JPH09208863A - Heat-absorbing coating composition and method for imparting heat-absorbing property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating compsn. which forms a heat-absorbing coating layer on a substrate and to provide a method for easily and conveniently imparting a heat absorbing property using the same. SOLUTION: This compsn. contains a film-forming resin component and an infrared-absorbing component comprising at least one infrared-absorber selected from among infrared absorber (a) [0.1-900 pts.mass (based on 100 pts. mass resin component; the same applies hereunder) metal oxide semiconductor powder], infrared absorber (b) (0.02-20 pts.mass copper ion), and infrared absorber (c) (0.01-10 pts.mass phthalocyanine compd.). This method comprises applying the compsn. to the surface of a substrate to form a coating layer contg. an infrared absorber. A light-transmitting material constituting conventional greenhouses can be used as the substrate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a heat ray absorbing coating composition and a heat ray absorbing method using the same.

[0002]

2. Description of the Related Art Conventionally, as a covering material for agriculture for covering a plant cultivation atmosphere and constructing a greenhouse facility, a soft translucent material made of a material such as soft vinyl chloride resin, poeritylene resin, or fluororesin, or A hard translucent material made of a material such as glass or hard vinyl chloride, or a multilayer translucent material formed by laminating films or sheets made of these materials is used. However, since these coating materials are not particularly considered for their ability to selectively absorb or transmit light rays in a specific wavelength range, a greenhouse facility using these coating materials may have a problem during the summer period. The temperature in the facility rises considerably. For this reason, it has been pointed out that the greenhouse facility cannot be used to grow agricultural products, especially agricultural products that dislike high temperatures, during the summer season.

[0003]

SUMMARY OF THE INVENTION The present invention has been made under such circumstances, and a coating which is practically useful is obtained by formulating a specific infrared absorber together with a resin component under specific conditions. It has been achieved based on this finding that a composition can be obtained.

An object of the present invention is to provide a heat ray absorbing coating composition capable of forming a heat ray absorbing coat layer on a substrate. Another object of the present invention is to provide a method capable of imparting heat ray absorbability to a substrate made of a translucent material very easily by using the coating composition.

[0005]

The heat ray absorbing coating composition of the present invention comprises a resin component having a film-forming property and an infrared absorbing agent, and the infrared absorbing agent is the infrared absorbing agent a described below. And at least one selected from infrared absorber b and infrared absorber c. Infrared absorber a: 0.1 with respect to 100 parts by mass of the resin component
To 900 parts by mass of metal oxide semiconductor fine powder infrared absorber b: 0.0 with respect to 100 parts by mass of resin component
Metal ion consisting of 1 to 20 parts by mass of divalent copper ion Infrared absorber c: 0.0 based on 100 parts by mass of resin component
1 to 10 parts by mass of phthalocyanine compound

In the coating composition of the present invention, the infrared absorbent preferably comprises an infrared absorbent a and at least one of infrared absorbent b and infrared absorbent c. Further, when the infrared absorbent contains the infrared absorbent b, it is preferable that a phosphoric acid group-containing compound composed of a phosphoric acid ester or a phosphonic acid ester is contained, and in this case, the phosphoric acid group-containing compound is A phosphoric acid ester represented by the following formula (1) or a phosphonic acid ester represented by the following formula (2) is preferable.

[0007]

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[0008]

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When the infrared absorbing agent contains the infrared absorbing agent a, the metal oxide semiconductor fine powder is at least one selected from conductive indium oxide, tin oxide, anhydrous zinc antimonate and zinc oxide. Is preferred.

In the heat ray absorbing coating composition of the present invention, the resin component is preferably in a state of being dissolved or dispersed in a liquid medium.

The heat ray absorbing method of the present invention is characterized by forming a coating layer containing an infrared absorbing agent on the surface of a substrate by applying the above heat ray absorbing coating composition. Here, as the substrate, a translucent material that constitutes an existing greenhouse facility can be used.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The heat ray absorbing coating composition and the heat ray absorbing method of the present invention will be described in detail below. The heat ray absorbing coating composition of the present invention,
A resin component having a film-forming property and a specific infrared absorber are contained. Specifically,
In a preferred example, the coating composition of the present invention functions as a vehicle, which is composed of a resin component and a solvent in which the resin component is dissolved or a liquid medium composed of a liquid compound in which the resin component is dispersed. The coating basic component has a specific infrared absorber contained in a specific ratio, and further contains an appropriate additive as necessary.

