JPH09108621A - Ultraviolet curing heat ray cut-off resin composition and film coated with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily form a coating film excellent in scuff resistance by preparing a heat ray cut-off resin composition from a specific fine particle of an inorganic metal having heat ray absorptivity and an actinic radiation polymerizable polyfunctional (metha)acrylate and curing with the irradiation of ultaviolet ray. SOLUTION: A heat ray cut-off resin composition consisting of the fine particle of inorganic metal having heat ray absorptivity and <=0.5μm in primary particle diameter and an actinic radiation polymerizable (metha)acrylate as the binder is used as a heat ray cut-off material exhibiting absorption in near infrared-far infrared region, small in coloring and excellent in durability. As the fine particle of the heat ray cut-off inorganic metal, a metal oxide based super fine particle powder such as tin oxide, ATO(antimony doped tin oxide) is cited and as the component of the binder, a polymer such as an acrylic resin is exemplified. Further, a dispersing agent such as a carboxylic acid is used for dispersing the fine particle of the heat ray cut-off inorganic metal in the binder.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to fine particles of an inorganic metal having a heat ray absorption capacity and a primary particle diameter of 0.5 μm or less and (meth).
Active energy-ray polymerizability (meth) with acryloyl group
The present invention relates to a heat ray-shielding resin composition curable with ultraviolet rays, which comprises an acrylate, and a scratch-resistant film coated with the same.

The heat ray-shielding material is a material which has been actively researched and developed in recent years, and it is a photosensitive material using a semiconductor laser light having a wavelength in the near infrared region as a light source, a recording material for an optical disk. It can be used as an information recording material such as, an infrared cut filter or a heat ray blocking film for a window of a building, a window of a vehicle and the like.

[0003]

2. Description of the Related Art Conventionally, chromium, cobalt complex salt thiol nickel complex, anthraquinone derivative and the like have been known as near infrared ray absorbing light transmitting materials. In addition,
A heat ray reflective film in which a metal such as aluminum or copper is vapor-deposited on one surface of a polyethylene terephthalate film is known. Such heat ray reflective film transmits visible light well, but reflects near infrared rays-infrared rays, so when applied to an opening such as a glass window, while maintaining transparency, it reflects sunlight rays or radiant heat from the room. And it has the effect of sunshine adjustment and heat insulation. By utilizing such characteristics, the transparent heat insulating film is used for windows of buildings, frozen / refrigerated showcases, heat insulating surfaces, windows for vehicles, etc., and is useful for improving the living environment and energy saving.

[0004]

However, the conventional heat ray-shielding materials have the drawback that organic materials have poor durability and initial performance deteriorates with changes in environmental conditions and the passage of time. . On the other hand, complex compounds have durability, but they have a drawback in that the compounds themselves are strongly colored not only in the near infrared region but also in the visible region, and the use thereof is limited.

Further, since the heat ray reflective film of the prior art reflects not only heat rays but also visible rays by the metal vapor deposition layer, there is a fatal defect that the lighting property is impaired and the interior becomes dark when attached to a window glass or the like. It was Further, in order to form such a vapor-deposited layer, the equipment is large and therefore the cost is high, so that the versatility as a product is poor.

Further, the heat ray absorbent is uniformly dispersed in the resin to form a film of the heat ray absorbent. As this resin binder, acrylic resin, polyester resin, alkyd resin, polyurethane resin, epoxy resin,
Thermoplastic resins such as amino resins and vinyl resins are generally used. However, these resins used as a binder have a low hardness of the film, are easily scratched, and have poor scratch resistance. In order to improve the scratch resistance of these heat ray reflective films in practice, it is desired that the outer surface of the heat ray reflective film be subjected to a hard coat treatment. However, after the heat ray absorbing material is coated, the outer surface is again hard coated, resulting in high cost and poor versatility.

