JPH09316115A - Heat-ray-shielding resin composition and coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat-ray-shielding composition having a good transparency by mixing inorganic metal microparticles having infrared-absorbing capacity with an anthraquinone compound and a (meth)acrylate and to obtain a heat-ray- shielding film excellent in processability and weathering resistance by applying this composition to a substrate. SOLUTION: This composition is obtained by mixing 20-70wt.% inorganic microparticles (A) having infrared-absorbing capacity and a particle diameter of primary particles of 0.5μm or below with 0.1-30wt.% anthraquinone compound (B) represented by the formula (wherein R is H or p-tolyl) and having a maximum absorption wavelength of 650nm or longer and 10-98wt.% (meth)acrylate (C) having at least one (meth)acryloyl group in the molecule and being polymerizable with an actinic radiation such as ultraviolet rays or electron beams. This composition may optionally contain 2-50wt.% resin component such as an acrylic resin, a polyester resin or a butyral resin. It is applied to a substrate to obtain a heat-ray-shielding film.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a heat ray-shielding resin composition and a film coated with the heat ray-shielding resin composition, and more particularly to a heat ray-shielding resin composition having a good transparency and a broad heat ray absorption spectrum. Further, according to the present invention, there is a feature that a film having a relatively low cost, excellent processability, and excellent weather resistance and a high heat ray absorbing ability can be obtained.

[0002]

2. Description of the Related Art Heat ray shielding materials have been actively researched and developed in recent years, and include photosensitive materials using a semiconductor laser beam having a wavelength in the infrared region as a light source, recording materials for optical disks, and the like. It can be used as an information recording material, an infrared cut filter or a heat ray shielding film for windows of buildings, windows of vehicles, and the like.

[0003] For these uses, chromium, cobalt complex thiol nickel complex, anthraquinone derivative and the like are conventionally known as a light-transmitting material capable of absorbing near infrared rays. In addition, a heat ray reflective film in which a metal such as aluminum or copper is deposited is known. Such a heat ray reflective film transmits visible light, but reflects near-infrared ray-infrared ray, so when applied to an opening such as a glass window, it reflects sunlight rays or radiant heat from a room to adjust sunlight and heat insulation. With the effect. Utilizing such characteristics, the transparent heat-insulating film is used for windows of buildings, freezer / refrigerated showcases, heat-insulating surfaces, vehicle windows, etc., and is useful for improving the living environment and saving energy.

[0004]

However, the conventional heat ray-shielding materials have the drawback that the organic heat-insulating materials are inferior in durability, and the initial heat ray-shielding effect deteriorates with changes in environmental conditions and time. there were. On the other hand, the complex type has durability, but has a large absorption not only in the near-infrared region but also in the visible region, and has a drawback that its use is limited because it is strongly colored.

[0005] In addition, since the conventional heat-reflective film on which a metal is vapor-deposited reflects not only heat rays but also visible light with a metal vapor-deposited layer, if it is attached to a window glass or the like, its lighting property is impaired and the interior becomes dark. There is also a drawback that there is a technical defect, and glare due to reflected light is unavoidable from outside.

Further, since the conventional heat ray blocking material has absorption only in a specific infrared wavelength region, a substance having a wide heat ray absorption spectrum has not been found yet. For this reason, there is a drawback in that conventional materials cannot be said to have sufficient heat ray absorbing ability. Here, it has been desired to develop a durable material having high visible light transmittance while blocking high heat rays.

Further, in the prior art, in order to form a film of the heat ray absorbent, as the resin for fixing the heat ray absorbent, mainly acrylic resin, polyester resin, alkyd resin, polyurethane resin, epoxy resin, amino resin,
A thermoplastic resin such as a vinyl resin is generally used. However, these resins have a weak film hardness and are easily scratched, and have poor scratch resistance. In addition, since the work of dispersing or dissolving the heat ray absorbent in these resins, or the work of coating and molding the film, is performed under heating, there is a disadvantage that the heat ray absorbent body is easily deteriorated and the performance is deteriorated. doing.