[Resin Component] The resin component in the coating composition of the present invention is a resin capable of forming a transparent film by itself, and constitutes a vehicle of the coating composition together with a liquid medium described later. Is. Specific examples of this resin component include an acrylic resin,
Polyolefin resin, styrene resin, fluorine resin, epoxy resin, urethane resin, alkyd resin, amino resin,
Examples thereof include polyester resins, cellulose resins, and the like. In the present invention, preferred resins are acrylic resins, fluororesins, urethane resins and polyester resins.

The resin component may be a polymerizable compound capable of forming a polymer by a suitable curing treatment to be applied later, and specific examples thereof include a monomer, an oligomer or a prepolymer which produces the above resin. be able to.

[Liquid medium] In the coating composition, the resin component is in the form of a solution dissolved in an appropriate organic solvent, or the resin fine particles constituting the resin component are dispersed in an aqueous medium or a liquid medium composed of a liquid organic compound. It is said that Specific examples of the organic solvent or organic compound include hydrocarbon compounds such as toluene, xylene, hexane and heptane, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and butyl alcohol, ethyl acetate, isopropyl acetate and butyl acetate. , Esters such as butyl cellosolve acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethers such as butyl cellosolve, and the like. Examples of the aqueous medium include water and a liquid prepared by mixing water with a water-soluble organic solvent such as alcohol.

The proportion of the resin component in the liquid medium varies depending on the type of the liquid medium, the type of the resin component, etc., but it is important that good coatability is obtained, and usually 1 to 70.
It is preferably part by mass. When the proportion of the resin component is too large, the coating property of the coating composition is low, while when the proportion of the resin component is too small,
The efficiency in coating is small.

[Infrared absorbing agent] The coating composition of the present invention contains at least one infrared absorbing agent selected from the following infrared absorbing agent a, infrared absorbing agent b and infrared absorbing agent c as an essential component. ing. (1) Infrared absorber a: metal oxide semiconductor fine powder This infrared absorber a is contained in a proportion of 0.1 to 900 parts by mass with respect to 100 parts by mass of the resin component. (2) Infrared absorber b: metal ion composed of divalent copper ion This infrared absorber b is contained in a proportion of 0.01 to 20 parts by mass with respect to 100 parts by mass of the resin component. (3) Infrared absorber c: Phthalocyanine compound This infrared absorber c is contained in a proportion of 0.01 to 10 parts by mass with respect to 100 parts by mass of the resin component.

(1) Infrared absorbing agent a The infrared absorbing agent a is composed of a fine powder of a metal oxide semiconductor, and specifically, conductive indium oxide, tin oxide, anhydrous zinc antimonate and oxide. One or more selected from zinc. This infrared absorbing agent a exhibits remarkable infrared absorbing characteristics in a wavelength region of approximately 1200 nm or more.

In the case of using a material containing indium oxide as a main component, some of the indium atoms in indium oxide were replaced with tin atoms, and further oxygen defects were introduced to increase the carrier electron density in indium oxide. ,
A composite oxide of indium oxide and tin oxide (hereinafter referred to as “I
Also referred to as "TO" (Indium Tin Oxide). ) Is preferable. When tin oxide as a main component was used, some of the tin atoms in the tin oxide were replaced with antimony atoms, and oxygen defects were introduced to increase the carrier electron density in tin oxide. , A composite oxide of tin oxide and antimony oxide (hereinafter referred to as "ATO" (Antimony Tin Oxid
Also called e). ) Is preferable.

Compared with indium oxide alone or tin oxide alone, the above ITO or ATO causes reflection of light rays in the near-infrared region from a region on the lower wavelength side, so that it is longer than 1200 nm. It seems that the transmittance of light in the wavelength range is further reduced.

As ITO or ATO, the maximum particle size is 0.1 μm or less, and the particle size distribution is 0.001.
Ultrafine powder in the range of ~ 0.05 μm is preferred. When the maximum particle diameter exceeds 0.1 μm, the coating layer formed from the obtained coating composition may have a reduced light transmittance in the visible light region. On the other hand, ITO or ATO has a particle size of 0.001μ.
When the content of the metal oxide semiconductor is less than m, it becomes difficult to prepare a coating composition in which the fine particles are agglomerated, and it is difficult to prepare such a metal oxide semiconductor fine particle. The production of powder is also very difficult.