[0007]

Means for Solving the Problems The present inventor has conducted extensive studies on a heat ray-shielding material which exhibits absorption in the near red-far infrared region, has little coloring, and is excellent in durability, and as a result, has a primary particle diameter of 0. Tin oxide of 0.5 μm or less, preferably 0.1 μm or less,
ATO (antimony-tin oxide) and ITO (indium-tin oxide) ultrafine metal oxide powders are dispersed in a UV-curable resin so that they are easily irradiated with UV light to cure. Then, they have found that an ultraviolet-curable resin composition having a heat ray-shielding property can be obtained with a coating film having excellent scratch resistance and a single coating, and the present invention was completed.

The present invention comprises fine particles of an inorganic metal having a heat ray absorption ability and a primary particle diameter of 0.5 μm or less and active energy ray-polymerizable (meth) acrylate having a (meth) acryloyl group as a binder thereof. Is cured with
A heat ray-shielding resin composition having scratch resistance, and the same
Related to the coated film. .

Examples of the metal that absorbs heat rays include titanium oxide, zinc oxide, indium oxide, tin oxide and zinc sulfide, but tin oxide, ATO (antimony tin oxide),
A metal oxide of ITO (indium tin oxide) is effective. 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 heat ray-shielding inorganic metal fine particles in the resin composition of this patent can be arbitrarily selected according to the required heat ray-shielding ability, but the particles are not stably aggregated in the resin and are kept stable. I have to lean. ATO can be produced, for example, by the method described in JP-A-58-117228 or JP-A-6-262717, and ITO can be manufactured, for example, in JP-A-63-1.
It can be produced by the method described in Japanese Patent No. 1519.

As the polymerizable (meth) acrylate having a (meth) acryloyl group of the ultraviolet curable resin used in the present invention, neopentyl glycol (meth) acrylate and 1,6-hexanediol di ( (Meth) acryl
, Triethylene glycol di (meth) acrylate,
Triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Rutetra (meth) acrylate, dipentaerythritol-hexa (meth) acrylate and the like can be used, but in order to obtain a coating film having excellent killing resistance, pentaerythritol tetra (meth) acrylate is required. -, Polypentaerythritol triacrylate and dipentaerythritol hexaacrylate are preferred. The ratio of the ultraviolet curable resin to the resin component of the composition is preferably 50% by weight to 98% by weight, more preferably 80% by weight to 98% by weight.

Further, an active energy having a (meth) acryloyl group as a binder component which can be added if necessary.
Acrylic resin, polyester resin, butyral resin for the purpose of improving the adhesiveness with the film or the compatibility between the fine particles of the inorganic metal and the ultraviolet curable resin in addition to the linearly polymerizable polyfunctional (meth) acrylate. A polymer such as a resin can be added. For example, Byron (polyester resin manufactured by Toyo Corporation) can be used as the polyester resin, and S-REC made by Sekisui Chemical Co., Ltd. can be used as the butyral resin. In particular, a polymer having a hydroxy group has a good dispersibility of a metal oxide and, at the same time, has a function of improving the adhesiveness of an ink and relaxing the shrinkage of a film. The ratio of the composition of the polymer to the resin component is 3% by weight or more and 50% by weight or less, more preferably 20% by weight.
% By weight or less is preferred. 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.

Further, in order to successfully disperse the ultrafine particles of the inorganic oxide in the ultraviolet curable resin, a dispersant can be added as 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. Activator, higher fatty acid polyethylene glycol ester-based nonionic surfactant, silicone-based surfactant,
There are a fluorosurfactant, a polymer activator having an amide ester bond and the like. Among them, especially carboxylic acid type,
A polycarboxylic acid-based dispersant is suitable, for example, R-
COOH, RSO ₂ NHCH ₂ COOH, RSCH ₂ C
OOH, RSOCH ₂ COOH, RCH ₂ COOH, R
CH (SO ₃ H) a carboxylic acid-based surfactant such as a sulfonic acid Karubon acid (R is, for example, carbon atoms to a saturated or unsaturated alkyl group having 10 to 20), such as COOH, repeating unit has the formula -CH ₂ - _{CH (COOH) -, CH 2} C
_{H (CH 2 COOH) -CH (} Ph) -CH 2 -, - C
H (COOH) -CH (COOH) -C (CH 3) 2 -
Examples thereof include polycarboxylic acid-based surfactants such as CH ₂ — and —CH ₂ —CH (CH ₂ COOH) —. More specifically, Floren AF-405, G-685, G-8.
20 etc. (manufactured by Kyoeisha Yushi Co., Ltd.) can be used.
The additive of the dispersant is preferably 0.1% by weight or more and 10% by weight or less with respect to tin oxide, ATO or ITO.