[0008]

DISCLOSURE OF THE INVENTION The inventors of the present invention have found that the absorption of heat rays in a wide range from near infrared to far infrared is high, the visible light transmittance is high and the durability is excellent, and the heat rays have a high heat ray absorption rate. As a result of repeated intensive studies on the barrier material, irradiation with the fine metal particles having a primary particle diameter of 0.5 μm or less, preferably 0.1 μm or less, and the specific anthraquinone compound represented by the formula (1) and active energy rays It was found that a heat ray-shielding resin composition composed of (meth) acrylate curable by means of achieving the above-mentioned object, and it was confirmed that a transparent film coated with this also exhibits the same effect, and thus the present invention was completed. Came to.

Embedded image (In the formula, R represents H or -p-tolyl group)

According to the present invention, by combining metal fine particles having a heat ray absorbing ability with a specific anthraquinone compound, a highly durable and wide heat ray absorbing spectrum can be obtained, and at the same time, a more excellent heat ray absorbing ability is exhibited. By using an active energy ray-curable (meth) acrylate as a resin for fixing the heat ray absorbent of
It is possible to efficiently form a film having excellent scratch resistance and durability.

Examples of the metal having the ability to absorb heat rays used in the present invention include titanium oxide, zinc oxide, indium oxide, tin oxide, antimony oxide, zinc sulfide, glass ceramics and the like, but particularly tin oxide and ATO (antimony-doped oxidation). Metal oxides such as tin), ITO (indium-doped tin oxide), and vanadium oxide are preferable because they have excellent heat ray absorbing ability. In order to form such a metal as a transparent metal-containing film having no absorption in the visible light region and having a primary particle diameter of 0.5 μm or less, preferably 0.1 μm or less, it is necessary to use ultrafine powder. . In addition, the fine particles must be kept stable in the resin without agglomeration. The content of the heat ray-shielding inorganic metal fine particles with respect to the solid content in the resin composition of the present patent can be arbitrarily selected according to the required heat ray-shielding ability, but is preferably 20% by weight to 70% by weight. It is suitable. ATO is, for example, JP-A-5
It can be produced by the method described in JP-A-8-117228, JP-A-6-262717, JP-A-2-105875, or the like, and ITO is, for example, JP-A-63.
It can be produced by the method described in Japanese Unexamined Patent Publication No. 11519. Further, vanadium oxide can be produced by a natural ore beneficiation method or by heating ammon metavanadate.

The specific anthraquinone compound used in the present invention is represented by the structure (1) and has a maximum absorption wavelength of 650.
nm or more. These compounds can be used alone or as a mixture. The ratio in the case of a mixture can be optionally adjusted to 1:99 to 99: 1, and the substances after the reaction may be mixed or may be taken out as a mixture during the reaction. This anthraquinone compound is applicable to the present invention if it is finely divided into particles having a particle size of 0.5 μm or less, preferably 0.1 μm or less, like a metal having a heat ray absorbing ability, but it is used after being dissolved in an organic solvent for its effect and ease of adjustment. Is more preferable. The present anthraquinone compound is obtained by using dinitrochrysazine as a raw material, condensing it with paratoluidine after bromination, and then subjecting 2-aminothiophenol to ring-closing condensation. The content of these anthraquinone compounds with respect to the solid content of the resin composition can be arbitrarily selected according to the required heat ray blocking performance, but is preferably 0.1% by weight to 30% by weight, more preferably 0% by weight. The range of 0.5 to 20% by weight is preferable.