Anhydrous zinc antimonate has the chemical formula (ZnS
b_TwoO₆) Or [Zn (Sb_TwoO _Three)_Two] Or group
Formula ZnO / Sb_TwoO_FiveIs represented by, for example,
Manufacturing method disclosed in JP-A-6-219743
With a primary particle size of 5-500 nm
Has good infrared absorption properties and good visible light transmission
It is preferable that such conductive anhydrous antimony is used.
Zinc acid is a zinc compound that produces zinc oxide when fired.
And antimony formation that produces antimony oxide by firing
And a conductive antimony anhydride finally produced.
ZnO / Sb in zinc_TwoO_FiveHas a molar ratio of 0.8-
Mix at a ratio of 1.2 at 500-680 ° C
It can be manufactured by firing.

As the zinc oxide, zinc hydroxide, an inorganic acid salt of zinc, for example, zinc carbonate, basic zinc carbonate, zinc nitrate, zinc chloride, zinc sulfate, etc., and as an organic acid salt of zinc, zinc formate, acetic acid, etc. It is obtained by calcining a zinc compound such as zinc or zinc oxalate. The zinc compound has a primary particle size of 200 nm or less, and is particularly obtained from a salt of an acid that is volatilized by firing, that is, a carbonate or an organic acid salt. Zinc oxide is preferred.

It is desirable that the ratio of the infrared absorbent a composed of the fine powder of metal oxide semiconductor as described above is as high as possible, but it is 0.1 to 90 per 100 parts by mass of the resin component.
It is 0 part by mass, preferably 5 to 400 parts by mass.

(2) Infrared absorber b The metal ion composed of divalent copper ion used as the infrared absorber b is obtained by a metal compound composed of an appropriate copper compound. Specific examples of such copper compounds include copper acetate, copper chloride, copper formate, copper stearate, copper benzoate, copper ethylacetoacetate, copper pyrophosphate,
Anhydrates or hydrates of copper naphthenate, copper citrate and the like can be mentioned. This infrared absorbing agent b is approximately 650-800.
It exhibits outstanding infrared absorption properties in the wavelength range over nm.

When the infrared absorbent b is used, in order to enhance the dispersibility of the divalent copper ion in the coating composition or the finally formed coating layer,
It is preferable to contain a phosphoric acid group-containing compound consisting of phosphoric acid ester or phosphonic acid ester. The phosphoric acid group-containing compound may be contained in the coating composition, and may be contained as one component of the coating composition, in a state of being dissolved or mixed in the resin constituting the resin component, or chemically. It may be contained in a state of being bound to the above, or may be contained in a state of being bound to other composition components.

In the present invention, "phosphate group" means PO
(OH) _n- (n is 1 or 2). As such a phosphoric acid group-containing compound, a phosphoric acid ester represented by the above formula (1) (hereinafter, also referred to as “specific phosphoric acid ester”) or a phosphonic acid ester represented by the above formula (2). (Hereinafter, also referred to as “specific phosphonate ester”) is preferably used.

Specific examples of the specific phosphoric acid ester include:
Monomethyl phosphate, dimethyl phosphate,
Monoethyl phosphate, diethyl phosphate,
Monoisopropyl phosphate, diisopropyl phosphate, mono n-butyl phosphate, di n-butyl phosphate, monobutoxyethyl phosphate, dibutoxyethyl phosphate, mono (2-ethylhexyl) phosphate, di (2-ethylhexyl) Phosphate, mono n-decyl phosphate,
Examples include di-n-decyl phosphate, monoisodecyl phosphate, diisodecyl phosphate, monooleyl phosphate, dioleyl phosphate, monoisostearyl phosphate, diisostearyl phosphate, monophenyl phosphate, diphenyl phosphate. To be

Further, as the specific phosphoric acid ester, as shown in the above formula (1), as the substituent R ¹ , an acryloyl group (when X is a hydrogen atom) or a methacryloyl group (where X is a hydrogen atom) to which an ethylene oxide group is bonded. A compound having a polymerizable functional group consisting of (when X is a methyl group) can be used. Here, the repeating number m of the ethylene oxide group is an integer of 0 to 5. If the value of m exceeds 5, the compatibility with the resin component will be low, and thus the transparency of the coating layer obtained from the coating composition may decrease.

Specific examples of the specific phosphoric acid ester having such a polymerizable functional group include 2-acryloxyethyl acid phosphate, 2-methacryloxyethyl acid phosphate, and bis (2-methacryloxyethyl). Acid phosphate) and the like.

Further, the specific phosphoric acid ester having such a polymerizable functional group is contained in a monomer composition for obtaining the resin relating to the above-mentioned resin component and polymerized to give a resin. It may be contained in the molecular structure of the component.

