WO2015037198A1

WO2015037198A1 - Composition for forming functional film, and functional film laminate

Info

Publication number: WO2015037198A1
Application number: PCT/JP2014/004350
Authority: WO
Inventors: 大作守屋
Original assignee: ナガセケムテックス株式会社
Priority date: 2013-09-11
Filing date: 2014-08-25
Publication date: 2015-03-19
Also published as: JP2015078338A; TW201527447A

Abstract

　Provided are a composition for forming a functional film provided with both far infrared reflection properties and near infrared absorption properties in a single layer, and a laminate formed by laminating said functional film on a substrate.　The composition for forming a functional film having both far infrared reflection properties and near infrared absorption properties includes a conductive polymer exhibiting electrical conductivity of at least 0.05S/cm, an inorganic material and a binder. Said composition is used to obtain a laminate formed by laminating, on a substrate, a functional film that has a shielding coefficient of less than 0.95 and a heat transfer coefficient of less than 5.9W/m²·K, and that exhibits far infrared reflection properties and near infrared absorption properties.

Description

Functional film forming composition and functional film laminate

The present invention relates to a composition for forming a functional film having far-infrared reflection performance and near-infrared absorption performance, and a laminate in which a functional film obtained using the composition is laminated on a substrate.

Infrared refers to electromagnetic waves having a longer wavelength than red light and shorter than millimeter-wave radio waves. Near infrared (about 300-2,500 nm), mid-infrared (about 2,500-4,000 nm), far infrared (About 4,000-300,000 nm). Far-infrared rays with long wavelengths are generated from heating equipment and are used to maintain the room temperature in winter comfortably. However, some of them are transmitted through the window glass and released outside, causing a reduction in heating efficiency. It was. Solar radiation includes near-infrared rays with a short wavelength, but the near-infrared rays that have passed through the window glass and are taken into the room raises the room temperature and lowers the cooling efficiency in summer.

Conventionally, attempts have been made to improve the heating efficiency in winter and the cooling efficiency in summer by providing a thin film having the property of reflecting and absorbing these infrared rays on the surface of the window glass.

As such an infrared reflective thin film, a thin film made of a metal such as gold or silver is known, but since these metal thin films are not transparent, there is a drawback that they cannot be applied to the surface of a transparent substrate such as a window glass. there were.

As the transparent infrared reflective thin film, a transparent thin film made of a metal oxide such as tin-doped indicium oxide (ITO) is used. However, since sputtering or vacuum deposition is used for forming the thin film, expensive equipment is used. And there was a disadvantage that a high temperature setting was required.

Therefore, it has been proposed to use a conductive organic polymer material as a transparent infrared reflective thin film instead of a metal oxide.

Patent Document 1 describes a thin film containing a conductive polymer such as poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT / PSS) that reflects far infrared rays. However, the reflection performance of near infrared rays of about 800 to 1200 nm is low.

Patent Document 2 describes an infrared absorption film comprising a cured product layer containing an inorganic pigment that efficiently absorbs near infrared rays of about 800 to 1200 nm and an antireflection layer. However, the cured product layer alone does not have infrared reflection performance.

International Publication No. 2012/105213 Japanese Patent Laid-Open No. 2007-21998

In the inventions described in Patent Documents 1 and 2, a transparent thin film having a far-infrared reflecting performance and a near-infrared absorbing performance with a single layer has not been realized.

Under such circumstances, the present invention is a composition for forming a functional film having a far-infrared reflecting performance and a near-infrared absorbing performance in a single layer, and a laminate in which the functional film is laminated on a substrate. The challenge is to provide a body.

The first of the present invention is used to form a functional film having far-infrared reflecting performance and near-infrared absorbing performance, and includes a conductive polymer exhibiting a conductivity of 0.05 S / cm or more, an inorganic material, And a composition comprising a binder.

The second of the present invention is obtained by using the above composition, has a shielding coefficient of less than 0.95, a heat transmissivity of less than 5.9 W / m ² · K, and has a far-infrared reflecting performance and a near-infrared absorbing performance. It is related with the laminated body which laminated | stacked the provided functional film on the base material.

According to the present invention, it is possible to provide a functional film having a single-layered far-infrared reflecting performance and near-infrared absorbing performance with the above configuration. Moreover, since it has the outstanding performance with a single layer, manufacture of a laminated body can be simplified.

Hereinafter, an example of a preferred embodiment of the present invention will be specifically described.

[Conductive polymer]
The conductive polymer in the composition according to the present invention is compared with the conductive polymer used in normal conductive film applications in order that the formed thin film exhibits excellent far-infrared reflection performance and near-infrared absorption performance. It is necessary to show high conductivity. Specifically, it is necessary to use a conductive polymer having a conductivity of 0.01 S / cm or more. If the electrical conductivity is less than 0.01 S / cm, a thin film exhibiting excellent far-infrared reflection performance and near-infrared absorption performance cannot be formed.

The conductivity of the conductive polymer is preferably 0.05 S / cm or more, more preferably 0.15 S / cm or more, and further preferably 0.25 S / cm or more.

A conductive polymer exhibiting a conductivity of 0.01 S / cm or more can be easily produced by appropriately selecting the polymerization conditions and molecular weight of the π-conjugated conductive polymer, for example. For example, by increasing the molecular weight, a conductive polymer exhibiting high conductivity as described above can be obtained. Examples of the conductive polymer include polythiophene, polyethylenedioxythiophene, polyisothianaphthene, polypyrrole, polyaniline, polyparaphenylene, polyparaphenylene vinylene, and derivatives thereof.

Among these, a polythiophene conductive polymer composed of a complex of polythiophene and a dopant is preferably used. In particular, when the conductive polymer is composed of a complex of poly (3,4-disubstituted thiophene) and a polyanion, a conductive material exhibiting high conductivity can be obtained by optimizing the pH exhibited by the polymerization system during production. Can be obtained. Conductive polymers exhibiting high conductivity are commercially available, and commercially available products may be used in the present invention.

The conductivity of the conductive polymer of the present invention is determined by the following formula by measuring the film thickness and surface resistivity indicated by the conductive layer after forming a conductive layer made of the conductive polymer on the substrate. Calculated based on
Conductivity (S / cm) = 1 / {Surface resistivity (Ω / □) × film thickness (cm)}
The poly (3,4-disubstituted thiophene) has the following formula (1):

It is preferable that it is a polythiophene of the cationic form which consists of a repeating structural unit shown by these. The cationic polythiophene refers to a polythiophene that is partly in a cationic form by extracting electrons from a part of the polythiophene in order to form a complex with a polyanion that is a dopant. .

