JPH1036415A - Ultraviolet-curing heat-ray-shielding resin composition and film coated with the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which is transparent, has a high visible light transmittance, is excellent in marring resistance and durability, and has heat-ray-shielding properties by dispersing fine metallic oxide particles with a primary particle size of less than a specific value in an ultraviolet-curing resin. SOLUTION: The resin composition comprises fine metal oxide particles having a primary particle size of 0.5μm or less and an infrared absorption capability (e.g. a gel of anhydrous zinc antimonate) and a binder comprising an actinic-radiation-polymerizable (meth) acrylate (preferably a polyfunctional (meth)acrylate monomer or oligomer having two or more (meth)acryloyl groups in the molecule because it gives a hard film after polymerization and has a good marring resistance). The composition may further comprise, in addition to the (meth)acrylate, a polymer such as an acrylic resin or a urethane resin as the resin component for the purpose of improving adhesion to the film or compatibility of the fine metal particles with the actinic-radiation-polymerizable resin. The resin composition is curable by ultraviolet light, excellent in marring resistance, and capable of shielding heat radiation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat ray-shielding resin composition and a film coated with the same, and more particularly to a heat ray-shielding resin composition having good transparency and excellent scratch resistance and a layer structure thereof. Further, according to the present invention, there is a characteristic that a film which is relatively inexpensive, has excellent workability, and has excellent weather resistance and 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 material has a drawback that the organic one is inferior in durability and the initial heat ray shielding effect is degraded with changes in environmental conditions and time. Was. 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. 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 a heat ray absorbent, resins for fixing the heat ray absorbent are mainly acrylic resins, polyester resins, alkyd resins, polyurethane resins, epoxy resins, amino resins, and the like.
A thermoplastic resin such as a vinyl resin is generally used. However, these resins have low film hardness, are easily scratched, and have poor abrasion 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.

[0007]

The inventors of the present invention have conducted intensive studies on a heat ray shielding material which absorbs light in the near-red to far-infrared region, has little coloration, and is excellent in durability. A gel of a metal oxide having a particle size of 0.5 μm or less, particularly anhydrous zinc antimonate (for example, Celnax CX-Z (ZnSb ₂
O ₆ ) (Nissan Chemical Industry Co., Ltd.) was dispersed in an ultraviolet-curable resin to obtain an ultraviolet-curable heat ray-shielding resin composition. Further, after applying this resin composition on a film and curing it by irradiating ultraviolet rays, it has been found that a heat-absorbing film which is transparent and has excellent scratch resistance can be easily obtained. Was completed.

As the metal oxide having an infrared absorbing ability used in the present invention, a gel of anhydrous zinc antimonate is preferable. Since anhydrous zinc antimonate also has absorption in the ultraviolet region having a shorter wavelength than the visible light region, an effect of improving light resistance can be expected. Further, anhydrous zinc antimonate has a function as a flame retardant aid caused by antimony pentoxide, and a film obtained by coating it has flame retardancy. As a method for producing antimony pentoxide, for example, published patent publications 6-17234 and 7
And a method for producing anhydrous zinc antimonate can be obtained by the method described in JP-A-6-219743. The fine particles of anhydrous zinc antimonate can be obtained, for example, by mixing a zinc compound and colloidal antimony oxide, drying, and firing at a high temperature. It is preferable that these metal oxides are adjusted to a form that can be dispersed in an organic solvent.
Further, in order to form a transparent metal oxide-containing film with low absorption in the visible light region, it is necessary to form ultrafine powder having primary particles of 0.5 μm or less, preferably 0.1 μm or less. The content of the fine particles of the heat-ray-shielding metal oxide in the resin composition of the present invention can be arbitrarily selected according to the required heat-ray-shielding ability, but the particles are stable without agglomeration in the resin. Must be kept.

The active energy ray-polymerizable (meth) acrylate used in the present invention may be any one of an ultraviolet ray or electron beam curable (meth) acrylate having at least one (meth) acryloyl group in a molecule. You can choose
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, tetrahydrofurfuryl (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 the active energy ray polymerizable (meth) acrylate to the resin component in the heat ray-shielding resin composition is preferably from 10% by weight to 98% by weight, more preferably from 30% by weight to 80% by weight.

Also, in addition to active energy ray-polymerizable (meth) acrylate having a (meth) acryloyl group as a resin component, it has an adhesive property to a film, or an inorganic metal fine particle and an active energy ray-polymerizable resin. For the purpose of improving compatibility, a polymer such as an acrylic resin, a polyester resin, a butyral resin, or a urethane resin can be added. The ratio of the polymer composition to the resin component is as follows:
The content is preferably 2% by weight or more and 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, a dispersant may be further added as required. As the dispersant, various surfactants are used. Examples of the surfactant include cationic surfactants such as quaternary salts of higher aliphatic amines, polyethylene glycol alkylamines, and nonionics such as higher fatty acid polyethylene glycol esters. Surfactants, amphoteric surfactants, silicon-based surfactants, fluorine-based surfactants, high-molecular-weight surfactants having an amide ester bond, and the like. The amount of the dispersant added is preferably from 0.1% by weight to 15% by weight based on the total weight of the inorganic metal oxide.