Specific examples of the specific phosphonate ester include monomethylmethylphosphonate, monoethylethylphosphonate, monobutylbutylphosphonate, mono (2-ethylhexyl) 2-ethylhexylphosphonate and the like.

Among them, the group R ¹ in the above formula (1) or the group R ² and the group R ³ in the above formula (2).
Is a 2-ethylhexyl group, specifically,
Mono (2-ethylhexyl) phosphate or di (2-ethylhexyl) phosphate or mono (2-ethylhexyl) 2-ethylhexylphosphonate has excellent compatibility with the resin component and enhances the dispersibility of the infrared absorbent b. It is preferable in that it can

In the present invention, the proportion of the infrared absorbent b is 0.01 to 20 parts by mass, preferably 1 to 20 parts by mass, relative to 100 parts by mass of the resin component.

The phosphoric acid group-containing compound is preferably used in a ratio of 1 to 10 mol per 1 mol of the metal ion composed of divalent copper ion.
It is possible to sufficiently disperse metal ions composed of valent copper ions.

(3) Infrared absorber c Specific examples of the phthalocyanine compound useful as an infrared absorber include, for example, JP-A-5-222047,
Compounds soluble in alcohols, ketones, aromatic hydrocarbons and the like, which are disclosed in JP-A-6-25548,
5-Octakisanilino- (3,6-octakisphenylthio) oxyvanadium phthalocyanine, 4-tetrakisanilino- (3,5,6-dodecakisphenylthio) zinc phthalocyanine, 4-tetrakisanilino-
(3,5,6-dodecakisphenoxy) zinc phthalocyanine and the like can be mentioned. This infrared absorber c is
It exhibits remarkable infrared absorption properties in a wavelength range of approximately 800 to 900 nm.

(4) Other infrared absorbing agent (infrared absorbing agent d) In the present invention, an infrared absorbing agent d composed of a phenylenediamine derivative represented by the following formula (3) is used as a part of the infrared absorbing agent. can do. The infrared absorbent d exhibits good infrared absorption characteristics in the wavelength range of approximately 900 to 1000 nm.

[0038]

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[In the above formula (3), R is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, X is SbF ₆ ,
ClO ₄ , PF ₆ , BF ₆ , NO ₃ or a halogen atom is shown, and n is 1 or 2. ]

Specific examples of the phenylenediamine derivative include N, N, N ', N'-tetrakis (p-di-n).
-Butylaminophenyl) -p-benzoquinone-bis (immonium perchlorate), N, N, N ', N'-tetrakis (p-diethylaminophenyl) -p-benzoquinone-bis (immonium hexafluoroantimonate) Salt), N, N, N ', N'-tetrakis (p-di-n
-Hexylaminophenyl) -p-benzoquinone-bis (immonium fluoroborate), N, N, N ',
N'-tetrakis (p-di-isopropylaminophenyl) -p-benzoquinone-bis (immonium nitrate), N, N, N ', N'-tetrakis (p-di-n-)
Octylaminophenyl) -p-benzoquinone-bis (immonium hexafluoroantimonate), N,
N, N ', N'-Tetrakis (p-diethylaminophenyl) -p-benzoquinone-bis (immonium bromine salt), N, N, N', N'-tetrakis (p-di-n-
Butylaminophenyl) -p-phenylenediaminium perchlorate, N, N, N ', N'-tetrakis (p-
Dimethylaminophenyl) -p-phenylenediaminium chloride salt, N, N, N ', N'-tetrakis (p-di-n-dodecylaminophenyl) -p-phenylenediaminium hexafluoroantimonate, N , N,
N ', N'-Tetrakis (p-diethylaminophenyl) -p-phenylenediaminium fluoroborate, N, N, N', N'-tetrakis (p-di-n-butylaminophenyl) -p -Phenylenediaminium fluorine salt, N, N, N ', N'-tetrakis (p-diethylaminophenyl) -p-phenylenediaminium perchlorate, and the like.

The ratio of the infrared absorbent d is the resin component 1
0.01 to 1 part by weight, especially 0.0
It is preferably 1 to 0.7 parts by mass.

In the coating composition of the present invention,
It is preferable to use the infrared absorbent a as an essential component of the infrared absorbent. Infrared absorber b or infrared absorber c
Can be used alone, but the infrared absorber b and / or the infrared absorber c can be used together with the infrared absorber a, and it is also possible to use the three of them together, and further the infrared absorber It is also possible to use all four of a to infrared absorber d together. According to the aspect in which a plurality of infrared absorbers are used in combination, the heat ray absorption characteristics of each infrared absorber are exerted in a weighted manner, so that a coating composition having a heat ray absorption property according to the purpose can be obtained.

