TW201522046A - Heat-insulating laminate and composition for forming said heat-insulating laminate - Google Patents

Abstract

The purpose of the present invention is to provide a heat-insulating laminate having excellent far-infrared ray reflecting performance and abrasion resistance, and to provide a composition for forming said heat-insulating laminate. Provided is a heat-insulating laminate, characterized in that a hard coat layer that includes a silicate resin is formed on at least one surface of a heat-insulating layer.

Description

Insulating laminate and composition for forming the adiabatic laminate

The present invention relates to an adiabatic laminate having excellent far-infrared reflection performance and scratch resistance by suppressing absorption of far-infrared rays of a hard coat layer, and a composition for forming the heat-insulating laminate.

Infrared refers to electromagnetic waves that are shorter than the wavelength of red light and have a shorter wavelength than the wavelength of millimeters. They are classified into near-infrared (about 300-2,500 nm), medium-infrared (about 2,500-4,000 nm), and far-infrared (about 4,000-300,000 nm). ). In particular, the infrared ray having a long wavelength is generated by a heating device and is used to maintain a comfortable room temperature in winter. However, a part of the transmission window glass is released to the outside, which is a cause of a decrease in heating efficiency.

Attempts have been made to improve the heating efficiency in winter by providing a film having the property of reflecting infrared rays on the surface of the window glass.

As such a film that reflects infrared rays, a film made of a metal such as gold or silver is known, but these metal films have problems of being easily scratched and easily corroded. Therefore, by providing a protective layer to the metal thin film, scratch resistance and the like are imparted, and the infrared reflection performance is prevented from being lowered. Patent Document 1 discloses an infrared-reflective substrate which can provide scratch resistance and suppress emissivity by forming a protective layer of an infrared-ray reflective layer from a polycycloolefin layer.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-104887

However, when the olefin-based resin is used as the material of the protective layer, since the olefin-based resin does not have a functional group or a small number of functional groups, the hard coat layer is difficult to absorb infrared rays and is excellent in that it is difficult to hinder infrared reflection of the heat-insulating laminated body. , but low scratch resistance. Therefore, it is necessary to use a harder material than the olefin-based resin, but such a material has many functional groups, so that it is easy to absorb infrared rays and hinder infrared reflection of the heat insulating layer. An adiabatic laminate having excellent far infrared ray reflection performance and excellent scratch resistance has not been previously realized.

An object of the present invention is to provide an adiabatic laminate having excellent far-infrared reflectance and scratch resistance and a composition for forming the heat-insulating laminate.

A first aspect of the invention relates to an insulating laminate, characterized in that a hard coat layer containing a citrate resin is formed on at least one side of the heat insulating layer.

The above-mentioned citrate-based resin is preferably a combination of a compound (A) having a silicon alkoxide group and a compound (B) having an alkoxide oxime group and selected from an acrylonitrile group ( At least one functional group of the group consisting of an acryl group, an epoxy group, an alkyl group, a vinyl group, a methacryl group, a thiol group, an amine group, and an isocyanate group.

The blend ratio of the above compound (A) to the above compound (B) is preferably 95:5 to 50:50 by mass ratio.

The compound (B) is obtained by dividing the number of alkoxide groups per molecule by the weight average molecular weight of the above compound (B), preferably the above compound (A) per molecule. The amount of the alkoxy group is divided by 90% or less of the value obtained by dividing the weight average molecular weight of the above compound (A).

The thickness of the hard coat layer is preferably from 0.1 to 3 μm.

Preferably, each layer is laminated on the substrate in the order of the above-mentioned heat insulating layer and the above hard coat layer.

Preferably, an adhesive layer is laminated.

The heat insulating layer preferably contains a metal sputter layer.

The hard coat layer preferably further contains a conductive polymer exhibiting a conductivity of 0.05 S/cm or more.

The conductive polymer exhibiting a conductivity of 0.05 S/cm or more is preferably a composite of poly(3,4-ethylenedioxythiophene) and polystyrenesulfonic acid.

The second aspect of the present invention relates to a composition for forming a hard coat layer in the above heat insulating laminate.

According to the present invention, it is possible to provide an adiabatic laminate having excellent far-infrared reflection performance and scratch resistance by suppressing far-infrared absorption of a hard coat layer without hindering far-infrared reflection of a heat insulating layer by the above configuration. A composition for forming an adiabatic laminate.

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

[heat insulation layer]

The heat insulating layer of the heat insulating laminated body of the present invention has good visible light transmittance and reflects far infrared rays, and exhibits heat insulating properties. The visible light transmittance of the heat insulating layer based on JIS A 5759 is preferably 50% or more, more preferably 60% or more.