In formula (1), R ¹ and R ² independently of each other represent a hydrogen atom or a C _1-4 alkyl group, or R ¹ and R ² combine to form a cyclic structure. It represents a substituted or unsubstituted C _1-4 alkylene group. Examples of the C _1-4 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. Examples of the substituted or unsubstituted C _1-4 alkylene group in which R ¹ and R ² combine to form a cyclic structure include a methylene group, a 1,2-ethylene group, a 1,3-propylene group, , 4-butylene group, 1-methyl-1,2-ethylene group, 1-ethyl-1,2-ethylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene group, etc. Is mentioned. Examples of the substituent that the C _1-4 alkylene group may have include a halogen group and a phenyl group. Suitable C _1-4 alkylene groups include methylene, 1,2-ethylene, and 1,3-propylene, with 1,2-ethylene being particularly preferred. As the polythiophene having an alkylene group, poly (3,4-ethylenedioxythiophene) is particularly preferable.

The dopant constituting the polythiophene-based conductive polymer is an anionic polymer that forms a complex by forming an ion pair with the polythiophene described above, and can stably disperse the polythiophene in water, that is, a polyanion. It is preferable. Examples of such dopants include carboxylic acid polymers (eg, polyacrylic acid, polymaleic acid, polymethacrylic acid, etc.), sulfonic acid polymers (eg, polystyrene sulfonic acid, polyvinyl sulfonic acid, etc.), and the like. These carboxylic acid polymers and sulfonic acid polymers may be copolymers of vinyl carboxylic acids and vinyl sulfonic acids with other polymerizable monomers (eg, acrylates, styrene, etc.). Of these, polystyrene sulfonic acid is particularly preferable.

The weight average molecular weight of poly (3,4-disubstituted thiophene) is preferably in the range of 500 to 100,000, more preferably in the range of 1000 to 50000, and most preferably in the range of 1500 to 20000. When it is less than 500, a thin film exhibiting excellent far-infrared reflection performance and near-infrared absorption performance cannot be formed, and when it exceeds 100,000, the dispersion stability of the conductive polymer may be lowered.

The weight average molecular weight of the polyanion is preferably in the range of 1,000 to 2,000,000, more preferably in the range of 2,000 to 1,000,000, and most preferably in the range of 2,000 to 500,000. If it is less than 1000 or exceeds 2000000, the dispersion stability of the conductive polymer may be lowered.

The weight average molecular weight of the polymer is a value measured by gel permeation chromatography (GPC). For the measurement, an ultrahydrogel 500 column manufactured by Waters is used.

The amount of the poly anion is preferably in the range of 10 to 2000 parts by mass, more preferably in the range of 30 to 1000 parts by mass, with respect to 100 parts by mass of the poly (3,4-disubstituted thiophene). The range of 50 to 500 parts by mass is most preferable. When the amount is less than 10 parts by mass, the dispersion stability decreases, and when it exceeds 2000 parts by mass, a thin film exhibiting excellent far-infrared reflection performance and near-infrared absorption performance may not be formed.

The polythiophene conductive polymer can be obtained by oxidative polymerization in water using an oxidizing agent. In the oxidative polymerization, two kinds of oxidizing agents (first oxidizing agent and second oxidizing agent) are used. Suitable first oxidizing agents include, for example, peroxodisulfuric acid, sodium peroxodisulfate, potassium peroxodisulfate, ammonium peroxodisulfate, hydrogen peroxide, potassium permanganate, potassium dichromate, alkali perborate, copper Examples include salts. Of these primary oxidants, sodium peroxodisulfate, potassium peroxodisulfate, ammonium peroxodisulfate, and peroxodisulfate are most preferred. The amount of the first oxidizing agent used is preferably 1.5 to 3.0 molar equivalents, more preferably 2.0 to 2.6 molar equivalents relative to the thiophene monomer used.

As a suitable second dioxide agent, it is preferable to add a metal ion (for example, iron, cobalt, nickel, molybdenum, vanadium ion) in a catalytic amount. Of these, iron ions are the most effective. The amount of metal ion added is preferably 0.005 to 0.1 molar equivalent, more preferably 0.01 to 0.05 molar equivalent, relative to the thiophene monomer used.

In this oxidative polymerization, water is used as a reaction solvent. In addition to water, alcohols such as methanol, ethanol, 2-propanol and 1-propanol, and water-soluble solvents such as acetone and acetonitrile can also be added. An aqueous dispersion of a conductive polymer is obtained by the above oxidative polymerization.

The composition of the present invention preferably further contains a solvent and / or a dispersion medium in addition to the conductive polymer. Thereby, the viscosity of a composition can be reduced and application | coating to a base material can be made easy. The solvent or dispersion medium is not particularly limited as long as it can dissolve or disperse the conductive polymer and other optional components.

In addition, when each component of the composition is completely dissolved, it is referred to as a “solvent”, and when any component is not dissolved but dispersed, it is referred to as a “dispersion medium”.

When the composition is aqueous, the solvent may be only water, but in addition to water, a solvent miscible with water may be used in combination. The solvent miscible with water is not particularly limited. For example, alcohols such as methanol, ethanol, 2-propanol, 1-propanol, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc. Glycol ether acetates, propylene glycols such as propylene glycol, dipropylene glycol, tripropylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, di Propylene glycol dimethyl ether, propylene glycol Propylene glycol ethers such as coal diethyl ether and dipropylene glycol diethyl ether, propylene glycol ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate and dipropylene glycol monoethyl ether acetate , Dimethylacetamide, acetone, acetonitrile, and mixtures thereof.

When the composition is an organic solvent, in addition to the above-mentioned solvents miscible with water, toluene, xylene, benzene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, diethyl ether, diisopropyl ether, methyl-t -Butyl ether, hexane, heptane, etc. can be used. Of the above solvents or dispersion media, methanol, ethanol and 2-propanol are particularly preferred.

The solid content concentration of the composition is not particularly limited as long as it is a uniform solution or dispersion, but is preferably about 0.01 to 50% by mass during coating. More preferably, it is 1 to 20% by mass. In this range, the coating can be carried out easily, and good far infrared reflection performance and near infrared absorption performance are exhibited. On the other hand, the concentration may be higher when the composition is sold or transported. In that case, a solvent and / or a dispersion medium may be added and diluted as appropriate at the time of use.

[Inorganic materials]
The inorganic material in the composition according to the present invention is preferably fine particles having an average particle size of about 0.01 μm to 10 μm, since the formed thin film exhibits excellent far-infrared reflection performance and near-infrared absorption performance.

The average particle diameter of the fine particles is preferably 0.01 μm to 5 μm, more preferably 0.01 μm to 3 μm, and still more preferably 0.01 μm to 1 μm. If it is smaller than 0.01 μm, the inorganic materials tend to aggregate together, and if it is larger than 10 μm, the dispersion stability may be lowered.

The shape of the fine particles is not particularly limited, but a spherical or fibrous one can be suitably used because a larger surface area absorbs near infrared rays more efficiently.

When the inorganic material is in the form of a fiber, it is preferable to use one having an average average aspect ratio according to the conductive fiber to be used. As a rough guide, the average aspect ratio is preferably 10 to 10,000. Here, the aspect ratio is calculated from the length and diameter (aspect ratio = length / diameter).