A photopolymerization initiator is used for curing the resin composition of the present invention to form a film (coating film), and the photopolymerization initiator is previously dissolved in the resin composition. The photopolymerization initiator is not particularly limited and various known ones can be used, and the amount thereof is 0.1-15% by weight, preferably 0.5-12, based on the resin composition.
If the content is too high and the content thereof is too small, the curability is lowered, which is not preferable, and if it is too large, the strength of the cured coating is deteriorated. Specific examples of the photopolymerization initiator include Irgacure-184, Irgacure-651 (manufactured by Ciba-Geigy), Darocur-1173 (manufactured by Merck), benzophenone, methyl O-benzoylbenzoate, p-dimethylbenzoic acid ester,
Examples include thioxanthone, alkylthioxanthone, amines and the like. The film thickness of the cured product (coating) is not particularly limited and can be selected, for example, in the range of 0.1 to 10 μm depending on the application.

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. Examples of the method for producing the ultraviolet-curable heat ray-shielding resin composition and the method for coating the film on the film according to the present invention include the following methods. It can be cured by irradiating an ultraviolet ray to a dispersion liquid of an inorganic metal such as tin oxide, ATO, or ITO, which has been differentially acidified to 0.5 μ, preferably 0.1 μm or less, in an organic solvent by a wet microparticulation method or the like ( An uncured monomer selected from polymerizable (meth) acrylates having a (meth) acryloyl group is added alone or in combination of two or more, and then a photopolymerization initiator is dissolved to obtain an ultraviolet curable heat ray-shielding resin composition. obtain. At this time, if necessary, a predetermined amount of a dispersant, a polymer, or an organic solvent can be added.
As a method for coating the composition with a film, for example, an ordinary method such as a dipping method, a gravure coating method, an offset coating method, a roll coating method, a bar coating method, and a spraying method is performed, and the solvent is volatilized with hot air after coating. Then, the composition coated on the film is instantaneously cured by irradiating with ultraviolet rays using a high pressure mercury lamp, a carbon arc lamp, a xenon lamp or the like. Examples of the solvent used in the above method include common organic solvents such as toluene and ethyl acetate, and examples of the coating film include polyester, polybutylene terephthalate, polypropylene, polyacetal, polycarbonate and the like.

[0015]

【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. All the addition ratios in the examples are shown by weight%. Example 1 0.1 μ dispersed in toluene in a vessel equipped with a stirrer
Solid content of ATO (antimony-tin oxide) of 5 or less
Take 30 parts of 0% fine particles and add the dispersant Floren A to it.
F-405 (polycarboxylic acid type dispersant manufactured by Kyoeisha Yushi)
6 parts of a 3% toluene solution of is added with thorough stirring. Add 20 parts of toluene with further stirring. While stirring well with this, polyester resin Byron 24
Add 7 parts of SS (manufactured by Toagosei) little by little. UV-curable resin dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.)
Add 20 parts little by little with good stirring. Finally, 1.4 parts of a photoinitiator Irgacure-184, 0.1 part of a slip agent SH-29PA (manufactured by Sanopco), and 1 part of toluene.
Add 0 parts and stir until the photoinitiator is completely dissolved to obtain an ultraviolet-curable resin composition (1) for blocking heat rays.
This composition had a solid content of 41% and a viscosity of 11.7 CPS. The dispersion was stable.

Example 2 As in Example 1, except that 6 parts of a 3% solution of Florene G-820 was used as the dispersant, the solid content was 41%, the viscosity was 13.4 CPS. To obtain a resin composition (2).