The active energy ray-polymerizable (meth) acrylate used in the present invention can be arbitrarily selected from ultraviolet ray or electron beam curable (meth) acrylate having one or more (meth) acryloyl groups in the molecule. ,
They can be used alone or as a mixture. Specific examples of the (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. , Stearyl acrylate, 2-ethylhexyl carbitol acrylate, ω
-Carboxypolycaprolactone monoacrylate, acryloyloxyethyl acid, acrylic acid dimer, lauryl (meth) acrylate, 2-methoxyethyl acrylate, butoxyethyl acrylate, ethoxyethoxyethyl acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol acrylate, stearyl ( (Meth) acrylate, cyclohexyl (meth) acrylate, tetosehydrofurfuryl (meth) acrylate, N-vinyl-2-pyrrolidone,
Isobonyl (meth) acrylate, dicyclopentenyl acrylate, benzyl acrylate, phenylglycidyl ether epoxy acrylate, phenoxyethyl (meth) acrylate, phenoxy (poly) ethylene glycol acrylate, nonylphenol ethoxylated acrylate, acryloyloxyethyl phthalic acid, tribromophenyl acrylate , Tribromophenol ethoxylated (meth) acrylate, methyl methacrylate, tribromophenyl methacrylate, methacryloyloxyethyl acid, methacryloyloxyethyl maleic acid, methacryloyloxyethyl hexahydrophthalic acid, methacryloyloxyethyl phthalic acid, polyethylene glycol (meth) acrylate , Polypropylene glycol (meth) a Relate, beta-carboxyethyl acrylate, N- methylolacrylamide acrylamide, N-
Methoxymethylacrylamide, N-ethoxymethylacrylamide, Nn-butoxymethylacrylamide, t-butylacrylamide sulfonic acid, vinyl stearylate, N-methylacrylamide, N-dimethylacrylamide, N-dimethylaminoethyl (meth)
Acrylate, N-dimethylaminopropylacrylamide, acryloylmorpholine, glycidyl methacrylate, n-butyl methacrylate, ethyl methacrylate, allyl methacrylate, cetyl methacrylate, pentadecyl methacrylate, methoxypolyethylene glycol (meth) acrylate, diethylaminoethyl (meth) ) Acrylate, methacryloyloxyethyl succinic acid, hexanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol mer diacrylate, hydroxypivalate neopentyl, pentaerythritol diacrylate monostea Rate, glycol diacrylate, -Hydroxyethyl methacryloyl phosphate, bisphenol A ethylene glycol adduct acrylate, bisphenol F ethylene glycol adduct acrylate, tricyclodecane methanol diacrylate, trishydroxyethyl isocyanurate diacrylate, 2-hydroxy-1-acryloxy-3-methacrylic Roxypropane, trimethylolpropane triacrylate, trimethylolpropane ethylene glycol adduct triacrylate, trimethylolpropane propylene glycol adduct triacrylate, pentaerythritol triacrylate, trisacryloyloxyethyl phosphate, trishydroxyethyl isocyanurate triacrylate, modified ε-caprolactone triacrylate, Trimethylolpropane ethoxy triacrylate, glycerin propylene glycol adduct triacrylate, pentaerythritol tetraacrylate, pentaerythritol ethylene glycol adduct tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexa (penta) acrylate, dipentaerythritol monohydroxypenta Examples include, but are not limited to, acrylates, urethane acrylates, epoxide acrylates, polyester acrylates, unsaturated polyesters, and the like. These can be used singly or arbitrarily as a mixture. Preferably, the polyfunctional (meth) acrylate monomer or oligomer containing two or more (meth) acryloyl groups in the molecule has a hard film after polymerization, and has an excellent resistance. The abrasion is good and suitable. The ratio of these active energy ray-polymerizable (meth) acrylates to the resin component of the resin composition is preferably 10% by weight or more and 98% by weight or less, more preferably 30% by weight or more and 80% by weight or less.