The heat insulating layer may be a heat insulating layer in a single layer, or may be used as a heat insulating layer by stacking at least one set of the high refractive index layer and the low refractive index layer. In the case where at least one set of the high refractive index layer and the low refractive index layer are stacked as a heat insulating layer, the substrate itself may function as a low refractive index layer or a high refractive index layer. Hereinafter, a case where at least one set of the high refractive index layer and the low refractive index layer are stacked as a heat insulating layer will be described in detail.

The infrared reflectance is easily obtained at the interface between the high refractive index layer and the low refractive index layer when infrared rays are incident from the high refractive index layer toward the low refractive index layer.

The refractive index of the high refractive index layer is adjusted to be higher than the refractive index of the low refractive index layer.

Here, the refractive index can be measured in the form of a refractive index of a wavelength of 550 nm.

The high refractive index layer is usually composed of a metal oxide, and indium tin oxide, TiO ₂ , ZrO ₂ , SnO ₂ , In ₂ O ₃ or the like can be used as the metal oxide.

The low refractive index layer is usually made of a metal, and for example, gold, silver, copper, or the like can be used.

The thickness of the low refractive index layer or the high refractive index layer is selected according to the wavelength of the infrared light to be reflected, and the thickness of the high refractive index layer is preferably adjusted in the range of 0.1 nm to 1000 nm, and the thickness of the low refractive index layer is adjusted. It is preferable to adjust in the range of 1 nm to 100 nm so that both the visible light transmittance and the far-infrared reflectance become high.

As the number of layers increases, the far-infrared reflectivity increases, but instead the visible line Since the transmittance is lowered, an appropriate number of layers can be selected in combination with the use. The thickness of the heat insulating layer is preferably from 1 nm to 5000 nm, more preferably 1 nm from the viewpoint of maintaining good visible light transmittance and reflecting far infrared rays. 1000nm.

Examples of the method for forming the low refractive index layer and the high refractive index layer include a sputtering method, a vacuum deposition method, and a plasma CVD method.

The heat insulating layer of the heat insulating laminate of the present invention preferably contains a sputtering layer formed by sputtering in terms of increasing the density of the material. In particular, the low refractive index layer is preferably a metal sputtered layer.

[hard coating]

The hard coat layer of the heat insulating laminate of the present invention is formed on at least one side of the heat insulating layer to suppress a decrease in far infrared ray reflection performance due to abrasion or corrosion of the heat insulating layer.

As the material for forming the hard coat layer of the heat insulating laminate of the present invention, a phthalate resin is preferably used. In the present invention, the citrate-based resin is not particularly limited as long as it has at least one alkyl alkoxide group (-Si-OR). The reason for this is that by using a phthalate-based resin, it is possible to provide excellent far-infrared reflection performance and scratch resistance without hindering the far-infrared reflection performance of the heat insulating layer.

The thermal conductivity of the heat insulating laminate of the present invention is preferably less than 1.5 W/m ² minus the thermal conductivity of the heat insulating layer before the formation of the hard coat layer. K.

The smaller the value obtained, the less the hard coat layer does not hinder the far infrared ray reflection performance of the heat insulating layer.

Here, the thermal conductivity is expressed by watts, and the amount of heat passing through the glass is 1 m ² per hour when the temperature difference between the inside and the outside of the glass is 1 ° C. The smaller the value of the thermal conductivity is, the more excellent the far-infrared reflection performance is.

Examples of the above-mentioned citrate-based resin include an alkane oxime acrylic resin, an alkoxide oxime epoxy resin, an alkoxide oxime vinyl resin, an alkano oxime methacrylic resin, an alkane oxime thiol resin, and an alkanol. An alkoxide oxime-based resin such as a guanamine-based resin, an alkoxide oxime isocyanate-based resin, an alkylene sulfonyl-based resin, or an alkoxide-based resin having no functional group other than the alkoxide oxime group.

More specifically, tetramethoxy decane, tetraethoxy decane, tetrapropoxy decane, methyl phthalate oligomer, ethyl decanoate oligomer, 2-(3, 4) -Epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyl Methyldiethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-methylpropenyloxypropylmethyldimethoxydecane, 3-methylpropenyloxypropyl Trimethoxydecane, 3-methacryloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, 3-mercaptopropylmethyldimethoxy Decane, 3-mercaptopropyltrimethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, N-2-(aminoethyl) 3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3- Aminopropyltriethoxydecane, 3-triethoxydecyl-N-(1,3- Methyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxydecane, 3-isocyanatepropyltriethoxydecane, methyltrimethoxydecane, dimethylformene Oxydecane, trimethylmethoxydecane, methyltriethoxydecane, methylphenoxydecane, n-propyltrimethoxydecane, diisopropyldimethoxydecane, isobutyltrimethoxy Base decane, diisobutyl dimethoxy decane, isobutyl triethoxy decane, n-hexyl trimethoxy decane, n-hexyl triethoxy decane, cyclohexyl methyl dimethoxy decane, n-octyl Triethoxy Basear, n-decyltrimethoxydecane, and the like.