The average length is preferably 1 μm to 100 μm, more preferably 3 μm to 50 μm, and even more preferably 5 μm to 30 μm. In addition, the relative standard deviation of the length is preferably 50% or less.

The average particle size of the inorganic material was a value measured with a dynamic light scattering particle size / particle size distribution measuring device (Nikkiso Co., Ltd .: Nanotrack® Wave).

When the inorganic material is fibrous, the average value of length, diameter, or aspect ratio is obtained from an arithmetic average of measured values of individual fiber images by taking electron micrographs of a sufficient number of fibrous inorganic materials. be able to. The length of the fiber should be measured in a linearly stretched state, but in reality it is often bent, so the projected diameter and projected area can be determined using an image analyzer from an electron micrograph. It is also possible to calculate and assume a cylindrical body (length = projected area / projected diameter).

The relative standard deviation of length and diameter is expressed by a value obtained by multiplying 100 by the value obtained by dividing the standard deviation of the measured value by the average value. The number of fibers to be measured is preferably at least 100, more preferably 300 or more.
Relative standard deviation [%] = standard deviation of measured value / average value × 100

The blending amount of the inorganic material in the composition according to the present invention is preferably 0.1 to 10000 parts by mass, more preferably 1 to 5000 parts by mass with respect to 100 parts by mass of the conductive polymer. More preferably, it is 10 to 1000 parts by mass. If the blending amount is outside this range, a thin film exhibiting excellent far-infrared reflection performance and near-infrared absorption performance cannot be formed.

Specifically, the inorganic material in the composition according to the present invention includes metal oxides such as indium tin oxide (ITO) and antimony tin oxide (ATO), composite tungsten oxide, and metal nanowires, metal nanoparticles, Silica (SiO ₂ ) can be preferably used.

Among these, since the formed thin film exhibits excellent far-infrared reflection performance and near-infrared absorption performance, from indium tin oxide (ITO), antimony tin oxide (ATO), composite tungsten oxide, and metal nanowires It is preferably at least one selected from the group consisting of

Furthermore, since the near-infrared absorption performance is excellent, the composite tungsten oxide is represented by the general formula W _y O _z (where W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999). Composite tungsten oxide,
In the general formula _M x _W y _{O z} (wherein, M represents, H, the He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn , Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, At least one element selected from the group consisting of V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1,. Composite tungsten oxide represented by 2 ≦ z / y ≦ 3.0), and
General formula M _E A _G W _(1-G) O _J (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, One element selected from Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, A is Mo, Nb, Ta, Mn, V, Re, Pt At least one element selected from the group consisting of Ti, Pd, and Ti, W is tungsten, O is oxygen, and composite tungsten represented by 0 <E ≦ 1.2, 0 <G ≦ 1, 2 ≦ J ≦ 3 It is preferably at least one selected from the group consisting of oxides.

There is no restriction | limiting in particular as a metal composition of the metal nanowire in this invention, Although it can comprise from the 1 type or several metal of a noble metal element or a base metal element, it is a noble metal (For example, gold, platinum, silver, palladium, rhodium, iridium) , Ruthenium, osmium, etc.) and at least one metal belonging to the group consisting of iron, cobalt, copper, and tin. It is preferable to include at least silver because it is excellent in infrared reflection performance. More preferably it is.

Here, the metal nanowire generally refers to a fibrous structure having a metal element as a main component. In particular, the metal nanowire in the present invention means a fibrous structure having a diameter from the atomic scale to the nm size.

[binder]
The binder in the composition according to the present invention is used for enhancing the adhesion between the thin film and the substrate and forming a homogeneous thin film, particularly when a resin film is used as the substrate.

The binder usable in the present invention is not particularly limited. Conventionally, a binder that has been used when a conductive polymer is coated on a substrate can be appropriately used.

Specifically, silicate resin, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and other polyester resins, polyacrylate, polymethacrylate, polyurethane, polyvinyl acetate, polyvinylidene chloride, Polyamide, polyimide and the like; and copolymers obtained by copolymerizing monomers such as styrene, vinylidene chloride, vinyl chloride, alkyl acrylate and alkyl methacrylate. These binders may be used independently and may use 2 or more types together.

In the present invention, the silicate resin is not particularly limited as long as it is a compound having at least one silicon alkoxide group (—Si—OR).

Examples of the silicate resin include silicon alkoxide acrylic resin, silicon alkoxide epoxy resin, silicon alkoxide vinyl resin, silicon alkoxide methacrylic resin, silicon alkoxide thiol resin, silicon alkoxide amino resin, silicon alkoxide isocyanate resin, silicon Examples thereof include silicon alkoxide resins such as alkoxide alkyl resins and silicon alkoxide resins having no functional group other than silicon alkoxide groups.

More specifically, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methylsilicate oligomer, ethylsilicate oligomer, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane , Vinyltrimethoxysilane, vinyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyl Trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxy Silane, 3-isocyanatopropyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methylphenoxysilane, n-propyltrimethoxysilane, diisopropyldimethoxy Run, isobutyltrimethoxysilane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, etc. Can be mentioned.

The binder in the composition according to the present invention is a compound having a silicon alkoxide group (A), a silicon alkoxide group, an acrylic group, an epoxy group, an alkyl group, from the viewpoint of obtaining a coating film having particularly high scratch resistance. It is preferably at least one selected from compounds (B) having at least one functional group selected from the group consisting of a vinyl group, a methacryl group, a thiol group, an amino group and an isocyanate group.

Furthermore, the binder in the composition according to the present invention is a compound having a silicon alkoxide group (A) and a silicon alkoxide because it exhibits excellent hardness when it is used as a cured film, and cracks due to curing shrinkage are less likely to occur. And a compound (B) having a group and at least one functional group selected from the group consisting of an acrylic group, an epoxy group, an alkyl group, a vinyl group, a methacryl group, a thiol group, an amino group, and an isocyanate group It is preferable. Further, when the compound (A) and the compound (B) are used in combination, the value obtained by dividing the number of alkoxide groups in the compound (B) by the weight average molecular weight of the compound (B) is the compound (A). ) Is preferably 90% or less of the value obtained by dividing the number of alkoxide groups by the weight average molecular weight of the compound (A).

The weight average molecular weight can be measured by gel permeation chromatography (GPC).

In the present invention, the compound (A) is preferably a compound represented by the following formula (2) from the viewpoint of hardness when it is used as a cured film.

In formula (2),
n is an integer of 0 to 1000, preferably 0 to 500, and more preferably 0 to 100.

When n is 0, at least one of R ₁ , R ₂ , R ₃ , and R ₅ is an alkoxide group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms,
When n is 1, at least one of R _1-6 is an alkoxide group having 1-20 carbon atoms, preferably 1-10 carbon atoms, more preferably 1-5 carbon atoms,
when n is 2 or _more, at least one 1 to 20 carbon atoms of _{R 1 ~ 6,} preferably 1 to 10, more preferably an alkoxide group of 1 ~ 5, _{R 4} there are a plurality, Each may be the same or different, and a plurality of R ₆ may be the same or different.