Example 3 The solid content was 41% and the viscosity was 1 in the same manner as in Example 1 except that 10 parts of Byron 24SS was used as the polyester resin.
1.5 CPS. To obtain a resin composition (3).

Example 4 A resin composition (4) was obtained in the same manner as in Example 1 except that 7 parts of Byron 20SS was used as the polyester resin.

Example 5 1% of a 3% toluene solution of the dispersant Floren G-405 was used.
A resin composition (5) was obtained in the same manner as in Example 1 except that 2 parts were used.

Example 6 ITO dispersed in toluene as fine particles of inorganic metal
A resin composition (6) was obtained in the same manner as in Example 1 except that a 50% solution of (tin-doped indium oxide) was used.

Example 7 A resin composition (7) was obtained in the same manner as in Example 1 except that a 50% tin oxide solution dispersed in toluene was used as the inorganic metal fine particles.

Comparative Example 1 To 100 parts of a 50% solution of ATO dispersed in toluene, 6 parts of a 3% solution of Florene G-820 as a dispersant was added and well stirred. 100 parts of polyester resin Vylon 20SS as a binder was added thereto and well stirred to obtain a resin composition (7) having a solid content of 38.9%.

Comparative Example 2 To 100 parts of a 50% solution of ATO dispersed in toluene, 6 parts of a 3% solution of Florene G-820 as a dispersant was added and well stirred. 50 parts of acrylic resin P-5109 (manufactured by Nippon Kayaku Co., Ltd.) as a binder was added thereto and well stirred to obtain a resin composition (8) having a solid content of 40.4%.

Comparative Example 3 A resin composition (9) was obtained in the same manner as in Comparative Example 1 except that a 50% solution of ITO dispersed in toluene was used.

Comparative Example 4 A resin composition (10) was obtained in the same manner as in Comparative Example 2 except that a 50% tin oxide solution dispersed in toluene was used.

[Preparation of Coating Film] (1) A polyester film having a thickness of 50 μm was coated with the resin composition obtained in Example 1-10 by a coating bar.
After coating and drying the solvent with hot air, the resin composition (1) to the resin composition (6) were irradiated with a high-pressure mercury lamp of 80 W at a conveyor speed of 20 m / min. After curing, a target coating film was obtained. The resin compositions (7) to (10) were dried with hot air to form films, which were used as coating film samples. Table 1 shows the scratch resistance, transparency, and near-infrared spectral characteristics of the obtained film. (2) The composition (3) of Example 3 was applied to a polyester film having a thickness of 50 μm, and the thickness was 2.7 μm, 3.5 μm, 4.6.
Films (a), (b), (c) coated on μ
The spectral characteristics of are shown in FIG.

[0027]

[Table 1] ◎: Very good XX: Very

[0028]

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]

1] Films (a) and (b) of the composition (1) of Example 1.
And spectral characteristics of uncoated polyester film (c)

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C01G 15/00 C01G 15/00 B 19/02 19/02 Z C08F 2/44 MCQ C08F 2/44 MCQ 2/48 2/48 MDJ MDJ E06B 5/00 E06B 5/00 B

Claims (4)

[Claims] 1. A primary particle diameter of 0.5 μm capable of absorbing heat rays.
A heat ray-blocking resin composition having scratch resistance and curable by ultraviolet rays, which comprises the following fine particles of an inorganic metal and an active energy ray polymerizable polyfunctional (meth) acrylate having a (meth) acryloyl group Coated film. 2. Fine particles of a heat ray-blocking inorganic metal are tin oxide and A
The resin composition according to claim 1, which is an ultrafine powder of a metal oxide of TO (antimony-tin oxide) or ITO (indium-tin oxide), and a film coated with 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. A binder containing fine particles of a heat ray-blocking inorganic metal.
A resin composition according to claim 1, wherein a carboxylic acid- or polycarboxylic acid-based dispersant is used to disperse the resin in the resin composition, and a film coated with the resin composition.