Further, in addition to an active energy ray-polymerizable (meth) acrylate having a (meth) acryloyl group as a resin component, adhesion to a film, or fine particles of an inorganic metal and an active energy ray-polymerizable resin Polymers such as acrylic resin, polyester resin and butyral resin may be added for the purpose of improving compatibility. For example, Byron (a polyester resin manufactured by Toyobo Co., Ltd.) can be used as the polyester resin, and S-REC made by Sekisui Chemical can be used as the butyral resin. In particular, a polymer having a hydroxyl group is preferable because it has good dispersibility of the metal oxide, and at the same time, it has the functions of improving the adhesion of the ink and relaxing the shrinkage of the film. The ratio of the composition of this polymer to the resin component is 2% by weight.
It is preferably 50% by weight or less, more preferably 20% by weight or less. If the content of this polymer is too large, the abrasion resistance of the coating film obtained is reduced, and it is not particularly suitable for the method of using the coating film surface outside.

In order to disperse the ultrafine particles of the inorganic metal in the ultraviolet curable resin well, a dispersant may be further added, if necessary. As the dispersant, various surfactants are used. For example, as the surfactant, anionic surfactants such as sulfate ester type, carboxylic acid type and polycarboxylic acid type surfactants, and cationic surface active agents such as quaternary salts of higher aliphatic amines are used. Examples include activators, nonionic surfactants such as higher fatty acid polyethylene glycol ester-based surfactants, silicon-based surfactants, fluorine-based surfactants, and polymeric surfactants having an amide ester bond. Among them, carboxylic acid-based and polycarboxylic acid-based dispersants are particularly preferable. Specifically, Floren AF-405, G-685, G-820 and the like (manufactured by Kyoeisha Yushi Co., Ltd.) can be used. The amount of the dispersant added is preferably 0.1% by weight or more and 10% by weight or less based on the total weight of the inorganic metal and the anthraquinone compound.

The resin composition of the present invention can be cured by irradiation with an electron beam or ultraviolet rays, but when it is polymerized and cured by ultraviolet rays, a photopolymerization initiator is used, and the photopolymerization initiator is previously contained in the resin composition. Dissolve in. The photopolymerization initiator is not particularly limited, and various known ones can be used.
15% by weight, preferably 0.5-12% by weight,
If the amount is too small, the curability decreases, which is not preferable. If the amount is too large, the strength of the cured film decreases. Specific examples of the photopolymerization initiator include Irgacure-184 and Irgacure-6.
51 (manufactured by Ciba Geigy), Darocure-1173 (manufactured by Merck), benzophenone, methyl O-benzoylbenzoate, p-dimethylbenzoate, thioxanthone, alkylthioxanthone, amines and the like. When polymerizing and curing using an electron beam, such a polymerization initiator is not particularly required.

Further, various slip agents can be added for the purpose of improving the slip property of the surface of the coating film.
Further, an antifoaming agent can be added for the purpose of controlling foam generated when the composition is applied. Further various organic solvents as required, for example, toluene, xylene, ethyl acetate,
Aromatic or aliphatic organic solvents such as alcohols and ketones can be added.

BEST MODE FOR CARRYING OUT THE INVENTION

Examples of the method for producing the active energy ray-curable heat ray-shielding resin composition and the method for coating the same on a film according to the present invention include the following methods. A dispersion liquid of a metal finely dispersed to 0.5 μm or less in an organic solvent and a dispersion liquid or a dissolution liquid of a specific anthraquinone compound represented by the formula (1) are mixed in advance, and preferably a dispersant and a polymer resin Is added in a small amount to stabilize the dispersion of fine particles. After that, an uncured (meth) acrylate monomer or oligomer that can be polymerized by irradiation with active energy rays is added alone or in combination of two or more kinds, and further, a polymerization initiator is dissolved if necessary to obtain a desired heat ray-shielding resin. Obtain the composition. At this time, an appropriate amount of a solvent or various additives can be added as needed. The mixing method of these respective components is not limited to this order, and is not particularly limited as long as it is a method capable of stabilizing the fine particles of the metal or anthraquinone compound. As a method for coating a film with this composition, for example, a dipping method, a gravure coating method, an offset coating method, a roll coating method, a bar coating method, a spraying method, or the like is performed by a conventional method, and the solvent is evaporated with hot air after coating. Then, the heat ray-shielding composition coated on the film surface is instantaneously polymerized and cured by irradiating with active energy rays such as electron rays or ultraviolet rays. The thickness of the dried coating film to be coated is 1 to 10 μm, preferably 2 to 5 μm from the viewpoint of curling prevention. Examples of the film substrate to be coated include polyester, polyethylene, polypropylene, polystyrene, polycarbonate, polyvinyl chloride, poly (meth) acryl, polyamide, and polyurethane. These film bases preferably have high transparency, but a colored film base may be used as desired.