When n is 0, 1, or 2 or more, each of R _{1 to 6} other than the alkoxide group is independently hydrogen, alkyl group, cycloalkyl group, cycloalkenyl group, aryl group, aralkyl group, Hydrocarbon group such as methylene group, vinyl group, allyl group, heterocyclic group, hydroxyl group, hydroxy (poly) alkyleneoxy group, acyl group, oxy group, thioxy group, phosphino group, halogeno group, amino group, imino group, It is selected from the group consisting of an N-oxide group, a nitro group, and a cyano group, and the hydrogen on the carbon chain and the hydrogen on the ring may each independently be substituted.

For R 1 _{~ 6,} and hydrogen on the carbon chain, as the substituent which can replace a hydrogen on the ring, for example, an alkyl group (a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, s- butyl group C _1-20 alkyl group such as t-butyl group), cycloalkyl group (C _3-10 cycloalkyl group such as cyclopentyl group, cyclohexyl group etc.), cycloalkenyl group (cyclopenter group, cyclohexel group etc.) C _3-10 cycloalkenyl group etc.), heterocyclic group (C _2-10 heterocyclic group containing a hetero atom such as oxygen atom, nitrogen atom, sulfur atom etc.), aryl group [phenyl group, alkylphenyl group (methylphenyl group) C _6-10 aryl groups such as (tolyl group), dimethylphenyl group (xylyl group), etc.], C _6- such as aralkyl groups (benzyl group, phenethyl group, etc.) ₁₀ aryl-C _1-4 alkyl group), unsaturated hydrocarbon group such as methylene group, vinyl group, allyl group, alkoxide group (C _1-4 alkoxide group such as methoxy group), hydroxyl group, hydroxy (poly ) Alkyleneoxy group (hydroxy (poly) C _2-4 alkyleneoxy group etc.), acyl group (C _1-6 acyl group such as acetyl group etc.), oxy group, thioxy group, phosphino group, halogeno group (fluoro group, Chloro group, etc.), amino group, imino group, N-oxide group, nitro group, cyano group and the like. In addition, the hydrogen on the carbon chain or the hydrogen on the ring may be partially substituted, or all may be substituted.

Specific examples of the compound (A) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, methyl silicate oligomer, and ethyl silicate oligomer.

In the compound (A), it is preferable that all of R _{1 to 6 represented by} the formula (2) are alkoxide groups.

In the present invention, the compound (B) is preferably a compound represented by the following formula (3) from the viewpoint that it can be cured and shrinkage moderately while exhibiting a certain hardness when formed into a cured film.

In formula (3),
X is a single bond, a divalent chain hydrocarbon group having 1 to 20, preferably 2 to 15, more preferably 3 to 10 carbon atoms (wherein the carbon chain may be linear or branched, Some of the carbon atoms may be substituted with heteroatoms, and some or all of the hydrogens on the carbon chain may be substituted), or 3 to 20, preferably 4 to 15, More preferably, it is a divalent cyclic hydrocarbon group of 5 to 10 (wherein the ring may be a monocyclic ring, a condensed ring or a spiro ring, or may have both a condensed ring and a spiro ring, Of the ring may be substituted with a heteroatom, and some or all of the hydrogen on the ring may be substituted).
Y is selected from the group consisting of acrylic, epoxy, alkyl, vinyl, methacryl, thiol, amino and isocyanate groups;
At least one of 1 to 20 carbon atoms of R _{7 ~ 9,} preferably 1 to 10, more preferably an alkoxide group of 1 to 5,
The rest are independently hydrogen, alkyl group, cycloalkyl group, cycloalkenyl group, aryl group, aralkyl group, methylene group, vinyl group, allyl group and other hydrocarbon groups, heterocyclic groups, hydroxyl groups, hydroxy groups. (Poly) alkyleneoxy group, acyl group, oxy group, thiooxy group, phosphino group, halogeno group, amino group, imino group, N-oxide group, nitro group, and cyano group, The hydrogen on the carbon chain and the hydrogen on the ring may each independently be substituted.

Examples of the substituent that can be substituted with hydrogen on the carbon chain or hydrogen on the ring include, for example, alkyl groups (methyl group, ethyl group, propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group, etc. _{C 1-20} alkyl group), and a cycloalkyl group (cyclopentyl group, and a _{C 3-10} cycloalkyl groups such as cyclohexyl group), a cycloalkenyl group (cyclo Pentel group, _{C 3-10} cycloalkenyl, such as cyclohexanol cell group Groups), heterocyclic groups (C _2-10 heterocyclic groups containing heteroatoms such as oxygen, nitrogen and sulfur atoms), aryl groups [phenyl groups, alkylphenyl groups (methylphenyl groups (tolyl groups), dimethyl groups) C _6-10 aryl group such as phenyl group (xylyl group), etc.], C _6-10 aryl-C ₁ such as aralkyl group (benzyl group, phenethyl group, etc.) _-4 alkyl groups), unsaturated hydrocarbon groups such as methylene groups, vinyl groups, allyl groups, alkoxide groups (C _1-4 alkoxide groups such as methoxy groups), hydroxyl groups, hydroxy (poly) alkyleneoxy groups ( Hydroxy (poly) C _2-4 alkyleneoxy group, etc.), acyl group (C _1-6 acyl group such as acetyl group), oxy group, thioxy group, phosphino group, halogeno group (fluoro group, chloro group etc.), Examples thereof include an amino group, an imino group, an N-oxide group, a nitro group, and a cyano group. In addition, the hydrogen on the carbon chain or the hydrogen on the ring may be partially substituted, or all may be substituted.

Specific examples of the compound (B) include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidyl. Sidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxy Propyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N- -(Aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-tri Ethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, Methyltriethoxysilane, methylphenoxysilane, n-propyltrimethoxysilane, diisopropyldimethoxysilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-he Sill trimethoxysilane, n- hexyl triethoxysilane, cyclohexyl methyl dimethoxy silane, n- octyltriethoxysilane, n- decyl trimethoxysilane and the like.

When the compound (A) and the compound (B) are used in combination, the cured film can have a higher hardness. Therefore, the compounding ratio of the compound (A) and the compound (B) is 30. ~ 95: 70-5 is preferred.

When the compound (A) and the compound (B) are used in combination, the compound (A) may not have a functional group (excluding a silicon alkoxide group) that the compound (B) has. preferable.

The amount of the binder in the composition of the present invention is preferably 0.1 to 10000 parts by mass, more preferably 1 to 5000 parts by mass, with respect to 100 parts by mass of the conductive polymer. More preferably, it is 10 to 2000 parts by mass. When the amount is less than 0.1 parts by mass, film formation may be difficult. When the amount exceeds 10000 parts by mass, a thin film exhibiting excellent far-infrared reflection performance and near-infrared absorption performance cannot be formed.