The resin composition of the present invention can be cured by irradiation with an electron beam or ultraviolet rays. In the case of polymerizing and curing with 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. Embodiment of the Invention

The method for producing the heat ray-shielding resin composition of the present invention and the method for coating the film with a film include, for example, the following method. In a dispersion of a metal oxide finely dispersed to 0.5 μm or less in advance in an organic solvent,
Preferably, a small amount of a dispersant and a polymer resin are added to stabilize the dispersion of the fine particles. Thereafter, an uncured (meth) acrylate monomer or oligomer which can be polymerized by irradiation with an active energy ray is added alone or in combination of two or more, and further, if necessary, a polymerization initiator is dissolved to obtain a desired polymer. A heat ray blocking resin composition is obtained. At this time, an appropriate amount of a solvent or various additives can be added as needed. The method of mixing these components is not limited to this order, and is not particularly limited as long as the method can stabilize the fine particles of the metal oxide. This composition is coated on a transparent film substrate in a single layer and then irradiated with an active energy ray, for example, an ultraviolet ray or an electron beam, so that the visible ray transmittance is extremely high, and the heat ray is excellent in abrasion resistance and heat ray blocking performance. A shielding film can be obtained. As a method of coating this composition on a film, for example, a dipping method, a gravure coating method, a roll coating method, a bar coating method, a spraying method and the like are performed by a conventional method, and after coating, the solvent is volatilized with hot air, followed by activation. By irradiating an energy ray, for example, an electron beam or an ultraviolet ray, the heat ray-blocking composition coated on the film surface is instantaneously polymerized and cured. The thickness of the dried coating film to be coated is 1 to 50 μm, preferably 2 to 10 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.

Preparation of the composition

EXAMPLES Next, the method of preparing the resin composition of the present invention will be described in detail with reference to examples, but all the addition ratios in the examples are shown by weight%.

Example 1 Preparation of (A) Solution In a vessel equipped with a stirrer, 50 parts of a methanol solution containing 40% of a sol of anhydrous antimony zinc (ZnSb ₂ O ₆ ) having a particle size of 0.1 μm or less was used. Then, 3.5 parts of a dispersing agent Pluronic TR-702 (manufactured by Asahi Denka Kogyo KK) is added thereto with good stirring. (B) Preparation of liquid UV-curable resin dipentaerythritol hexaacrylate (KAYARADDPHA manufactured by Nippon Kayaku Co., Ltd.)
To 64 parts, 30 parts of toluene was added while stirring, and then 0.6 parts of a photopolymerization initiator Irgacure-184 and 0.05 parts of a slipping agent SH-29PA (manufactured by San Nopco) were added, followed by photoinitiation. Stir until the agent is completely dissolved.
30 parts of the liquid (B) are gradually added to the liquid (A) with good stirring, thereby obtaining an ultraviolet-curable resin composition (1) for blocking heat rays.

Example 2 A resin composition (2) was obtained in the same manner as in Example 1 except that Adecacol CC-42 (manufactured by Asahi Denka Kogyo KK) was used as a dispersant.

Example 3 A resin composition (3) was obtained in the same manner as in Example 1 except that 40 parts of the liquid (B) was used.

Comparative Example 1 3.5 parts of Pluronic TR-702 as a dispersant was added to 50 parts of a methanol solution containing 40% of a sol of anhydrous antimony zinc dispersed in toluene to 0.1 μm or less and stirred well. 30 parts of a 30% methanol solution of butyral resin S-LEC BX-L (manufactured by Sekisui Chemical Industry Co., Ltd.) was added as a binder to the resin composition (4).
I got

Preparation of Coating Film (1) A resin composition obtained in Example 1-3 and Comparative Example 1 was applied to a transparent polyester film having a thickness of 50 μm by applying
After coating the solid content with a coating bar to a thickness of 4.1 μm and drying the solvent with hot air, the resin composition (1) to the resin composition (3) were conveyed by a high-pressure mercury lamp of 80 W on a conveyor spinner. Irradiation was carried out at a speed of 20 m / min. And a curing was performed to obtain a target coating film. With respect to the resin composition (4), a coating film was obtained by drying with hot air to form a film.

For further reference, a 50 micron thick transparent polyester film without any coating was subjected to the test. Table 1 shows the properties of the obtained film.
FIG. 1 shows a spectral characteristic diagram.

[0022]

[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 absorptivity, the better the heat ray shielding performance)

[0023]

According to the present invention, the coating film of the ultraviolet ray-curable heat ray shielding resin composition of the present invention can be applied to a coating film having a high transparency in the visible light region, a transparent coating film having excellent abrasion resistance and a heat ray shielding ability. Since it is easily formed by irradiation, it is most suitable for application to a window of a building, a window of a vehicle, and the like as a heat ray shielding film.

[Brief description of the drawings]

FIG. 1 is a diagram showing spectral characteristics of a film of Example 1 and a transparent polyester film.

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Claims (4)

[Claims] 1. A primary particle size of 0.5 having an infrared absorbing ability.
A heat ray-shielding resin composition which is hardened by ultraviolet rays comprising fine particles of a metal oxide having a size of not more than μm and active energy ray-polymerizable (meth) acrylate having a (meth) acryloyl group as a binder and has scratch resistance. Objects and films coated with them. 2. The resin composition according to claim 1, wherein the fine particles of the metal oxide are a gel of anhydrous zinc antimonate, and a film obtained by coating the resin composition. 3. The resin composition according to claim 1, which contains a polymer such as an acrylic resin, a polyester resin, or a butyral resin as a component of the binder, and a film coated with the resin composition. 4. The resin composition according to claim 1, wherein a cationic, nonionic or amphoteric ion dispersant is used to disperse the metal oxide fine particles in the binder, and a film coated with the resin composition.