KR102211975B1 - Composion for hot radiation shielding film - Google Patents

Abstract

The present invention relates to improvement of the disadvantages of the conventional IR-shielding films used for windows of cars, buildings, or the like. The present invention provides a composition for an IR-shielding film used for windows of cars, buildings, or the like, which has improved IR-shielding performance and durability against bleaching and discoloration, and uses a metal nitride dispersion in combination with the equivalent level of a carbon black dispersion. The composition for an IR-shielding film according to the present invention shows improved IR-shielding performance and durability against bleaching and discoloration, as compared to the conventional window films, and reduces the amount of expensive antinomy tin oxide (ATO), indium tin oxide (ITO), tungsten, or the like, added for improving IR-shielding ratio to save the costs required for manufacturing a shielding film and to provide high industrial applicability.

Description

Composition for infrared shielding film and infrared shielding film using the same

The present invention relates to a composition for an infrared shielding film used for glass windows such as vehicles and buildings in order to selectively block visible light and minimize glare, and an infrared shielding film using the same.

Existing window films applied to buildings, electronic materials, and automobile glass are a method of blocking only the visible light region with metal coloring dyes, and sputtering of Ag, Au, Cu, Ni, Al, Ti, etc. with metal coloring dyes. There is a window film having a structure that blocks visible and infrared wavelengths by reflecting an infrared region as a composition with a film.

When the metal sputtering film is applied, visible light and infrared reflectivity increases, which may cause damage to others, and the window film composed of a metal coloring dye and sputtering film has the initial visible light blocking rate, color and color when exposed to natural light. The change in the infrared wavelength shielding function is fast, and there are problems such as loss of the initial function.

In addition, an infrared reflective substrate having an infrared reflective layer on a substrate such as glass or film is known. In an infrared reflective film using a film substrate, a protective layer is formed on the opposite side of the substrate of the infrared reflective layer for the purpose of protecting the infrared reflective layer. Is widely used in which a metal layer made of silver and a metal oxide layer made of indium-tin composite oxide (ITO) are alternately stacked, and can provide heat shielding by reflecting near-infrared rays such as sunlight.

As an example of the prior art related to the infrared shielding film, in Patent Document 1, in the infrared shielding material fine particle dispersion obtained by dispersing the infrared shielding material fine particles in a medium, the infrared blocking material fine particles are of the general formula WyOz (where W is tungsten , O is oxygen, tungsten oxide fine particles represented by 2.45≤z/y≤2.999), general formula MxWyOz (however, M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn , Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, etc. at least one element selected from, W is tungsten, O is oxygen, 0.001≤x/y≤1, 2.2≤z/y≤3.0) Disclosed is an infrared shielding material fine particle dispersion, characterized in that it contains infrared shielding material fine particles selected from the group consisting of composite tungsten oxide fine particles denoted by and a mixture of these fine particles. Patent Document 2 discloses an infrared reflective film comprising an infrared reflecting layer and a transparent protective layer on a transparent film substrate in this order, with a visible light transmittance of 65% or more, a shielding coefficient of less than 0.60, and measured from the transparent protective layer side. The corrected emissivity is 0.20 or less, and the infrared reflecting layer includes a first metal oxide layer, a metal layer made of a silver alloy containing silver as a main component, and a second metal oxide layer from the side of the transparent film substrate, and the first metal Each of the oxide layer and the second metal oxide layer is in direct contact with the metal layer, the transparent protective layer is made of an organic material, and between the transparent film substrate and the infrared reflecting layer, and between the infrared reflecting layer and the transparent protective layer In E, the infrared reflecting film which does not have any metal layer is disclosed.

In addition, Patent Document 3 has an ITO particle-containing layer and an overcoat layer covering the upper surface of the ITO particle-containing layer, and exists in a state in which core shell particles are in contact with each other in the ITO particle-containing layer, and the core shell particles, An infrared shielding laminate having ITO particles as a core and an insulating material as a shell covering the core is disclosed.

The inventor of the present application confirmed that the infrared shielding function and durability against discoloration are improved by mixing and using a carbon black dispersion at the same level as the dispersion of metal nitride, thereby improving the disadvantages of the existing window film. Was completed.

KR 10-0701735 B KR 10-1609525 B KR 10-2017-0099834 A

The problem to be solved in the present invention relates to the provision of a composition for an infrared shielding film used for glass windows such as vehicles and buildings in order to selectively block visible light and minimize glare.

More specifically, by using a combination of a metal nitride dispersion and a carbon black dispersion of the same level, the shortcomings of the existing infrared shielding film used for windows such as vehicles and buildings are improved, and the infrared shielding function and durability against discoloration It is an object of the present invention to provide a composition for an infrared shielding film used for glass windows of vehicles and buildings, and an infrared shielding film using the same.