[Additive]
The composition of the present invention may further include a leveling agent, an antioxidant, a catalyst, a surfactant (surface conditioner), an antifoaming agent, a rheology control agent, an adhesion-imparting agent, a thickener, if necessary. It is possible to add a compatibilizer or the like as appropriate.

The addition of the leveling agent can form a coating film with no aesthetics and good aesthetics. There is no particular limitation as long as the film formability can be improved and a uniform coating film can be obtained. Examples of such leveling agents include polyether-modified polydimethylsiloxane, polyether-modified siloxane, polyetherester-modified hydroxyl group-containing polydimethylsiloxane, polyether-modified acrylic group-containing polydimethylsiloxane, and polyester-modified acrylic group-containing polydimethylsiloxane. Siloxane compounds such as perfluoropolydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, and perfluoropolyester-modified polydimethylsiloxane; fluorine-containing organic compounds such as perfluoroalkylcarboxylic acid and perfluoroalkylpolyoxyethyleneethanol; polyoxy Polyether compounds such as ethylene alkylphenyl ether, propylene oxide polymer, ethylene oxide polymer; Carboxylic acids such as oil fatty acid amine salts and gum rosins; Castor oil sulfates, phosphate esters, alkyl ether sulfates, ester compounds such as sorbitan fatty acid esters, sulfonate esters, phosphate esters, succinate esters; alkylaryl sulfones Examples thereof include sulfonate compounds such as acid amine salts and sodium dioctyl sulfosuccinate; phosphate compounds such as sodium lauryl phosphate; amide compounds such as coconut oil fatty acid ethanolamide; and acrylic copolymers.

Among these, siloxane-based, fluorine-based and acrylic compounds are preferable from the viewpoint of film formability and repellency prevention, and polyether-modified polydimethylsiloxane is particularly preferable.

The blending amount of the leveling agent in the composition of the present invention is preferably 0.001 to 500 parts by mass, more preferably 0.01 to 300 parts by mass with respect to 100 parts by mass of the conductive polymer. preferable. When the amount is out of this range, repelling occurs and the coating film becomes uneven.

The antioxidant is not particularly limited, and examples thereof include reducing or non-reducing water-soluble antioxidants. Examples of water-soluble antioxidants having reducing properties include substitution with two hydroxyl groups such as L-ascorbic acid, sodium L-ascorbate, potassium L-ascorbate, erythorbic acid, sodium erythorbate, and potassium erythorbate. Compounds having a lactone ring; monosaccharides and disaccharides such as maltose, lactose, cellobiose, xylose, arabinose, glucose, fructose, galactose, mannose; flavonoids such as catechin, rutin, myricetin, quercetin, kaempferol; curcumin, rosmarinic acid Compounds having two or more phenolic hydroxyl groups such as chlorogenic acid, tannic acid, hydroquinone, 3,4,5-trihydroxybenzoic acid; cysteine, glutathione, pentaerythritol tetrakis (3-mercapto butyrate) include compounds having a thiol group such as. Non-reducing water-soluble antioxidants include, for example, oxidative degradation such as phenylimidazolesulfonic acid, phenyltriazolesulfonic acid, 2-hydroxypyrimidine, phenyl salicylate, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid sodium, etc. The compound which absorbs the ultraviolet-ray which causes this is mentioned. In the composition of the present invention, it is particularly preferable to use a compound having a lactone ring substituted with two hydroxyl groups, a monosaccharide and a disaccharide, a flavonoid compound, or a compound having two or more phenolic hydroxyl groups. These may be used alone or in combination of two or more.

The blending amount of the antioxidant in the composition of the present invention is preferably 0.001 to 500 parts by mass, and 0.01 to 300 parts by mass with respect to 100 parts by mass of the conductive polymer. Is more preferable. When it is less than 0.001 part by mass, the weather resistance cannot be maintained. When the amount is more than 500 parts by mass, the ratio of the antioxidant becomes too high, so that excellent far-infrared reflection performance and near-infrared absorption performance cannot be achieved.

The catalyst in the composition according to the present invention may be used to accelerate the polymerization reaction of the binder during the formation of the functional film and to shorten the curing time. Examples of such a catalyst include a radical photopolymerization initiator and a radical thermal polymerization initiator, and a radical photopolymerization initiator is preferable from the viewpoint of shortening the curing time.

Such radical polymerization initiators include 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propan-1-one (BASF: Irgacure 127) 1-hydroxy-cyclohexyl-phenyl-ketone (BASF: Irgacure 184), 1-hydroxy-cyclohexyl-phenyl-ketone (BASF: Irgacure 184) and benzophenone (BASF) Irgacure 500), 2,2-dimethoxy-1,2-diphenylethane-1-one (BASF: Irgacure 651), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane -1-one (manufactured by BASF: Irgacure 907), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hy Droxy-2-methyl-1-propan-1-one (BASF: Irgacure 2959), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (BASF: Darocur 1173), etc. It is done.

The compounding amount of the catalyst in the composition of the present invention is preferably 0.001 to 500 parts by mass, more preferably 0.01 to 300 parts by mass with respect to 100 parts by mass of the conductive polymer. preferable.

Examples of the antifoaming agent include compounds having a siloxane skeleton: polyester-modified methylalkylpolysiloxane, polyether-modified polymethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, and the like. The blending amount of the antifoaming agent in the composition of the present invention is preferably 0.001 to 500 parts by mass, more preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the conductive polymer.

Examples of the rheology control agent include cellulose derivatives and protein derivatives such as albumin and casein, alginic acid, agar, starch, polysaccharides, vinyl compounds, vinylidene compounds, polyester compounds, polyether compounds, and polyglycols. Compounds, polyvinyl alcohol compounds, polyalkylene oxide compounds, polyacrylic acid compounds, and the like. The blending amount of the rheology control agent in the composition of the present invention is preferably 0.001 to 500 parts by mass, more preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the conductive polymer.

The adhesion imparting agent can also be used. The blending amount of the adhesion-imparting agent in the composition of the present invention is preferably 0.001 to 500 parts by mass, more preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the conductive polymer.

A thickener may be added for the purpose of improving the viscosity. Examples of such thickeners include alginic acid derivatives, xanthan gum derivatives, water-soluble polymers such as saccharide compounds such as carrageenan and cellulose. The blending amount of the thickener in the composition of the present invention is preferably 0.001 to 500 parts by mass, more preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the conductive polymer.

[Method for producing composition]
The method for producing the composition of the present invention is not particularly limited, and the above components may be mixed while stirring with a stirrer such as a mechanical stirrer or a magnetic stirrer, and then stirred and mixed for about 1 to 60 minutes.