In the coating composition of the present invention, the infrared absorbing agent may be present in basically any state as long as it is contained in the coating layer formed by the coating composition. Specifically, it is contained as a component of the coating composition in a state of being dissolved or dispersed in a liquid medium, a state of being dissolved or mixed in a resin constituting a resin component, or chemically bound. It may be either a form contained in a state or a form combined with other composition components.

The ratio of the infrared absorbent varies depending on the kind of the infrared absorbent, including the case where a plurality of kinds of infrared absorbents are used in combination, but the infrared absorbent contained in the resin component and / or the liquid medium in a state of being dissolved or chemically bound thereto. In absorbent, resin component 1
The range of 0.01 to 30 parts by mass with respect to 00 parts by mass is 0.1 to 90 parts by mass with respect to 100 parts by mass of the resin component in the infrared absorbent contained in a state of being dispersed in the liquid medium.
The range is 0 parts by mass.

When the content ratio of the infrared absorbing agent is too small, it is necessary to form a coating layer having a large film thickness in order to obtain the necessary heat ray absorption, and the coating amount becomes large, which is uneconomical. However, the light transmittance of visible light may be unnecessarily reduced. On the other hand, when the content ratio of the infrared absorbing agent is excessively large, it becomes difficult to make the necessary amount of the infrared absorbing agent uniformly exist in the coating composition or the coating layer, and the strength of the coating layer to be formed and applied. The characteristics such as the adhesiveness of the coat layer to the substrate are deteriorated.

[Additives] Various additives can be added to the coating composition of the present invention as necessary. As the additive, a drying accelerator, a wetting agent, a defoaming agent, a dispersion stabilizer, a preservative, an ultraviolet absorber, a plasticizer, an antioxidant,
Although other examples can be mentioned, it may be preferable to add a visible light absorber in the present invention.

[Visible Light Absorber] In the present invention, for example, a specific visible light absorber having a light absorbing property in a wavelength range of 500 to 600 nm can be further contained. As such a specific visible light absorber, 2
A metal ion composed of a valent cobalt ion can be used.

The metal ion composed of a divalent cobalt ion used in the specific visible light absorber is obtained from a metal compound composed of an appropriate cobalt compound. Specific examples of the cobalt compound include cobalt acetate, cobalt formate, cobalt benzoate, cobalt naphthenate, cobalt bromide, cobalt chloride, cobalt nitrate, cobalt sulfate, and anhydrous or hydrated cobalt diammonium sulfate. To be

When a metal ion composed of a divalent cobalt ion is used as the specific visible light absorber, a phosphoric acid group-containing compound composed of a phosphoric acid ester or a phosphonic acid ester is used as in the infrared absorbent b described above. It is preferable that the metal ion is contained in a ratio of 1 to 10 mol per mol of the metal ion. Examples of the phosphoric acid group-containing compound include the specific phosphoric acid ester and the specific phosphonic acid ester exemplified as the phosphoric acid group-containing compound that is preferably used together with the infrared absorber b.

Further, as the phosphoric acid group-containing compound, the group R ¹ in the above formula (1) or the group R ^{1 in the} above formula (2) is used.
² and a compound in which the group R ³ is a 2-ethylhexyl group,
Specifically, mono (2-ethylhexyl) phosphate or di (2-ethylhexyl) phosphate,
Alternatively, mono (2-ethylhexyl) 2-ethylhexylphosphonate is particularly preferable because it has excellent compatibility with the resin component and can enhance the dispersibility of metal ions composed of divalent cobalt ions.

The specific visible light absorber is used in an amount of 0.01 to 20 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the resin component. When this ratio is less than 0.01 part by mass, the wavelength is 500 to 600 n.
The performance of absorbing visible light of m is hardly obtained. on the other hand,
If this ratio exceeds 20 parts by mass, it will be difficult to uniformly disperse the metal ions, and the amount will be 500 to 60.
It becomes difficult to selectively absorb 0 nm visible light and sufficiently transmit visible light in other wavelength regions. Further, the specific visible light absorber is preferably used in such a ratio that the total amount with the infrared absorber is 900 parts by mass or less with respect to 100 parts by mass of the resin component.

The phosphoric acid group-containing compound is used together with the above infrared absorber b and / or the specific visible light absorber, but the total amount thereof is 200 parts by mass or less, particularly 100 parts by mass of the resin component. It is preferably 100 parts by mass or less.