As a solution to the problem according to the present invention, the composition for an infrared shielding film includes a metal nitride dispersion and a carbon black dispersion, and the metal nitride is silicon nitride, zirconium nitride, titanium nitride, aluminum nitride, TiCN , TiAlN, AlTiN, CrN, VN, TaN, NbN, GaN, Mo2N, W2N, GaN and at least one metal nitride selected from InN.

Another embodiment according to the present invention is from silicon nitride, zirconium nitride, titanium nitride, aluminum nitride, TiCN, TiAlN, AlTiN, CrN, VN, TaN, NbN, GaN, Mo2N, W2N, GaN and InN based on 100 parts by weight of the synthetic resin. It consists of a composition comprising one or more selected metal nitride (metal nitride) dispersions 0.01 to 35 parts by weight, carbon black dispersions 0.01 to 35 parts by weight, inorganic pigments 10 to 20 parts by weight, and organic pigments 100 to 200 parts by weight.

As a solution to another problem according to the present invention, an infrared shielding film using a composition for an infrared shielding film is composed of a synthetic resin film layer (1) and an infrared shielding layer (2), and the infrared shielding layer (2) is 100 weight of synthetic resin. A dispersion of any one metal nitride selected from silicon nitride, zirconium nitride, titanium nitride, aluminum nitride, TiCN, TiAlN, AlTiN, CrN, VN, TaN, NbN, GaN, Mo2N, W2N, GaN and InN with respect to the part 0.01 to 35 parts by weight, 0.01 to 35 parts by weight of a carbon black dispersion, 10 to 20 parts by weight of an inorganic pigment, and 100 to 200 parts by weight of an organic pigment.

The composition for an infrared shielding film according to the present invention has an effect of improving the infrared shielding function and durability against discoloration compared to a conventional window film by using a combination of a metal nitride dispersion and a carbon black dispersion.

In addition, there is an industrial advantage by reducing the amount of expensive antimony tin oxide (ATO), indium tin oxide (ITO), and tungsten added to improve the infrared shielding rate, thereby reducing the cost required for manufacturing the shielding film.

1 is a graph showing the relationship between durability and transmittance by an accelerated weathering test for an infrared shielding film according to the present invention
FIG. 2 is a diagram showing the direction of color change after measuring Δa and Δb with a color difference meter at ΔE (color change rate including contrast) described in FIG. 1
3 is a graph showing the relationship between durability and transmittance by an accelerated weathering test for the infrared shielding film and the comparative film of the present invention
4 is a diagram schematically showing a laminated structure of an embodiment of an infrared shielding film of the present invention

Hereinafter, the present invention will be described in more detail with reference to specific contents and examples for carrying out the present invention, but the present invention is not limited by the following description.

The composition for an infrared shielding film according to the present invention comprises silicon nitride, zirconium nitride, titanium nitride, aluminum nitride, TiCN, TiAlN, AlTiN, CrN, VN, TaN, NbN, GaN, Mo2N, W2N, GaN and InN based on 100 parts by weight of synthetic resin. Any one metal nitride dispersion selected from 0.01 to 35 parts by weight, carbon black dispersion 0.01 to 35 parts by weight, 10 to 20 parts by weight of inorganic pigment, and 100 to 200 parts by weight of organic pigment. .

The metal nitride dispersion according to the present invention is prepared by dispersing the metal nitride together with a dispersant, a dispersing aid, and a solvent at the same time as pulverization using a ball mill. It is not limited.

The dispersant selected for the preparation of the dispersion is a polymer non-aqueous dispersant such as polyacrylic acid partial alkyl ester and polyalkylene polyamine, and a polymer cationic dispersant such as polyethyleneimine and aminoalkyl methacrylate copolymer is selected. It does not exclude having a structure other than the dispersant in the form as described above.

In addition, the solvent consists of one or more components selected from methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), and isopropyl alcohol.

The method of preparing a metal nitride dispersion or carbon black dispersion according to the present invention will be described as an example, a ball mill that is dispersed using a homogenizer and a bead, a horizontal mill such as a DYNO-mill, or an Attrition mill. 48 hours by combining metal nitride or carbon black with an acrylic polymer dispersant and one or more mixed solvents selected from methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), and isopropyl alcohol using a vertical mill. It consists of pulverizing and dispersing to prepare a dispersion.

The metal nitride or carbon black, the dispersant and the mixed solvent are preferably used in combination in a ratio of 1:1 by weight, and consists of preparing a dispersion having a particle diameter of 1 nm to 55 nm.