The above-mentioned citrate-based resin is preferably a combination of a compound (A) having an alkyl alcohol group and a compound (B) having an alkyl alcohol group and selected from an acryl group, an epoxy group, At least one functional group of the group consisting of an alkyl group, a vinyl group, a methacryloyl group, a thiol group, an amine group, and an isocyanate group.

Further, the blending ratio of the compound (A) and the compound (B) is not particularly limited, and it is more preferably in the range of the mass ratio of the compound (A): the compound (B) = 95:5 to 50:50.

Further, the amount of the alkoxy group per molecule of the above compound (B) is divided by the weight average molecular weight of the above compound (B), and it is further preferred that the amount of the alkoxy group per molecule of the above compound (A) is divided by the above. The weight average molecular weight of the compound (A) is 90% or less. The reason for this is that cracks are less likely to occur in the hard coat layer after film formation, and the performance of the heat insulating layer is liable to be lowered.

Further, when the compound (A) and the compound (B) are used in combination, it is preferred that the amount of the alkoxy group per molecule of the compound (A) is 4 or more, and the compound (B) per molecule The number of alkoxy groups is 3 or less.

Further, the above weight average molecular weight can be measured by gel permeation chromatography (GPC).

The compound (A) is preferably those represented by the following formula (1).

In the formula (1), n is from 0 to 1,000, preferably from 0 to 500, and further preferably from 0 to 100.

When n is 0, at least one of R ₁ , R ₂ , R ₃ and R ₅ is an alkoxy 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 to 6} is a carbon number of 1 to 20, preferably 1 to 10, more preferably 1 to 5 alkoxy; and when n is 2 or more When at least one of R _{1 to 6} is a carbon number of 1 to 20, preferably 1 to 10, more preferably 1 to 5 alkoxy groups, and a plurality of R _{4 's} may be the same or different. There may be a plurality of R ₆ which may be the same or different.

In the case where n is 0, 1 or 2 or more, R _{1 to 6} are each independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, cycloalkenyl, and aryl, with the exception of alkoxy groups. Hydrocarbyl group such as aralkyl group, methylene group, vinyl group, allyl group, heterocyclic group, hydroxyl group, hydroxy (poly) alkoxy group, fluorenyl group, oxy group, thio group, phosphino group, halogen group, amine group The group consisting of an imine group, an N-oxide group, a nitro group, and a cyano group, and the hydrogen on the carbon chain and the hydrogen on the ring are independently or substituted.

With respect to R _{1 to 6} , as a substituent which may substitute hydrogen on the carbon chain or hydrogen on the ring, for example, an alkyl group (methyl group, ethyl group, propyl group, isopropyl group, butyl group, and second butyl group) may be mentioned. , a C _1-20 alkyl group such as a tributyl group, a cycloalkyl group (such as a C _3-10 cycloalkyl group such as a cyclopentyl group or a cyclohexyl group), a cycloalkenyl group (cyclopentenyl group, a cyclohexenyl group, etc.). C _3-10 cycloalkenyl, etc.), heterocyclic group (C _2-10 heterocyclic group containing an oxygen atom, a nitrogen atom, a sulfur atom or the like), an aryl group [phenyl group, alkylphenyl group (methyl group) Phenyl (tolyl), dimethylphenyl (xylenyl), etc., such as C _6-10 aryl, etc., aralkyl (benzyl, phenethyl, etc. C _6-10 aryl-C _{1- 4} alkyl or the like), an unsaturated hydrocarbon group such as a methylene group, a vinyl group or an allyl group, an alkoxy group (such as a C _1-4 alkoxy group such as a methoxy group), a hydroxyl group or a hydroxy group (poly) alkoxy group ( a hydroxy (poly) C _2-4 alkoxy group, etc., a fluorenyl group (such as a C _1-6 fluorenyl group such as an ethenyl group), an oxy group, a thiol group, a phosphino group, or a halogen group (a fluoro group, a chloro group, etc.) ), an amine group, an imido group, an N-oxide group, a nitro group, a cyano group or the like. Further, the hydrogen on the carbon chain or the hydrogen on the ring may be partially substituted or entirely substituted.

The compound (B) is preferably represented by the following formula (2).