As described above, in the present invention, in addition to the infrared absorbent, a metal ion composed of a divalent cobalt ion can be used as the specific visible light absorbent.
In addition to these metal ions, ions of other metals may be contained as long as the object of the present invention is not impaired. Examples of such other metal ions include sodium ion, potassium ion, iron ion, manganese ion, magnesium ion, nickel ion, and tungsten ion. Ions derived from other metals are obtained from an appropriate metal compound like divalent copper ions or divalent cobalt ions. By using the ions of such another metal, the light absorption characteristics corresponding to the ions of the other metal can be obtained.

[Other Visible Light Absorbing Agent] In the present invention, as other visible light absorbing agent, a compound having a pyrazine ring, a perylene-based dye, an anthraquinone-based dye, a naphthoquinone-based dye, an aminium-based dye or the like metal complex, etc. Other pigments, dyes, organic pigments, etc. can be used. These dyes and compounds can be used in a ratio of 0.01 to 5 parts by mass with respect to 100 parts by mass of the resin component.

The coating composition of the present invention also comprises
As a cross-linking agent, a polyisocyanate compound, melamine, and various metal compounds can be contained, whereby properties such as coatability can be improved.

The coating composition of the present invention is most generally mixed with the solution or dispersion of the above-mentioned resin component, an infrared absorbing agent and a specific visible light absorbing agent or other additive which is optionally used. It is obtained by doing. It is also possible to use a method in which the infrared absorbent is dissolved in or chemically bound to the resin component, and the resin component is dissolved or dispersed in the liquid medium. Further, for example, when a metal ion composed of a divalent copper ion is used as the infrared absorber or when a divalent cobalt ion is used as the specific visible light absorber, these metal ions are added to the above-mentioned polymerizable functional group. The specific phosphoric acid ester may be contained in a monomer composition for obtaining a resin component, and the monomer composition may be subjected to polymerization treatment. Thus, depending on the type of infrared absorber,
It can also be added to the monomer for obtaining the resin component.

The coating composition of the present invention is, if necessary, diluted with heat rays in the state of having appropriate fluidity and consistency, like the ordinary coating composition, to impart a heat ray absorbing property, for example, a light-transmitting property. A coat layer is formed on the surface of the substrate made of a conductive material by being applied to the surface of the substrate, dried, and optionally cured. This coat layer is a layer in which an infrared absorber is contained in a thin film formed of a resin component or a state in which the infrared absorber is bound by a resin component, and among the light transmitted through the coat layer. Since the infrared ray is a heat ray absorbing coat layer having an action of being absorbed by the infrared absorber,
Heat absorption can be imparted to the substrate. Therefore, it is particularly useful for application to a base made of a translucent material, which is required to prevent irradiation of heat rays.

For example, the coating composition of the present invention
A glass, sheet or film having a heat ray absorbing property can be obtained by forming the coat layer by applying it to transparent glass or a translucent sheet or film. And, by using such glass, sheet or film as an agricultural coating material for constructing a greenhouse facility by covering a plant cultivation atmosphere, for example, to suppress a rise in temperature in the facility during the summer season. Can
The usage period of greenhouse facilities can be extended. Here, the glass, sheet or film used as the substrate may have heat ray absorbing property by itself, and the additive effect can be obtained together with the heat ray absorbing property of the coat layer.

Further, according to the heat ray absorbing property imparting method of the present invention, the heat ray absorbing coat layer is formed by applying the above-mentioned coating composition to the surface of the substrate, so that the desired substrate can be absorbed very easily. Can be imparted with
When the substrate is a translucent material, a heat ray-shielding translucent material is obtained. Therefore, by applying the coating composition of the present invention to a light-transmissive material that constitutes an existing greenhouse facility, a greenhouse facility having a heat ray-shielding property can be extremely easily formed. Further, the heat ray prevention layer can be formed on the substrate which should avoid receiving heat rays.

The coating amount of the coating composition of the present invention is
The thickness may be such that the required heat ray absorption characteristics are obtained, and the thickness is not particularly limited, but is usually 100 μm or less. The practically effective coating amount varies depending on the type of the infrared absorbing agent contained in the coating composition, but is, for example, 0.1 to 50 for the infrared absorbing agent a per 1 m ^2.
g, the infrared absorber b is 0.1 to 20 g, the infrared absorber c is 1 to 1000 mg, and the infrared absorber d is 1 to 10 g.
This is the range that will be present in an amount of 00 mg.