[Laminate]
A laminate including a functional film can be formed by applying the composition of the present invention to a substrate to be coated and then drying the composition. The substrate to be coated on which the composition is applied may be a transparent substrate or an opaque substrate. Although it does not specifically limit as a material which comprises a base material, For example, polyolefin resin, such as polyethylene, a polypropylene, an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid ester copolymer, an ionomer copolymer, a cycloolefin resin, Polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyoxyethylene, modified polyphenylene, polyphenylene sulfide, nylon 6, nylon 6,6, nylon 9, semi-aromatic polyamide 6T6, semi-aromatic polyamide 6T66, semi-aromatic polyamide Organic materials such as polyamide resin such as 9T, acrylic resin, polystyrene, acrylonitrile styrene, acrylonitrile butadiene styrene, vinyl chloride resin; and inorganic materials such as glass Kill.

The method for applying the composition is not particularly limited and can be appropriately selected from known methods. Examples thereof include spin coating, gravure coating, bar coating, dip coating, curtain coating, die coating, and spray coating. In addition, printing methods such as screen printing, spray printing, ink jet printing, relief printing, intaglio printing, and lithographic printing can also be applied.

For drying the coating film made of the composition, a normal ventilation dryer, a hot air dryer, an infrared dryer or the like is used. Of these, drying and heating can be performed simultaneously by using a dryer having a heating means (hot air dryer, infrared dryer, etc.). As the heating means, in addition to the dryer, a heating / pressurizing roll having a heating function, a press machine, or the like can be used.

The drying conditions of the coating film are not particularly limited, but are, for example, about 25 seconds to 200 ° C. for about 10 seconds to 2 hours, preferably about 80 ° C. to 150 ° C. for about 1 to 30 minutes.

The dry film thickness of the coating film formed from the composition of the present invention can be appropriately selected according to the purpose, but is generally 1 nm to 5 μm. However, from the viewpoint of high transparency and cost reduction, a thinner film thickness is preferable. In this respect, 0.50 μm or less is preferable, 0.40 μm or less is more preferable, and 0.30 μm or less is even more preferable. In the present invention, since a conductive polymer exhibiting high conductivity is used, even with such an extremely thin film, high far-infrared reflection performance and near-infrared absorption performance can be achieved.

In addition, the dry film thickness of the coating film formed on the substrate surface was measured using a stylus type surface shape measuring device Dektak 6M (manufactured by ULVAC, Inc.).

The laminate of the present invention including the functional film formed on the transparent substrate surface can be produced by applying and drying the composition of the present invention on the surface of the transparent substrate. Since the thin film to be formed is thin and extremely transparent, the laminate of the present invention can exhibit a visible light transmittance of 50% or more. Preferably, visible light transmittance of 60% or more can be exhibited.

The laminate has excellent far-infrared reflective performance, and a thermal conductivity of less than 5.9 W / m ² · K, preferably a thermal conductivity of less than 5.7 W / m ² · K, more preferably 5. A heat transmissivity of less than 5 W / m ² · K can be exhibited.

The heat transmissivity is the amount of heat that passes through 1 m ² of glass per hour when the temperature difference between the inside and outside of the glass is 1 ° C. In the present invention, the conductive polymer exhibiting far-infrared reflection performance. By providing a functional layer on a substrate such as glass using a composition containing, far infrared rays generated by a heating device or the like are confined in the room (the indoor heat is not released to the outside). It is possible to reduce.

The laminate has excellent near-infrared absorption performance and can exhibit a shielding coefficient of less than 0.95, preferably a shielding coefficient of less than 0.90, and more preferably a shielding coefficient of less than 0.85.

Shielding coefficient is a value representing the rate at which incident solar radiation (wavelength: about 300 nm-2500 nm) passes, and is an index indicating near infrared absorption performance.

Thus, while maintaining high transparency, it is possible to achieve far infrared reflection performance and near infrared absorption performance with a single layer.

The laminate of the present invention can be used for various applications. For example, the laminate of the present invention may be applied to a resin film such as a PET film. The functional film obtained in this way is affixed to the window glass (single-layer glass or double-layer glass), the walls of buildings or vehicles, vinyl houses, food packaging materials, or refrigerator or freezer walls. Can be used. Since the laminate of the present invention is extremely highly transparent, when applied to a window glass, it can exhibit excellent far-infrared reflection performance and near-infrared absorption performance without hindering the transparency of the window glass. it can. As a result, while enjoying high transparency, it is possible to expect an effect of not letting indoor heat escape to the outside (heat insulation) and an effect of not transferring external heat to the room (heat insulation).

Also, the composition of the present invention can be used by directly coating the surface of window glass, building or vehicle walls, vinyl houses, food packaging materials, or refrigerator or freezer walls.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Hereinafter, “part” or “%” means “part by mass” or “% by mass”, respectively, unless otherwise specified.

<Measurement of conductivity of conductive polymer>
The conductivity of the conductive polymer in the present invention was measured by the following procedure.

Each conductive polymer-containing aqueous dispersion was placed on a substrate with a wire bar No. 8 (wet film thickness 18 μm) was applied by a bar coating method and dried at 130 ° C. for 15 minutes to form a thin film on the substrate. About the formed thin film, the film thickness was measured with the stylus type film thickness measuring device. Thereafter, the surface resistivity of the thin film was measured with Loresta-GP (MCP-T600) manufactured by Mitsubishi Chemical Corporation. The measured film thickness and surface resistivity were substituted into the following equation to determine the conductivity of the conductive polymer.

Conductivity (S / cm) = 1 / {Surface resistivity (Ω / □) × film thickness (cm)}

Example 1
As a conductive polymer, 100 mass parts of a composite of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid in terms of a composite of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid aqueous dispersion (Heraeus Co.: CleviosPH1000, conductivity 0.46S / cm, solid content 1.0%), as an inorganic material, the _{Cs 0.33} WO ₃ particles 200 parts by CsMoWO ₃ particles converted water Dispersion (prepared according to the method described in JP-A-2011-195442, solid content 10%), 1000 parts by mass of silicon urethane acrylate (MIWON: MIRAMER SIU1000, solid content 100%) as a binder, as a leveling agent 100 parts by mass of siloxane leveling agent polyether-modified polydimethyl Siloxane (manufactured by Big Chem: BYK-307, solid content 100%), 100 parts by mass of Irgacure 127 (manufactured by BASF: solid content 100%) as a catalyst, and ethanol as a solvent were mixed to give a solid content concentration of 0.00. The content was adjusted to 1 to 20% by mass. Stir for 30 minutes. The obtained mixture was filtered through a 400 mesh SUS sieve to prepare a composition.

The obtained composition was placed on a 50 μm thick PET film (manufactured by Toray Industries, Inc .: Lumirror T-60) with a wire bar no. 34 (wet film thickness 39 μm) was applied by a bar coating method, dried at 130 ° C. for 2 minutes, and then exposed to an exposure amount of 1000 mJ / cm ² to obtain a laminate. The dry film thickness was 2 μm.

The obtained laminate was subjected to various evaluations based on the following methods, and the results are shown in Table 2.

(1) Visible light transmittance and shielding coefficient The visible light transmittance and shielding coefficient exhibited by various laminates were measured using a spectrophotometer V-670 (manufactured by JASCO Corporation) in accordance with JIS A5759.