In the formula (2), X is a single bond having 1 to 20 carbon atoms, preferably 2 to 15, more preferably 3 to 10 divalent chain hydrocarbon groups (here, the carbon chain may be linear or may be Branched, one of the carbon atoms may be substituted by a hetero atom, and some or all of the hydrogen on the carbon chain may be substituted, or a carbon number of 3 to 20, preferably 4 to 15, more preferably 5 to 10. a divalent cyclic hydrocarbon group (here, 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, and a part of the carbon atom may be substituted by a hetero atom, a part of the hydrogen on the ring Or all may be substituted); Y is selected from the group consisting of an acryloyl group, an epoxy group, an alkyl group, a vinyl group, a methacryl group, a thiol group, an amine group, and an isocyanate group; R _{7 to 9} At least one of the alkoxy groups having a carbon number of 1 to 20, preferably 1 to 10, and more preferably 1 to 5; the others are independently selected from the group consisting of hydrogen, an alkyl group, a cycloalkyl group, and a cycloalkenyl group. Aromatic, aralkyl, methylene, vinyl, allyl and the like hydrocarbon group, heterocyclic group, hydroxyl group, hydroxy (poly) alkoxy group, fluorenyl group, oxy group, thio group, phosphino group, halogen group , an amine group, an imido group, an N-oxide group, a nitro group, and Group in those of the group consisting of hydrogen and hydrogen on the carbon chain of the ring are each independently, may be substituted.

Examples of the substituent which may substitute hydrogen on the carbon chain or hydrogen on the ring include an alkyl group (methyl group, ethyl group, propyl group, isopropyl group, butyl group, second butyl group, third butyl group, etc.). C _3-10 cycloalkyl C _1-20 alkyl, etc.), cycloalkyl (cyclopentyl, cyclohexyl, etc.), cycloalkenyl (cyclopentenyl, cyclohexenyl and the like C _3-10 cycloalkenyl Base, etc.), heterocyclic group (C _2-10 heterocyclic group containing a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom, etc.), aryl [phenyl, alkylphenyl (methylphenyl (tolyl)) , dimethylphenyl (xylenyl), etc., such as C _6-10 aryl, etc., aralkyl (benzyl, phenethyl, etc., C _6-10 aryl-C _1-4 alkyl, etc.), An unsaturated hydrocarbon group such as a methylene group, a vinyl group or an allyl group, an alkoxy group (such as a C _1-4 alkoxy group such as a methoxy group), a hydroxyl group or a hydroxy group (poly) alkoxy group (hydroxy(poly) C ₂ ) _-4 alkoxy group, etc.), anthracenyl (such as a C _1-6 fluorenyl group such as an ethenyl group), an oxy group, a thiol group, a phosphino group, a halogen group (fluoro group, a chloro group, etc.), an amine group, or a sub Amine group, N-oxide group, nitro group, cyano group and the like. Further, the hydrogen on the carbon chain or the hydrogen on the ring may be partially substituted or entirely substituted.

The dry film thickness of the hard coat layer can be appropriately selected depending on the purpose, and is usually 0.1 nm to 5 μm. In order to obtain higher far infrared reflection performance and scratch resistance, it is preferably from 0.1 μm to 3 μm. More preferably, it is 0.1 μm to 2 μm, and further preferably 0.1 μm to 1 μm. If the thickness of the hard coat layer is less than 0.1 μm, the scratch resistance tends to be lowered. On the other hand, when the thickness of the hard coat layer is 3 μm or more, the far-infrared absorbing property is increased to be a heat insulating laminate. The far infrared ray reflection performance tends to decrease.

Further, the dried film thickness of the above hard coat layer was measured using a stylus type surface shape measuring device Dektak 6M (manufactured by Aifike Co., Ltd.).

The hard coat layer of the heat insulating laminated body of the present invention can be formed by adding a catalyst, a leveling agent, a conductive polymer or the like within a range that does not inhibit the effects of the present invention, and can be formed by: a citrate resin, The catalyst, the leveling agent, and the like are mixed with the solvent and stirred to adjust the composition, and the obtained composition is applied to at least one surface of the heat insulating layer, and then dried.

The coating method of the above composition is not particularly limited, and can be appropriately selected from known methods. For example, a spin coating method, a gravure coating method, a bar coating method, a dip coating method, a curtain coating method, a die coating method, a spray coating method, and the like can be mentioned. Further, a printing method such as screen printing, spray printing, inkjet printing, letterpress printing, gravure printing, or lithography may be used.

A drying machine such as a general air dryer, a hot air dryer, or an infrared dryer can be used for drying the coating film composed of the above composition. When such a dryer (hot air dryer, infrared dryer, etc.) having a heating means is used, drying and heating can be simultaneously performed. As the heating means, a heating/pressurizing roll having a heating function, a press, or the like may be used in addition to the above-described dryer.

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

(catalyst)

In order to promote the hydrolysis and polycondensation reaction of the compound (A) and the compound (B), a catalyst may be added to the hard coat layer.

As such a catalyst, including an acid or a basic compound, it can be used directly, or The state in which the solvent or the like is dissolved in a solvent such as water or alcohol (hereinafter, referred to as an acidic catalyst or an alkaline catalyst, respectively) is used.