The specific means for applying the coating composition is not particularly limited, and various conventionally known means can be used. For example, dipping method, roll coater method, bar coater method, brush coating method,
A spraying method or the like can be used.

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In the following, "part" means "part by mass".

[Example 1] Prescription Resin component: Polyester resin "Etailer" (manufactured by Unitika Ltd.) 100 parts Organic solvent: Toluene-methyl ethyl ketone mixed liquid (mass ratio 1: 1) 550 parts Infrared absorber a: ATO super. Fine particle powder (manufactured by Sumitomo Cement Co., Ltd.) 150 parts Coating composition 1 by dissolving resin component in the above organic solvent, mixing infrared absorbent a in the obtained resin solution, and stirring Was prepared.

A transparent polyethylene terephthalate film "E5001" (manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm was used as a substrate, and the coating composition 1 was applied to one surface of the substrate using a bar coater and dried to obtain A.
A heat ray absorbing film was prepared by forming a coat layer having a film thickness of 10 μm in which TO was dispersed.

The light transmittance of the film on which this coat layer was formed was measured using a spectrophotometer. The results are shown in Table 1.

Example 2 In Example 1, 100 parts of a mixture of the resin solution, together with the infrared absorbent a, 28 parts of copper acetate, which is the infrared absorbent b, and 100 parts of di (2-ethylhexyl) phosphate was used. A coating composition 2 of the present invention was produced in the same manner except that (the amount of divalent copper ions was 7.7 parts based on 100 parts of the resin component) was added. A heat ray absorbing film was prepared in the same manner as in Example 1 except that the obtained coating composition 2 was used, and the light transmittance was measured. The results are shown in Table 1.

[Example 3] In Example 2, the resin solution was mixed with the mixture of the infrared absorbing agent a and the infrared absorbing agent b, and the phthalocyanine-based compound "Excolor 901B" of the infrared absorbing agent c (Nippon Shokubai Co., Ltd.). A coating composition 3 of the present invention was produced in the same manner as in Example 2 except that 1 part was added. A heat ray absorbing film was produced in the same manner as in Example 1 except that the coating composition 3 thus obtained was used, and the light transmittance was measured. The results are shown in Table 1.

Example 4 In Example 2, the resin solution was mixed with the mixture of the infrared absorbing agent a and the infrared absorbing agent b, and the phenylenediamine derivative “IRG-022” of the infrared absorbing agent d (Nippon Kayaku Co., Ltd. A coating composition 4 of the present invention was produced in the same manner as in Example 3 except that 1 part was added. A heat ray absorbing film was prepared in the same manner as in Example 1 except that the coating composition 4 thus obtained was used, and the light transmittance was measured. The results are shown in Table 1.

Example 5 In Example 3, the resin solution was mixed with infrared absorber a, a mixture of infrared absorber b and infrared absorber c, and further 30 parts of cobalt acetate tetrahydrate and di (2-ethylhexyl) were used. ) A coating composition of the present invention was prepared in the same manner as in Example 3 except that 27.5 parts of a mixture with 100 parts of phosphate (the amount of divalent cobalt ion was 1.5 parts based on 100 parts of the resin component) was added. Item 5 was manufactured. A heat ray absorbing film was prepared in the same manner as in Example 1 except that the obtained coating composition 5 was used, and the light transmittance was measured. The results are shown in Table 1.

[Example 6] Formulation Monomer component: butyl acrylate 60 parts Monomer component: 2-ethylhexyl acrylate 26 parts Monomer component: methyl methacrylate 14 parts Polymerization reaction solvent: toluene 200 parts

A monomer composition was prepared by thoroughly mixing the above components with stirring, and further adding 0.5 part of benzoyl peroxide as a polymerization initiator and mixing.
A polymer solution was obtained by subjecting this monomer composition to a polymerization treatment at 60 ° C. for 15 hours. Then 100 parts of a reaction mixture of 28 parts of copper acetate and 100 parts of di (2-ethylhexyl) phosphate was mixed into the polymer solution.
The amount of divalent copper ions was 7.7 parts with respect to 100 parts of the resin component in this mixed polymer solution. The coating composition 6 of the present invention was produced by adding 150 parts of ATO ultrafine particle powder to the polymer solution and thoroughly stirring and mixing. A heat ray absorbing film was produced in the same manner as in Example 1 except that the coating composition 6 thus obtained was used, and the light transmittance was measured. The results are shown in Table 1.