(2) Thermal conductivity The thermal conductivity exhibited by various substrates was measured using FT-IR Frontier (Perkin Elmer) according to JIS A5759.

(3) Scratch resistance The scratch resistance exhibited by the various laminates is determined by one round trip with a 200 g load using steel wool # 0000 on a Gakuden dyeing friction fastness tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.). It was visually confirmed that it was judged as x if there were several hundred or more scratches, Δ if there were several tens of scratches, ◯ if there were several scratches, and ◎ if there were no scratches.

(4) Film-formability The film-formability exhibited by the various laminates is confirmed visually by checking whether the coating film is uniform after coating film formation. △, if judged uniform, judged as ◯.

(5) Weather resistance The weather resistance exhibited by the various laminates is 0% after heat irradiation for 1 hour at a metering weather meter (manufactured by Suga Test Instruments Co., Ltd .: temperature 63 ° C., humidity 50%, illuminance 1.55 kWh). It was judged as x when it changed by 5 W / m ² · K or more, Δ when it was 0.2 to 0.5, and ○ when it was less than 0.2.

(Example 2)
A laminate was obtained in the same manner as in Example 1 except that an aqueous dispersion of Cs _0.33 Mo _0.5 W _0.5 O ₃ was used as the inorganic material. The dry film thickness was 2 μm. Similar to Example 1, the evaluation results are shown in Table 2.

Example 3
A laminate was obtained in the same manner as in Example 1 except that an aqueous dispersion of silver nanowires was used as the inorganic material. The dry film thickness was 2 μm. Similar to Example 1, the evaluation results are shown in Table 2.

Example 4
A laminate was obtained in the same manner as in Example 1 except that ATO was used as the inorganic material. The dry film thickness was 2 μm. Similar to Example 1, the evaluation results are shown in Table 2.

(Example 5)
A laminate was obtained in the same manner as in Example 1 except that a fluorine-based leveling agent perfluoroalkyl group-containing surfactant (AGC Seimi Chemical Co., Ltd .: Surflon S-231) was used as the leveling agent. The dry film thickness was 2 μm. Similar to Example 1, the evaluation results are shown in Table 2.

(Example 6)
A laminate was obtained in the same manner as in Example 1, except that an acrylic leveling agent acrylic copolymer (Big Chem Co., Ltd .: BYK-381) was used as the leveling agent. The dry film thickness was 2 μm. Similar to Example 1, the evaluation results are shown in Table 2.

(Example 7)
A laminate was obtained in the same manner as in Example 1 except that 100 parts by mass of tannic acid (manufactured by Ajinomoto Omnichem) was further added as an antioxidant. The dry film thickness was 2 μm. Similar to Example 1, the evaluation results are shown in Table 2.

(Example 8)
A laminate was obtained in the same manner as in Example 1 except that 100 parts by mass of L-ascorbic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was further added as an antioxidant. The dry film thickness was 2 μm. Similar to Example 1, the evaluation results are shown in Table 2.

Example 9
As a binder, 1000 parts by weight of a polyester resin aqueous dispersion (manufactured by Nagase ChemteX Corporation: Gabsen ES-210, solid content 25%) was used without adding a catalyst, and after drying at 130 ° C. for 2 minutes. A laminate was obtained in the same manner as in Example 1 except that the exposure treatment was not performed. The dry film thickness was 2 μm. Similar to Example 1, the evaluation results are shown in Table 2.

(Example 10)
A laminate was obtained in the same manner as in Example 1 except that the leveling agent was not added. The dry film thickness was 2 μm. Similar to Example 1, the evaluation results are shown in Table 2.

(Example 11)
As the binder, except that 500 parts by mass of silicon urethane acrylate (manufactured by MIWON: MIRAMER SIU1000, solid content 100%) and 500 parts by mass of silicate oligomer (manufactured by Colcoat Co., Ltd .: ethylsilicate 40, solid content 100%) were used. In the same manner as in Example 1, a laminate was obtained. The dry film thickness was 2 μm. Similar to Example 1, the evaluation results are shown in Table 2.

Example 12
Except for using 500 parts by mass of silicon urethane acrylate (manufactured by MIWON: MIRAMER SIU 1000, solid content 100%) and 500 parts by mass of silicate oligomer (manufactured by Colcoat Co., Ltd .: ethyl silicate 48, solid content 100%) as the binder. In the same manner as in Example 1, a laminate was obtained. The dry film thickness was 2 μm. Similar to Example 1, the evaluation results are shown in Table 2.

(Example 13)
300 parts by mass of silicon alkoxide epoxy (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-303, solid content 100%) and 700 parts by mass of silicate oligomer (manufactured by Colcoat Co., Ltd .: ethyl silicate 40, solid content 100%) are used as binders. A laminate was obtained in the same manner as in Example 1 except that no catalyst was added and the exposure treatment was not performed after drying at 130 ° C. for 2 minutes. The dry film thickness was 2 μm. Similar to Example 1, the evaluation results are shown in Table 2.

(Example 14)
300 parts by mass of silicon alkoxide epoxy (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-402, solid content 100%) and 700 parts by mass of silicate oligomer (manufactured by Colcoat Co., Ltd .: ethyl silicate 40, solid content 100%) are used as binders. A laminate was obtained in the same manner as in Example 1 except that no catalyst was added and the exposure treatment was not performed after drying at 130 ° C. for 2 minutes. The dry film thickness was 2 μm. Similar to Example 1, the evaluation results are shown in Table 2.

(Example 15)
300 parts by mass of silicon alkoxide epoxy (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-403, solid content 100%) and 700 parts by mass of silicate oligomer (manufactured by Colcoat Co., Ltd .: ethyl silicate 40, solid content 100%) are used as binders. A laminate was obtained in the same manner as in Example 1 except that no catalyst was added and the exposure treatment was not performed after drying at 130 ° C. for 2 minutes. The dry film thickness was 2 μm. Similar to Example 1, the evaluation results are shown in Table 2.

(Example 16)
300 parts by mass of silicon alkoxide epoxy (manufactured by Shin-Etsu Chemical Co., Ltd .: KBE-403, solid content 100%) and 700 parts by mass of silicate oligomer (manufactured by Colcoat Co., Ltd .: ethyl silicate 40, solid content 100%) are used as binders. A laminate was obtained in the same manner as in Example 1 except that no catalyst was added and the exposure treatment was not performed after drying at 130 ° C. for 2 minutes. The dry film thickness was 2 μm. Similar to Example 1, the evaluation results are shown in Table 2.

(Example 17)
As a binder, 300 parts by mass of silicon alkoxide methacryl (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-503, solid content 100%) and 700 parts by mass of a silicate oligomer (manufactured by Colcoat Co., Ltd .: ethyl silicate 40, solid content 100%) are used. A laminate was obtained in the same manner as in Example 1 except that no catalyst was added and the exposure treatment was not performed after drying at 130 ° C. for 2 minutes. The dry film thickness was 2 μm. Similar to Example 1, the evaluation results are shown in Table 2.