The concentration when the acid or the basic compound is dissolved in the solvent is not particularly limited, and may be appropriately selected depending on the acid to be used, the properties of the basic compound, the content required for the catalyst, and the like. Here, when the concentration of the acid or the basic compound constituting the catalyst is high, the hydrolysis and the polycondensation rate tend to increase.

The amount of the catalyst added is preferably from 0.1 part by mass to 10 parts by mass per 100 parts by mass of the bismuth-based resin.

The type of the acidic catalyst or the basic catalyst is not particularly limited, and specific examples of the acidic catalyst include hydrogen halide such as hydrochloric acid; nitric acid, sulfuric acid, sulfurous acid, hydrogen sulfide, perchloric acid, and hydrogen peroxide; a carboxylic acid such as carbonic acid, formic acid or acetic acid; a substituted carboxylic acid in which R of the structural formula represented by RCOOH is substituted with another element or a substituent; a sulfonic acid such as benzenesulfonic acid or the like, and examples of the basic catalyst include: An amine base such as ammonia or an amine such as ethylamine or aniline.

(leveling agent)

A leveling agent can be added to the hard coat. By adding a leveling agent, the adhesion between the hard coat layer and the heat insulating layer can be improved, and a homogeneous film can be formed.

As such a leveling agent, a usual leveling agent can be used, and examples thereof include a decane-based leveling agent, an acrylic leveling agent, and a fluorine-based leveling agent. Specifically, examples of the decane-based leveling agent include polydimethyl siloxane, polyether modified polydimethyl siloxane, polyether modified polymethyl alkyl siloxane, and poly Ether-modified oxime, polydimethyl methoxy olefin containing polyester modified hydroxy group, polydimethyl methoxy olefin containing polyether modified hydroxy group, polyether modified polydimethyl group with propylene fluorenyl group Polyoxane, polyether modified oxirane with propylene fluorenyl group, polyester modified propylene group Further, as the fluorine-based leveling agent, perfluorobutanesulfonate, perfluoroalkyl-containing carboxylate, perfluoroalkylethylene oxide adduct, and Perfluoroalkyl phosphate, perfluoroalkyl-containing phosphate-type amine neutralizer, fluorine-containing-lipophilic group-containing oligomer, fluorine-containing-hydrophilic group-containing oligomer, containing Fluorine-hydrophilic-lipophilic group oligomer, fluorine-containing-hydrophilic-lipophilic group-carboxyl-containing oligomer, fluorine-containing-hydrophilic-lipophilic group-UV reactivity Based on oligomers and the like.

One type or two or more types of these may be used, and a siloxane-based leveling agent is preferred because it has good compatibility with a citrate-based resin.

The amount of the leveling agent added is preferably from 0.1 part by mass to 10 parts by mass, more preferably from 0.5 part by mass to 5 parts by mass, per 100 parts by mass of the bismuth-based resin.

(conductive polymer)

In order to improve the far-infrared reflection performance of the heat insulating laminate of the present invention, a conductive polymer may be added to the hard coat layer.

The conductive polymer is not particularly limited, and the conductivity of the conductive polymer is preferably 0.05 S/cm or more, more preferably 0.15 S/cm or more, still more preferably 0.25 S/cm or more.

The reason for this is that if it is 0.05 S/cm or more, the far-infrared reflection performance can be sufficiently exhibited.

The conductive polymer exhibiting a conductivity of 0.05 S/cm or more is easily produced by, for example, appropriately selecting a polymerization condition or a molecular weight for the π-conjugated conductive polymer. For example, a conductive polymer exhibiting high conductivity as described above can be obtained by increasing the molecular weight. Examples of the conductive polymer include polythiophene, polyethylene dioxythiophene, and polyisophthalide. Polyisothianaphthene, polypyrrole, polyaniline, polyparaphenylene, polyparaphenylene acetylene, derivatives thereof, and the like.

Among these, a polythiophene-based conductive polymer composed of a composite of polythiophene and a dopant is preferably used. In particular, when the conductive polymer is composed of a composite of poly(3,4-ethylenedioxythiophene) and polystyrenesulfonic acid, the pH is the highest as shown by the polymerization system at the time of production. It is preferable to obtain a conductive polymer which exhibits high conductivity. A conductive polymer exhibiting high conductivity is commercially available, and a commercially available product can also be used in the present invention.

Further, the conductivity of the conductive polymer of the present invention is such that a conductive layer composed of the conductive polymer is formed on a substrate, and the film thickness and surface resistivity indicated by the conductive layer are measured, and based on the following formula And calculate.

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

[substrate]

The heat insulating layer and the hard coat layer of the heat insulating laminate of the present invention may be disposed on the substrate.

In the heat insulating laminate of the present invention, it is preferred that the respective layers are laminated on the substrate in the order of the heat insulating layer and the hard coat layer. By making the heat insulating layer sandwiched between the substrate and the hard coat layer, the heat insulating layer is more excellent in scratch resistance, and the hard coat layer can be incident from the side of the hard coat layer which does not hinder the far infrared ray reflection property of the heat insulating layer. The infrared rays are reflected by the heat insulating layer.