[0018]

【Example】

Preparation Method of Composition Next, the preparation method of the resin composition of the present invention will be described in detail with reference to Examples.
Indicated by Example 1 In a container equipped with a stirrer, 50 parts of a toluene solution containing 50% of ATO finely dispersed to 0.1 μm or less was placed, and then while being well stirred, dispersant Floren AF-405 (Kyoeisha Yushi ( 6 parts of a toluene solution containing 3% of a polycarboxylic acid type dispersant manufactured by K.K.) was added. Then, an anthraquinone compound A of the formula (1) (wherein R is H is 25%, p-
13.5 parts of a toluene solution in which 1 part of a toluyl-based 75% mixture is dissolved is added, and the polyester resin Byron 24SS (manufactured by Toyobo Co., Ltd.) is further stirred.
7 parts was added little by little and dissolved. Subsequently, UV curable monomer dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.) 2
1.5 parts of the photopolymerization initiator Irgacure 184 was added and dissolved therein, and 2 parts of the photopolymerization initiator Irgacure 184 was dissolved to obtain an ultraviolet curable heat ray-shielding resin composition (1). The solid content of this composition was 51.5%, the viscosity was 15 CPS, and the dispersion was stable.

Example 2 In Example 1, the amount of anthraquinone compound A was doubled to 14.5 parts of a toluene solution containing 2 parts of anthraquinone compound A, and to adjust the solid content,
Increase the amount of dipentaerythritol hexaacrylate to 2
A heat ray-shielding resin composition (2) was obtained in the same manner as in Example 1 except that the amount was 0.5 part. The solids content of this composition is
The dispersion was stable with the same 51.5% and a viscosity of 16 CPS.

Comparative Example 1 A heat ray-shielding resin composition (3) containing no anthraquinone compound A in Example 1 was obtained by the following formulation. That is, in a container equipped with a stirrer, put 50 parts of a toluene solution containing 50% of ATO finely dispersed to 0.1 μm or less,
While well stirring, 6 parts of a toluene solution containing 3% of dispersant Floren AF-405 (polycarboxylic acid type dispersant manufactured by Kyoeisha Yushi Co., Ltd.) was added. Subsequently, while further stirring, 7 parts of the polyester resin Byron 24SS was added little by little and dissolved. Subsequently, 12.5 parts of toluene and 22.5 parts of dipentaerythritol hexaacrylate, which is a UV-curable monomer, are added and dissolved, and 2 parts of Irgacure 184, a photopolymerization initiator, is further dissolved to block UV-curable heat rays. A resin composition was obtained. The solid content of this composition was 51.5%, the viscosity was 15 CPS, and the dispersion was stable.

Comparative Example 2 Anthraquinone compound A containing no metal fine particles ATO
A heat ray-shielding resin composition (4) consisting of the above was obtained by the following method. Put 20 parts of toluene in a container equipped with a stirrer and stir well to add 0.3 parts of anthraquinone compound A.
A portion was added and dissolved. Subsequently, 19 parts of dipentaerythritol hexaacrylate and then 1 part of the photopolymerization initiator Irgacure 184 were added and completely dissolved to obtain an ultraviolet curable heat ray-shielding resin composition.

