near-infrared-absorbing coating films and laminates can be suitably used for windows in buildings and houses, for windows in vehicles such as trains and automobiles, arcades, greenhouses, etc. It can also be used for prevention of operation, protection of solar battery panels, sunglasses, general glasses, protective glasses, contact lenses, and the like. Moreover, it can also apply | coat and use a near-infrared absorptive resin composition for the desired part (for example, glass surface, such as a window) of said articles | goods or a structure.

Since the near-infrared-absorbing coating film of the present invention has the above-described configuration, it is possible to suppress the deterioration of the near-infrared-absorbing dye and form a laminate that can exhibit excellent weather resistance, It can be suitably used for windows for houses, windows for vehicles such as trains and cars, arcades, greenhouses, etc., for infrared remote control malfunction prevention in plasma displays, for protection of solar panels, sunglasses, and general glasses It can also be used for protective glasses, contact lenses and the like.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Synthesis example 1
84 g of toluene was added to a 500 ml flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and a nitrogen gas inlet, and heated to 105 ° C. 69 g of cyclohexyl methacrylate, 16.5 g of 2-ethylhexyl acrylate, 0.5 g of methacrylic acid, 14 g of 2-hydroxyethyl methacrylate, and 2 g of 2,2′-azobis- (2-methylbutyronitrile) as an initiator The solution was continuously added dropwise over 3 hours and further heated for 2 hours. Thereafter, 18 g of toluene was added to obtain a 50% acrylic resin solution. In addition, the number average molecular weight of the polymer which comprises this acrylic resin was 5800. Table 1 shows the composition of the monomer components used for the synthesis of the acrylic resin and the characteristic values of the obtained acrylic resin.

Synthesis Examples 2, 4 and 5
An acrylic resin was obtained in the same manner as in Synthesis Example 1 except that the composition of the monomer component used for the synthesis of the acrylic resin was as shown in Table 1. Table 1 shows the characteristic values of the obtained acrylic resin.

Synthesis example 3
84 g of toluene was added to a 500 ml flask equipped with a stirrer, a dripping port, a thermometer, a cooling pipe and a nitrogen gas inlet, and heated to 115 ° C. To this, 81 g of cyclohexyl methacrylate, 18.5 g of 2-ethylhexyl acrylate, 0.5 g of methacrylic acid, and 1 g of t-butylperoxy-2-ethylhexanoate as an initiator were continuously added dropwise over 3 hours. After heating for 18 hours, 18 g of toluene was then added to obtain a 50% solution of acrylic resin. In addition, the number average molecular weight of the polymer which comprises this acrylic resin was 17000. Table 1 shows the composition of the monomer components used for the synthesis of the acrylic resin and the characteristic values of the obtained acrylic resin.

Synthesis Example 6
An acrylic resin was obtained in the same manner as in Synthesis Example 3 except that the composition of the monomer component used for the synthesis of the acrylic resin was as shown in Table 1. Table 1 shows the characteristic values of the obtained acrylic resin.

Synthesis example 7
100 g of methyl ethyl ketone, 2- [2'-hydroxy-5 '-(methacryloyloxyethyl) phenyl] -2H-benzoitriazole in a 500 ml flask equipped with a stirrer, dropping port, thermometer, condenser and nitrogen gas inlet (Trade name “RUVA93”, manufactured by Otsuka Chemical Co., Ltd.) 18 g, cyclohexyl methacrylate 34 g, styrene 3 g, 2-ethylhexyl methacrylate 3 g, butyl acrylate 2 g, initiator (2,2′-azobis- (2-methylbutyro Nitrile)) 0.2 g was charged and nitrogen gas was introduced and heated to reflux temperature with stirring. To this, 80 g of methyl ethyl ketone, 18 g of 2- [2′-hydroxy-5 ′-(methacryloyloxyethyl) phenyl] -2H-benzotriazole (trade name “RUVA93”, manufactured by Otsuka Chemical Co., Ltd.), 34 g of cyclohexyl methacrylate, 3 g of styrene, A mixture of 2 g of 2-ethylhexyl methacrylate, 2 g of butyl acrylate and 0.2 g of initiator was added dropwise over 2 hours, and the mixture was further heated for 2 hours to obtain a 50% solution of acrylic resin. The number average molecular weight of the polymer constituting this acrylic resin was 20000.