Such a substrate may be a transparent substrate or an opaque substrate. The material constituting the substrate is not particularly limited, and examples thereof include polyolefins such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, ionic polymer copolymer, and cycloolefin resin. 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 9T and other polyamine resins; acrylic resin, polystyrene, acrylonitrile styrene, acrylonitrile butadiene styrene, chlorine Organic materials such as vinyl resin; inorganic materials such as glass.

[Adhesive layer]

Further, an adhesive layer can be provided in the heat insulating laminate of the present invention. The adhesive layer can be formed, for example, by using an acrylic adhesive, a rubber-based adhesive, a urethane-based adhesive, or an anthrone-based adhesive.

The above adhesive layer is preferably laminated to the substrate to be laminated. The reason for this is that the function of the portion to be reflected by the far infrared rays is facilitated without impairing the function of each of the heat insulating layer or the hard coat layer.

The film thickness of the above-mentioned adhesive layer is preferably a film thickness which is generally used in the field, and is, for example, preferably 0.1 to 100 μm, more preferably 0.1 to 10 μm.

Since the heat insulating laminate of the present invention has many uses for transparency, it is preferable that the adhesive is also transparent and has high weather resistance itself. As such an adhesive, a high molecular weight acrylic adhesive having a urethane crosslinkability or an epoxy crosslinkability is used. Further, an adhesive having properties such as antistatic properties can also be used.

The coating liquid to which the adhesive agent is added may be directly applied to the surface of the substrate, or the adhesive may be applied to the release film in advance and dried to form a film, and the adhesive surface of the film is bonded to the present The surface of the substrate of the insulative laminate of the invention is laminated and laminated.

[Insulation laminate]

The heat insulating laminate of the present invention has excellent far infrared reflection performance and can be displayed up to 5.3 W/m ² . The thermal conductivity of K is preferably less than 4.7 W/m ² . The thermal conductivity of K is more preferably less than 4.0 W/m ² . The thermal conductivity of K, as a material of the protective layer, has excellent scratch resistance as compared with the case of using an olefin-based resin.

Further, since the heat insulating laminate of the present invention can be formed to be thin, it can exhibit a visible light transmittance of 50% or more by laminating on the surface of the transparent substrate, and preferably exhibits a visible light transmittance of 60% or more.

The heat insulating laminated system of the present invention can be applied to users of various applications, besides window glass (single-layer glass or multi-layer glass), or attached to the wall of a building or vehicle, a plastic greenhouse, a food packaging material, or a refrigerator or Use the surface of the wall of the freezer or the like. Since the heat insulating laminated body of the present invention has extremely high transparency, when applied to a window glass, excellent far infrared ray reflection performance can be exhibited without impairing the transparency of the window glass. As a result, it is possible to expect the effect that the heat in the room does not escape to the outside (insulation property) while enjoying high transparency.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited by the examples. Hereinafter, "parts" or "%" means "parts by mass" or "% by mass" unless otherwise specified.

<Measurement of Conductivity of Conductive Polymer>

The conductivity of the conductive polymer was measured in the following order. An aqueous dispersion containing each conductive polymer was applied onto a substrate by a bar coating method using a wire bar No. 8 (wet film thickness: 18 μm), and dried at 130 ° C for 15 minutes. Thereby a film is formed on the substrate. For the formed film, the film thickness was measured using a stylus film thickness gauge. Thereafter, the surface resistivity of the film was measured using a Loresta GP (MCP-T600) manufactured by Mitsubishi Chemical Corporation. The conductivity of the conductive polymer was determined by substituting the measured values of the film thickness and the surface resistivity into the following formula.

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

(Example 1)

100 parts by mass of tetraethoxydecane (manufactured by Tama Chemical Co., Ltd.: TEOS, solid content component 100%, molecular weight 208.4) and 20 parts by mass of 2-(3,4-epoxycyclohexyl) as a resin constituting the hard coat layer Ethyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-303, 100% solid content, molecular weight: 246.4), and 3 parts by mass of nitric acid (manufactured by Wako Pure Chemical Industries, Inc.: 70% nitric acid) as a catalyst 1 part by mass of the leveling agent BYK-307 (manufactured by BYK Chemical Co., Ltd.: 100% solid content), and 4000 parts by mass of ethanol as a solvent were mixed and stirred for 30 minutes. A coating agent was prepared by filtering the obtained composition into a sieve made of SUS mesh of 400 mesh.

The obtained coating agent was applied to a film having a silver sputter film laminated on a PET film according to a usual method using a bar coater No. 34 (wet film thickness: 39 μm) by a bar coating method (visible light transmittance) = 69.0%, thermal conductivity = 3.8 W/m ² .K, scratch resistance = ×), and dried at 130 ° C for 2 minutes, whereby an adiabatic laminate was obtained.