The synthetic resin according to the present invention is polyethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene resin, polypropylene resin, ethylene vinyl acetate copolymer, polyester resin, polyethylene terephthalate resin, fluororesin , At least one component is selected from polycarbonate resin, polyvinyl butyral resin, acrylic resin, and polyurethane resin, and at least one component is preferably selected from acrylic resin, polyurethane resin, and polyester.

The inorganic pigment is any one of silica, TiO ₂ , antimony tin oxide (ATO), indium tin oxide (ITO), and tungsten, and the organic pigment is yellow color such as diazo, Hansa, Diarylide, isoindolinone, benzimidazolone, pyrazolone, Orange color such as dianisidine, azo, red color such as toluidine, napthol, quinacridone, diazo, benzimidazolone, blue color of phthalocyanine, indanthrone, green color such as phthalocyanine, violet color of quinacridone, carbazole, etc. have.

The infrared shielding film (F) using the composition for an infrared shielding film according to the present invention is composed of a synthetic resin film layer (1), an infrared shielding layer (2), or a synthetic resin film layer (1), an infrared shielding layer (2) and a synthetic resin It includes a shielding film formed by laminating in the order of the film layer (1).

The synthetic resin film layer (1) may be formed with a hard coating layer (H) to prevent damage such as abrasion of the outer surface, and the hard coating layer (H) formed on the outer surface of the synthetic resin film layer (1) is a film Since a well-known known method of coating a protective film on is selected, a detailed description will be omitted.

And the synthetic resin film layer (1) includes a pressure-sensitive adhesive layer (P) to adhere to glass or the like. The pressure-sensitive adhesive layer (P) may contain a color.

The synthetic resin film layer (1) is not particularly limited as long as it is an infrared shielding film used for glass windows of vehicles and buildings, and a polyethylene terephthalate (PET) film is preferable.

The infrared shielding layer 2 is selected from silicon nitride, zirconium nitride, titanium nitride, aluminum nitride, TiCN, TiAlN, AlTiN, CrN, VN, TaN, NbN, GaN, Mo2N, W2N, GaN and InN based on 100 parts by weight of synthetic resin. Any one metal nitride (metal nitride) dispersion comprising 0.01 to 35 parts by weight, carbon black dispersion 0.01 to 35 parts by weight, inorganic pigment 10 to 20 parts by weight, and an organic pigment consisting of 100 to 200 parts by weight.

In addition, the infrared shielding film (F) using the composition for an infrared shielding film according to the present invention comprises a plurality of layers of an infrared shielding layer (2) with a polyethylene terephthalate (PET) film therebetween. The thickness of the infrared shielding layer 2 is about 3 to 20 μm, and the inorganic and organic pigments are the same as those described in the composition for an infrared shielding film.

<Example 1> Preparation of metal nitride and carbon black dispersion

100 parts by weight of an acrylic polymer dispersant (BYK-2050, BYK, Germany) 100 parts by weight of AlTiN (Aluminium Titanium Nitride) 100 parts by weight, and a mixed solvent (MIBK)/MEK/isopropyl alcohol = mixed in a weight ratio of 2/7/1) 100 A part by weight was put into a ball mill, pulverized and dispersed for 48 hours or more to prepare an AlTiN (Aluminium Titanium Nitride) dispersion having an average particle diameter of 55 nm, and the carbon black dispersion was pulverized and dispersed in the same manner as the AlTiN dispersion. Was prepared.

<Example 2> Preparation of a shielding film

2 parts by weight of AlTiN dispersion prepared in <Example 1>, 4 parts by weight of carbon black dispersion, and 50 parts by weight of organic solvent were added to the mixing container equipped with a stirrer, stirred for 10 minutes, and then 100 parts by weight of polyester resin was added. The composition was further stirred for 30 minutes to prepare a Charcoal Black color infrared shielding film composition.

The prepared infrared shielding film composition was applied to a PET film prepared in advance to a thickness of 5 μm and dried to prepare an infrared shielding film according to the present invention.

<Test Example 1>

The relationship between durability and transmittance was tested for the infrared shielding film according to the present invention prepared in <Example 2>, and the results are shown in FIGS. 1 and 2.

The test method for the relationship between weather resistance and transmittance is an accelerated weather resistance test, which is a graph showing before and after the test for transmittance (100%) in which the wavelength from 300nm to 2500nm was measured in 1nm units by testing for 1500hr according to the test method of ASTMG-155. I paid.

As shown in Fig. 1, the <Example 2> (mixed film of an AlTiN dispersion and carbon black dispersion), which is an infrared shielding film according to the present invention, has no specific change in transmittance before and after the accelerated weathering test. It can be seen that the infrared shielding film has no effect on the effect of infrared shielding even after the use period elapses.