Synthesis example 8
An acrylic resin was obtained in the same manner as in Synthesis Example 3 except that the monomer components were as shown in Table 1. Table 1 shows the characteristic values of the obtained resin.

Table 1 will be described below.
1) CHMA is cyclohexyl methacrylate, 2) 2-EHA is 2-ethylhexyl acrylate, 3) MMA is methyl methacrylate, 4) EA is ethyl acrylate, 5) MAA is methacrylic acid, 6) HEMA is 2-hydroxyethyl methacrylate, 7) initiator 1 is 2,2'-azobis- (2-methylbutyronitrile), 8) initiation Agent 2 is t-butyl peroxy-2-ethylhexanoate.

Example 1
10 parts of the acrylic resin of Synthesis Example 1 as a binder resin, 0.23 part of dye 1 and 4.3 parts of toluene, and 1 part of Sumidur N3200 (trade name) manufactured by Sumitomo Bayer Urethane Co., Ltd. as a curing agent were mixed. An infrared absorbing resin composition was prepared. This was coated on a PET film (trade name “Lumirror T60”, 50 μm, manufactured by Toray Industries, Inc.) as a base material and dried at 80 ° C. to form a near-infrared absorbing layer having a thickness of 5 μm. Further, 10 parts of the acrylic resin of Synthesis Example 7, 3 parts of methyl ethyl ketone, and 0.3 part of Sumijour N3200 are mixed as an ultraviolet absorbing layer, coated on the near infrared absorbing layer and dried at 80 ° C. A 5 μm ultraviolet absorbing layer was formed. The sample prepared by the above method was stored at 50 ° C. for 7 days, and then an accelerated weather resistance test was performed. Moreover, the haze (cloudiness value) of the test sample was measured.

Examples 2-7, 9
With the composition of raw materials shown in Table 2, a test sample was prepared and an accelerated weather resistance test was conducted in the same manner as in Example 1. That is, in Example 2, the acrylic resin obtained in Synthesis Example 2 was used as the binder resin, and in Example 3, the acrylic resin obtained in Synthesis Example 3 was used as the binder resin, and Sumidur N3200 was not blended. In Example 4, 0.16 part of dye 2 was used as the near infrared absorbing dye, 0.13 part of dye 3 was used in the near infrared absorbing dye in Example 5, and the acrylic resin of Synthesis Example 1 was used in Example 6. A test sample was prepared in the same manner as in Example 1 except that 0.5 part of trimethyl orthoformate (OFM) was added to 10 parts as a dehydrating agent and used one day later, and an accelerated weather resistance test was conducted. Carried out. In Example 7, a test sample was prepared in the same manner as in Example 1 except that the ultraviolet absorbing layer was not provided, and an accelerated weather resistance test was performed. In Example 9, a test sample was prepared in the same manner as in Example 1 except that the acrylic resin obtained in Synthesis Example 8 was used as the binder resin, Sumijour N3200 was not blended, and no ultraviolet absorbing layer was provided. The accelerated weather resistance test was conducted. Moreover, the haze (cloudiness value) of the test sample was measured.

Example 8
A near-infrared absorbing layer was formed on the PET film in the same manner as in Example 1. Further, an ultraviolet absorbing layer was formed on the PET film opposite to the near infrared absorbing layer under the same conditions as in Example 1. This sample was stored at 50 ° C. for 7 days and then subjected to an accelerated weathering test. Moreover, the haze (cloudiness value) of the test sample was measured.

Comparative Examples 1-3
With the composition of the raw materials shown in Table 2, test materials were prepared and accelerated weather resistance tests were conducted in the same manner as in Example 1. That is, in Comparative Example 1, Synthesis Example 4 was used as the binder resin, in Comparative Example 2, Synthesis Example 5 was used as the binder resin, and in Comparative Example 3, Synthesis Example 6 was used as the binder resin and Sumidule N3200 was not blended. Except that, a test sample was prepared in the same manner as in Example 1, and an accelerated weather resistance test was performed.