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

(1) Dry film thickness

The dry film thickness of the heat insulating laminate was measured using a stylus type surface shape measuring device Dektak 6M (manufactured by Aifeike Co., Ltd.). Here, the film thickness means the film thickness of only the hard coat layer.

(2) Visible light transmittance

The visible light transmittance of the heat insulating laminate was measured in accordance with JIS A5759 using a spectrophotometer V-670 (manufactured by JASCO Corporation).

(3) Thermal conductivity

The thermal conductivity of the adiabatic laminate was measured in accordance with JIS A5759 using FT-IR Frontier (manufactured by Perkin Elmer Co., Ltd.). The thermal conductivity of the heat insulating laminate minus the thermal conductivity of the heat insulating layer before forming the hard coat layer is 1.5 W/m ² . K or more is recorded as ×, if it is less than 1.5W/m ² . K is recorded as ○.

(4) Scratch resistance

The abrasion resistance of the hard coat layer of the heat-insulating laminated body is visually confirmed by using a vibration-hardness tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) using steel wool #0000 at a weight of 500 g under a load of 10 g. If there is a deep scar, it is judged as ×, and if there is no deep scar, it is judged as ○.

(5) Cracking

The crack of the heat-insulating laminated body was visually confirmed to be cracked after the film formation, and it was judged to be × if there was a crack, and was judged to be ○ if there was no crack.

(Example 2)

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-303, solid content component 100%, molecular weight 246.4) as a resin constituting the hard coat layer was changed to 3 Adiabatic laminate was obtained in the same manner as in Example 1 except that glycidoxypropylmethyldimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-402, solid content component: 100%, molecular weight: 220.3) was used. . The evaluation results are shown in Table 2 in the same manner as in Example 1.

(Example 3)

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-303, solid content component 100%, molecular weight 246.4) as a resin constituting a hard coat layer Adiabatic laminate was obtained in the same manner as in Example 1 except that it was changed to 3-glycidoxypropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-403, solid content component: 100%, molecular weight: 236.3). . The evaluation results are shown in Table 2 in the same manner as in Example 1.

(Example 4)

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-303, solid content component 100%, molecular weight 246.4) as a resin constituting the hard coat layer was changed to 3 An adiabatic laminate was obtained in the same manner as in Example 1 except that glycidoxypropyltriethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBE-403, solid content component: 100%, molecular weight: 278.4) was used. The evaluation results are shown in Table 2 in the same manner as in Example 1.

(Example 5)

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-303, solid content component 100%, molecular weight 246.4) as a resin constituting the hard coat layer was changed to 3 -Methyl propylene methoxy propyl trimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-503, solid content: 100%, molecular weight: 248.4), and the catalyst was changed to 3 parts by mass of nitric acid (manufactured by Wako Pure Chemical Industries, Ltd.) : Nitric acid component 70%) and 5 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Steam Bart Chemicals Holding Co., Ltd.: IRGACURE 184), and dried at 130 ° C for 2 minutes, followed by UV irradiation (oxtail An adiabatic laminate was obtained in the same manner as in Example 1 except that the motor was manufactured by a motor company: UVH-1500M, a light source: a metal halide lamp. The evaluation results are shown in Table 2 in the same manner as in Example 1.

(Example 6)

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-303, solid content component 100%, molecular weight 246.4) as a resin constituting a hard coat layer An adiabatic laminate was obtained in the same manner as in Example 1 except that it was changed to 3-mercaptopropyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-803, solid content component: 100%, molecular weight: 196.4). The evaluation results are shown in Table 2 in the same manner as in Example 1.

(Example 7)

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-303, solid content component 100%, molecular weight 246.4) as a resin constituting a hard coat layer was changed to ethylene. Triethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBE-1003, solid content component 100%, molecular weight 190.3), and the catalyst was changed to 3 parts by mass of nitric acid (manufactured by Wako Pure Chemical Co., Ltd.: 70% nitric acid) 5 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Autobus Chemicals Holding Co., Ltd.: IRGACURE 184), and dried at 130 ° C for 2 minutes, and then subjected to UV irradiation (manufactured by Oxtail Electric Co., Ltd.: UVH) A heat insulating laminate was obtained in the same manner as in Example 1 except that -1500 M, a light source: a metal halide lamp. The evaluation results are shown in Table 2 in the same manner as in Example 1.