[0022]

Comparative Example 3 Anthraquinone compound A in Comparative Example 2
Was doubled to obtain a heat ray-shielding resin composition (5) consisting only of the anthraquinone compound A by the following method. 20 parts of toluene was placed in a container equipped with a stirrer, and 0.6 part of anthraquinone compound A was added and dissolved while stirring well. Subsequently, 18.7 parts of dipentaerythritol hexaacrylate and then 1 part of the photopolymerization initiator Irgacure 184 were added and completely dissolved to obtain a UV-curable heat ray-shielding resin composition.

[Preparation of coating film] (1) Example 1-2 was applied to a transparent polyester film having a thickness of 50 μm.
And, the heat ray-shielding resin composition obtained in Comparative Example 1 was applied with a wire bar so that the solid coating amount was 6.7 g / m 2, and in Comparative Examples 2 and 3, the wire bar was similarly applied with 8.8.
After coating to g / m2, apply solvent at 80 ℃
After drying with hot air, the coating film was polymerized and cured by irradiating it with a high-pressure mercury lamp of 80 W at a conveyor speed of 20 m / min to obtain a target heat ray-shielding coating film. Further, as a reference object, a commercially available vehicle-mounted film in which aluminum was vapor-deposited on a PET film using a vacuum metal sputtering device and a black-colored commercially available film for the same purpose were subjected to the test. Table 1 shows the properties of the obtained film.

[0024]

[Table 1] Visible light transmittance was measured according to JIS A 5759. The solar absorptivity was measured according to JIS R 3106. (The higher the numerical value of the solar radiation absorption rate, the better the heat ray blocking performance.) Scratch resistance was measured with steel wool No. 0000 at a load of 200 g and 20 reciprocations. ：: not damaged at all ×: damaged

As is clear from Table 1, the visible light transmittance of Example 1 is located between Comparative Examples 2 and 3, but the solar radiation absorptivity showing the actual heat ray shielding performance is higher than that of Comparative Examples 2 and 3. It is remarkably large and has excellent heat ray shielding performance. This suggests that the combination of a specific anthraquinone compound and ATO (an example of an inorganic metal) synergistically improves the heat ray blocking performance at the same visible light transmittance.
In Example 2, the effect is further increased. In addition, the films according to Examples 1 and 2 exhibit much higher heat ray-shielding performance while maintaining high visible light transmittance, as compared with the vapor-deposited film and the colored film which are commercially available as heat ray-cut films shown as Reference Examples. .

[0026]

The film coated with the heat ray-shielding resin composition of the present invention has excellent scratch resistance, is highly transparent in the visible light region, is transparent, and has a wide heat ray absorption spectrum, so that it is remarkably excellent in heat ray shielding. Show performance. In addition, since the composition easily forms a hard film by irradiating with active energy rays, it has excellent workability, and can be used for windows of buildings and vehicles,
Most suitable for application to optical equipment.

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Claims (8)

[Claims] 1. A primary particle diameter of 0.5 μm having an infrared absorbing ability.
A heat ray blocking resin composition comprising fine particles of an inorganic metal of m or less, an anthraquinone compound represented by the formula (1) and an active energy ray-polymerizable (meth) acrylate having a (meth) acryloyl group. Embedded image (In the formula, R represents H or -p-tolyl group) 2. A film coated with the resin composition according to claim 1. 3. The resin composition according to claim 1, wherein the fine particles of the inorganic metal are metal oxides such as tin oxide, ATO (antimony-doped tin oxide), ITO (indium-doped tin oxide) and vanadium oxide. 4. A film coated with the resin composition according to claim 3. 5. A resin component of a heat ray-shielding resin composition,
The resin composition according to claim 1, which contains a polymer such as an acrylic resin, a polyester resin, or a butyral resin. 6. A film coated with a resin composition. 7. The resin composition according to claim 1, wherein a carboxylic acid-based dispersant is used to disperse the inorganic metal fine particles in the resin component. 8. A film coated with a resin composition.