In Figure 1, △VLT is a value for the rate of change before and after the accelerated weathering test calculated based on KS L 2514 after measuring the wavelength of 380nm ~ 780nm, △IR is the test calculated based on KS L 2514 after measuring the wavelength of 780nm ~ 2500nm A numerical value for the rate of change before and after, △E is the color change rate including contrast and can be obtained by measuring before and after the accelerated weathering test with a color difference meter, and △a and △b are equally measured before and after the test with a color difference meter, and then the color change progresses. You can see the direction.

As shown in FIG. 2, it can be seen that a larger value of a leads to a red color, a smaller value leads to a green tone, a larger value of b leads to a yellow tone, and a smaller value leads to a blue tone.

<Comparative Test Example>

In order to compare the test results of the relationship between durability and transmittance of the infrared shielding film according to the present invention prepared in <Example 2>, carbon black and carbon black were prepared by the same method as in <Example 1> and <Example 2>. An infrared shielding film composed of 8 parts by weight of Isoindoline, 10 parts by weight of Quina cridone, 8 parts by weight of Copper Phthalocyanine as an organic dispersion pigment <Comparative Film 1>, an infrared shielding film composed of 12 parts by weight of carbon black <Comparative Film 2> and AlTiN 12 An infrared shielding film composed of parts by weight <Comparative Film 3> was prepared, and each film was tested for 1500 hr according to the test method of ASTMG-155 as an accelerated weather resistance test, and the wavelength from 300 nm to 2500 nm was measured in 1 nm increments. The results before and after the test for transmittance (100%) are shown in FIG. 3.

As shown in FIG. 3, the visible light transmittance (380nm ~ 780nm wavelength) of the shielding film <Comparative Film 1> in which the shielding film of <Example 2> according to the present invention is mixed with the carbon black dispersion and organic dispersion pigments is equivalent In contrast, the infrared (780nm ~ 2500nm wavelength) transmittance of the comparative film is high, it can be seen that the infrared shielding function of the shielding film of <Example 2> is high, so that the infrared prepared by the mixed composition of the metal nitride and carbon black according to the present invention It can be seen that the shielding film has superior infrared shielding effect according to durability compared to the shielding film using each of metal nitride and carbon black alone, and infrared shielding according to durability compared to the shielding film using conventional carbon black and organic dispersion pigments. It can be seen that the effect is more excellent.

And as shown in Figure 4, the infrared shielding film (F) according to the present invention is a shielding film made of a synthetic resin film layer (1), an infrared shielding layer (2), a synthetic resin film layer (1), an infrared shielding layer (2) ) And a synthetic resin film layer (1) and a shielding film in which a synthetic resin film layer (1), an infrared shielding layer (2), and a synthetic resin film layer (1) are sequentially repeatedly formed.

F: Infrared shielding film of the present invention
1: synthetic resin film layer, 2: shielding layer, H: hard coating layer, P: adhesive layer

Claims (6)

Any one metal nitride selected from silicon nitride, zirconium nitride, titanium nitride, aluminum nitride, TiCN, TiAlN, AlTiN, CrN, VN, TaN, NbN, GaN, Mo2N, W2N, GaN and InN based on 100 parts by weight of synthetic resin nitride), polyacrylic acid partial alkyl ester, polyalkylene polyamine, and at least one polymer non-aqueous dispersant selected from methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), and isopropyl alcohol. Metal nitride dispersion obtained by grinding and dispersing at the same time using a ball mill with a mixed solvent 0.01 to 35 parts by weight, carbon black and polyacrylic acid partial alkyl ester, at least one polymer non-aqueous dispersant selected from polyalkylene polyamine and methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), isopropyl alcohol (Isopropyl alcohol) with one or more mixed solvents selected from a ball mill using a ball mill to disperse and pulverize the obtained carbon black dispersion 0.01 ~ 35 parts by weight, inorganic pigment 10 ~ An infrared shielding film composition comprising 20 parts by weight and 100 to 200 parts by weight of an organic pigment. The method according to claim 1,
A composition for an infrared shielding film, characterized in that the metal nitride dispersion and the carbon black dispersion are composed in a ratio of 1:1 by weight of a metal nitride or carbon black, a dispersant, and a mixed solvent.
delete It includes a shielding layer (2) made of the composition for an infrared shielding film according to claim 1 or 2, a synthetic resin film layer (1), and an adhesive layer (P), and the outer surface of the synthetic resin film layer (1) is a hard coating layer (H ) Infrared shielding film, characterized in that formed.
delete The method of claim 4,
An infrared shielding film, characterized in that a hard coating layer (H) is formed on the outer surface of the synthetic resin film layer (1), and a plurality of synthetic resin film layers (1), shielding layers (2), and adhesive layers (P) are sequentially formed. .

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