(Example 18)
As a binder, 300 parts by mass of silicon alkoxide thiol (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-803, solid content 100%) and 700 parts by mass of a silicate oligomer (manufactured by Colcoat Co., Ltd .: ethyl silicate 40, solid content 100%) are used. A laminate was obtained in the same manner as in Example 1 except that no catalyst was added and the exposure treatment was not performed after drying at 130 ° C. for 2 minutes. The dry film thickness was 2 μm. Similar to Example 1, the evaluation results are shown in Table 2.

(Example 19)
300 parts by mass of silicon alkoxide vinyl (manufactured by Shin-Etsu Chemical Co., Ltd .: KBE-1003, solid content 100%) and 700 parts by mass of silicate oligomer (manufactured by Colcoat Co., Ltd .: ethyl silicate 40, solid content 100%) are used as binders. A laminate was obtained in the same manner as in Example 1 except that. The dry film thickness was 2 μm. Similar to Example 1, the evaluation results are shown in Table 2.

(Example 20)
300 parts by mass of silicon alkoxide acrylic (manufactured by Shin-Etsu Chemical Co., Ltd .: KBM-5103, solid content 100%) and 700 parts by mass of silicate oligomer (manufactured by Colcoat Co., Ltd .: ethyl silicate 40, solid content 100%) are used as binders. A laminate was obtained in the same manner as in Example 1 except that. The dry film thickness was 2 μm. Similar to Example 1, the evaluation results are shown in Table 2.

(Example 21)
As a binder, 300 parts by mass of silicon alkoxide isocyanate (manufactured by Shin-Etsu Chemical Co., Ltd .: KBE-9007, solid content 100%) and 700 parts by mass of a silicate oligomer (manufactured by Colcoat Co., Ltd .: ethyl silicate 40, solid content 100%) are used. A laminate was obtained in the same manner as in Example 1 except that no catalyst was added and the exposure treatment was not performed after drying at 130 ° C. for 2 minutes. The dry film thickness was 2 μm. Similar to Example 1, the evaluation results are shown in Table 2.

(Example 22)
Example except that silicate oligomer (manufactured by Colcoat Co., Ltd .: ethyl silicate 40, solid content: 100%) was used as a binder, no catalyst was added, and the mixture was further dried at 130 ° C. for 2 minutes and then was not exposed. 1 to obtain a laminate. The dry film thickness was 2 μm. Similar to Example 1, the evaluation results are shown in Table 2.

(Comparative Example 1)
With respect to a PET film having a thickness of 50 μm (Toray Industries, Inc .: Lumirror T-60), the visible light transmittance, the shielding coefficient, and the heat transmissivity were measured in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 2)
No inorganic material, no wire bar no. A laminate was obtained in the same manner as in Example 1 except that 2. The dry film thickness was 100 nm. Similar to Example 1, the evaluation results are shown in Table 2.

(Comparative Example 3)
A laminate was obtained in the same manner as in Example 1 except that the conductive polymer was not used and the composition AB of Table 1 was used. The dry film thickness was 2 μm. Similar to Example 1, the evaluation results are shown in Table 2.

The composition of the composition is shown in Table 1.

About each component in Table 1, it shows as follows.

Conductive polymer: a composite of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid (manufactured by Heraeus Co., Ltd .: Clevios PH1000, conductivity 0.46 S / cm, solid content 1.0%)
Inorganic materials: Cs _0.33 WO ₃ (average particle size 200 nm, solid content 10%), Cs _0.33 Mo _0.5 W _0.5 O ₃ (average particle size 100 nm, solid content 10%), silver nanowire ( Average length 10 μm, average aspect ratio 300, solid content 2%), ATO (average particle size 100 nm, solid content 10%)
Catalyst: Irgacure 127 (manufactured by BASF)
Leveling agent: siloxane-based leveling agent polyether-modified polydimethylsiloxane (manufactured by Big Chem: BYK-307), fluorine-based leveling agent, perfluoroalkyl group-containing surfactant (manufactured by AGC Seimi Chemical Co., Ltd .: Surflon S-231), Acrylic leveling agent (Big Chem: BYK-381)
Antioxidants: Tannic acid (Ajinomoto Omnichem), L-ascorbic acid (Wako Pure Chemical Industries, Ltd.)

As is apparent from Tables 1 and 2, in Examples 1 to 12, it is understood that the shielding coefficient and the heat transmissivity are reduced as compared with the comparative example containing no conductive polymer or inorganic material.

Claims

Used to form a functional film with far-infrared reflection performance and near-infrared absorption performance,
A composition comprising a conductive polymer exhibiting a conductivity of 0.05 S / cm or more, an inorganic material, and a binder.
The binder is a compound having a silicon alkoxide group, and at least one selected from the group consisting of a silicon alkoxide group and an acrylic group, an epoxy group, an alkyl group, a vinyl group, a methacryl group, a thiol group, an amino group, and an isocyanate group. The composition according to claim 1, which is at least one selected from compounds having a functional group.
The inorganic material is at least one selected from the group consisting of indium tin oxide (ITO), antimony tin oxide (ATO), composite tungsten oxide, and metal nanowires. Composition.
The composite tungsten oxide is
A composite tungsten oxide represented by the general formula W y O z (W is tungsten, O is oxygen, 2.2 ≦ z / y ≦ 2.999),
In the general formula M x W y O z (wherein, M represents, H, the He, alkali metals, alkaline earth metals, rare earth elements, Mg, Zr, Cr, Mn , Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, At least one element selected from the group consisting of V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1,. Composite tungsten oxide represented by 2 ≦ z / y ≦ 3.0), and
General formula M E A G W (1-G) O J (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, One element selected from Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I, and the A element are Mo, Nb, Ta, Mn, V, Re, and Pt. , Pd, and Ti, at least one element selected from the group consisting of W, tungsten, O is oxygen, and 0 <E ≦ 1.2, 0 <G ≦ 1, 2 ≦ J ≦ 3) The composition according to claim 3, wherein the composition is at least one selected from the group consisting of tungsten oxides. .
The composition according to claim 3, wherein the metal nanowire is a silver nanowire.
The conductive polymer exhibiting a conductivity of 0.05 S / cm or more is a composite of poly (3,4-ethylenedioxythiophene) and polystyrene sulfonic acid according to any one of claims 1 to 5. Composition.
The composition according to any one of claims 1 to 6, further comprising a leveling agent.
The composition according to claim 7, wherein the leveling agent is at least one selected from the group consisting of siloxane-based, fluorine-based and acrylic compounds.
The composition according to any one of claims 1 to 8, further comprising an antioxidant.
Obtained using the composition according to claim 1,
A laminate in which a functional film having a shielding coefficient of less than 0.95, a thermal transmissivity of less than 5.9 W / m 2 · K, and having far-infrared reflection performance and near-infrared absorption performance is laminated on a substrate.