[Example 7] In Example 1, instead of 150 parts of ATO ultrafine particle powder, ITO ultrafine particle powder 15 was used.
A coating composition 7 of the present invention was produced in the same manner except that 0 part was used. A heat ray absorbing film was prepared in the same manner as in Example 1 except that the obtained coating composition 7 was used, and the light transmittance was measured. The results are shown in Table 1.

[Example 8] In Example 1, in place of 150 parts of ATO ultrafine particle powder, conductive anhydrous zinc antimonate sol "Cernax CX-Z200M" (manufactured by Nissan Chemical Industries, Ltd.) was evaporated. A coating composition 8 of the present invention was produced in the same manner except that 150 parts of fine particle powder obtained by drying was used. A heat ray absorbing film was prepared in the same manner as in Example 1 except that the obtained coating composition 8 was used, and the light transmittance was measured. Table 1 shows the results
Shown in

Example 9 In Example 1, instead of 150 parts of ATO ultrafine particle powder, zinc oxide dispersion “FX
-UFZ-D "(manufactured by Nippon Shokubai Co., Ltd.) was used to prepare coating composition 9 of the present invention in the same manner except that 150 parts of zinc oxide powder obtained by evaporation to dryness was used. A heat ray absorbing film was produced in the same manner as in Example 1 except that the obtained coating composition 9 was used, and the light transmittance was measured. The results are shown in Table 1.

[0075]

[Table 1]

As is clear from Table 1, according to the coating composition containing the infrared absorbing agent a made of fine powder of metal oxide semiconductor, the heat ray for surely blocking or attenuating near infrared rays having a wavelength of 1200 nm or more with high efficiency. An absorptive coat layer can be formed, and a coat layer having infrared absorbing properties in various wavelength regions can be formed depending on the type of infrared absorber contained.

[0077]

The coating composition of the present invention can be applied to a substrate to form a heat ray absorbing coat layer very easily, and can impart heat ray absorbing property to the substrate. Therefore, by using a translucent material as the substrate, a heat ray absorbing translucent material can be obtained, and this translucent material is applied to various applications in which it is required to prevent irradiation of heat rays. For example, the translucent material obtained by applying it to a translucent sheet or film is extremely useful as an agricultural covering material for constructing a greenhouse facility by covering a plant cultivation atmosphere. Furthermore, by applying the coating composition of the present invention to the translucent material of an existing greenhouse facility, it is possible to impart a suitable heat ray absorbing property to the greenhouse facility very easily.

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Claims (8)

[Claims] 1. A resin component having film-forming properties and an infrared absorbing agent are contained, and the infrared absorbing agent is at least one selected from the following infrared absorbing agent a, infrared absorbing agent b and infrared absorbing agent c. A heat ray absorbing coating composition comprising a seed. Infrared absorber a: 0.1 with respect to 100 parts by mass of the resin component
To 900 parts by mass of metal oxide semiconductor fine powder infrared absorber b: 0.0 with respect to 100 parts by mass of resin component
Metal ion consisting of 1 to 20 parts by mass of divalent copper ion Infrared absorber c: 0.0 based on 100 parts by mass of resin component
1 to 10 parts by mass of phthalocyanine compound 2. The heat ray absorbing coating composition according to claim 1, wherein the infrared absorbing agent comprises an infrared absorbing agent a and at least one of infrared absorbing agent b and infrared absorbing agent c. 3. The infrared ray absorbing agent containing the infrared ray absorbing agent b contains a phosphoric acid group-containing compound consisting of a phosphoric acid ester or a phosphonic acid ester, which is characterized in that: The heat ray absorbing coating composition as described in 1. 4. The phosphoric acid group-containing compound is a phosphoric acid ester represented by the following formula (1) or a phosphonic acid ester represented by the following formula (2), wherein: Heat ray absorbing coating composition. Embedded image Embedded image 5. When the infrared absorbent contains an infrared absorbent a, the metal oxide semiconductor fine powder is at least selected from conductive indium oxide, tin oxide, anhydrous zinc antimonate and zinc oxide. The heat ray absorbing coating composition according to any one of claims 1 to 4, which is one kind. 6. The heat ray absorbing coating composition according to claim 1, wherein the resin component exists in a state of being dissolved or dispersed in a liquid medium. 7. A coating layer containing an infrared absorbing agent is formed by applying the heat ray absorbing coating composition according to any one of claims 1 to 6 to the surface of a substrate. A characteristic method for imparting heat ray absorption. 8. The heat ray absorbing property imparting method according to claim 7, wherein the substrate is a translucent material which constitutes an existing greenhouse.