Evaluation methods <br/> near-infrared absorbing resin composition prepared in Measurement Example 1 of water absorption of the coating dry thickness and dried for 3 minutes in the coating after 80 ° C. as a 1 mm, separated from the substrate And the near-infrared absorptive coating film of 3 cm x 3 cm was produced. This was stored at 50 ° C. for 7 days, heated to 80 ° C. under reduced pressure conditions (about 20 mPa), dried for 12 hours, and then weighed (W ₀ ). The membrane was immersed in water, after storage for 20 days at room temperature, (the W ₁₎ was weighed removed. From these measured values, the water absorption was measured according to the following formula.
The water absorption of the coating film (mass%) = {(W ₁ −W ₀ ) / W ₀ } × 100 Measurements were similarly performed for Examples 2 to 8 and Comparative Examples 1 to 3. The results are shown in Table 2. In Examples 3 and 9 and Comparative Example 3, a curing agent (Sumidule N3200) is not used.

Weather Resistance of Dye The light transmittance at the maximum absorption wavelength of the test samples prepared by the methods of Examples 1 to 9 and Comparative Examples 1 to 3 was measured with a spectrophotometer ( _Ti initial value). The measured transmittance at the wavelength of the substrate film (T _0). Using this test sample, a continuous irradiation test with an ultraviolet autofade meter (trade name “FAL-AU-B”, manufactured by Suga Test Instruments Co., Ltd.) was conducted at 63 ° C. for 48 hours to make an accelerated weathering test, and the maximum absorption after the test The transmittance at the wavelength was measured (T). In the irradiation test, light (ultraviolet rays) was irradiated from the ultraviolet absorbing layer side except for Example 7 and in Example 7 from the near infrared absorbing layer side. From these measured values, the near infrared absorptivity remaining rate R (%) was determined by the following equation. The results are shown in Table 2.
R (%) = (T ₀ −T) / (T ₀ −T _i )

Table 2 will be described below. The dye 1 is VOPc (2,5-Cl ₂ PhO) ₈ {2,6- (CH ₃ ) ₂ PhO} ₄ {Ph (CH ₃ ) CHNH} ₃ F, and the dye 2 is VOPc (2,5 -Cl ₂ PhO) ₈ is _{{2,6- (CH 3) 2 PhO} } 4 (PhCH 2 NH) 4, dye _{3,: CuPc (2,5-Cl 2} PhO) 8 {2,6- ( CH ₃ ) ₂ PhO} ₄ (PhCH ₂ NH) ₄ , and the dehydrating agent OFM is trimethyl orthoformate.

Measurement of haze (cloudiness value) The haze of the test samples prepared by the methods of Examples 1 to 9 was measured according to JIS K7105 using a Nippon Denshoku haze meter. The results are shown in Table 3.

Claims (4)

A near-infrared absorbing coating film containing a near-infrared absorbing dye having a maximum absorption wavelength at 780 nm to 1200 nm,
In the accelerated weathering test with an ultraviolet autofade meter, the near-infrared absorbing ability remaining rate after 48 hours of light irradiation is 50% or more,
The near-infrared absorbing coating film has the following general formula (1):

(Wherein R ⁴ represents a hydrogen atom or a methyl group. Z represents an alicyclic hydrocarbon group having 6 to 25 carbon atoms). Formed from a near-infrared absorbing resin composition containing a polymer obtained by polymerization,
The near-infrared absorbing coating film, wherein the near-infrared absorbing dye is at least one dye selected from the group consisting of a phthalocyanine dye, a naphthalocyanine dye, an anthraquinone dye, and a naphthoquinone dye. The near-infrared absorbing coating film has the following general formula (1);

(In the formula, R ⁴ represents a hydrogen atom or a methyl group. Z represents a hydrocarbon group having 6 to 25 carbon atoms.) The near-infrared absorptive coating film according to claim 1, wherein the near-infrared absorptive coating film is formed from a near-infrared absorptive resin composition containing a polymer obtained by polymerizing the polymer. The near-infrared absorbing coating film according to claim 1, wherein the near-infrared absorbing dye is a phthalocyanine dye. A near-infrared absorbing dye having a maximum absorption wavelength at 780 nm to 1200 nm and the following general formula (1);

(In the formula, R ⁴ represents a hydrogen atom or a methyl group. Z represents a hydrocarbon group having 6 to 25 carbon atoms.) A polymer comprising
The near-infrared absorbing dye composition is at least one dye selected from the group consisting of phthalocyanine dyes, naphthalocyanine dyes, anthraquinone dyes, and naphthoquinone dyes. .