(Example 8)

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-303, solid content component 100%, molecular weight 246.4) as a resin constituting the hard coat layer was changed to 3 - propylene methoxy propyl trimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-5103, solid content component: 100%, molecular weight: 234.3), and the catalyst was changed to 3 parts by mass of nitric acid (manufactured by Wako Pure Chemical Industries, Ltd.: nitric acid 70%) and 5 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone (manufactured by Steam Batt Chemicals Holding Co., Ltd.: IRGACURE 184), and dried at 130 ° C for 2 minutes, UV irradiation (Oxtail Motors Co., Ltd.) Co., Ltd. manufactured: UVH-1500M, light source: metal halide lamp), except that heat insulation was obtained in the same manner as in Example 1. Laminated body. The evaluation results are shown in Table 2 in the same manner as in Example 1.

(Example 9)

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-303, solid content component 100%, molecular weight 246.4) as a resin constituting the hard coat layer was changed to 3 An insulating laminate was obtained in the same manner as in Example 1 except that the isocyanate propyl triethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBE-9007, solid content component: 100%, molecular weight: 247.4). The evaluation results are shown in Table 2 in the same manner as in Example 1.

(Embodiment 10)

The tetraethoxy decane (manufactured by Tama Chemical Co., Ltd.: TEOS, solid content component 100%, molecular weight 208.4) which is a resin constituting the hard coat layer was changed to a methyl phthalate oligomer (manufactured by Mitsubishi Chemical Corporation: MS- An insulating laminate was obtained in the same manner as in Example 1 except that the solid content component was 100% and the weight average molecular weight was 600. The evaluation results are shown in Table 2 in the same manner as in Example 1.

(Example 11)

The tetraethoxy decane (manufactured by Tama Chemical Co., Ltd.: TEOS, solid content component 100%, molecular weight 208.4) which is a resin constituting the hard coat layer was changed to a methyl phthalate oligomer (manufactured by Mitsubishi Chemical Corporation: MS- A heat insulating laminate was obtained in the same manner as in Example 1 except that 56S, a solid content of 100%, and a weight average molecular weight of 600). The evaluation results are shown in Table 2 in the same manner as in Example 1.

(Embodiment 12)

Tetraethoxy decane (manufactured by Tama Chemical Co., Ltd.: TEOS, solid content component 100%, molecular weight 208.4) as a resin constituting a hard coat layer was changed to methyl phthalate oligomer (Mitsubishi) An insulating laminate was obtained in the same manner as in Example 1 except that the chemical company produced: MS-58, a solid content of 100%, and a weight average molecular weight of 600). The evaluation results are shown in Table 2 in the same manner as in Example 1.

(Example 13)

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-303, solid content component 100%, molecular weight 246.4) in the resin constituting the hard coat layer was changed to 10 An insulating laminate was obtained in the same manner as in Example 1 except for the mass parts. The evaluation results are shown in Table 2 in the same manner as in Example 1.

(Example 14)

2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd.: KBM-303, solid content component 100%, molecular weight 246.4) in the resin constituting the hard coat layer was changed to 100 An insulating laminate was obtained in the same manner as in Example 1 except for the mass parts. The evaluation results are shown in Table 2 in the same manner as in Example 1.

(Example 15)

An insulating laminate was obtained in the same manner as in Example 1 except that 10 parts by mass of poly(3,4-ethylenedioxythiophene) was used as the conductive polymer, without using a catalyst. The evaluation results are shown in Table 2 in the same manner as in Example 1.

(Embodiment 16)

An insulating laminate was obtained in the same manner as in Example 1 except that the coating was carried out by a bar coating method using a bar coater No. 8 (wet film thickness: 9 μm). The evaluation results are shown in Table 2 in the same manner as in Example 1.

(Example 17)

An insulating laminate was obtained in the same manner as in Example 1 except that the coating was carried out by a bar coating method using a bar coater No. 90 (wet film thickness: 103 μm). The evaluation results are shown in Table 2 in the same manner as in Example 1.

(Comparative Example 1)

In the same manner as in the first embodiment, the resin constituting the hard coat layer was changed to 100 parts by mass of polydecene (manufactured by JEOL Co., Ltd.: ZEONOR, solid content: 100%), and the catalyst was not used. In this way, an adiabatic laminate is obtained. The evaluation results are shown in Table 2 in the same manner as in Example 1.

(Comparative Example 2)

The resin constituting the hard coat layer was changed to 100 parts by mass of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.: DPHA, solid content: 100%), and the catalyst was changed to 5 parts by mass of 1-hydroxy-cyclohexyl group. Phenyl-ketone (manufactured by Vapart Chemicals Holding Co., Ltd.: IRGACURE 184), and dried at 130 ° C for 2 minutes, then subjected to UV irradiation (manufactured by Ngau Electric Co., Ltd.: UVH-1500M, light source: metal halide lamp), except Otherwise, an adiabatic laminate was obtained in the same manner as in Example 1. The evaluation results are shown in Table 2 in the same manner as in Example 1.

The blending composition of the above composition is shown in Table 1.

As is clear from Tables 1 and 2, Examples 1 to 17 have high far-infrared reflection performance and scratch resistance as compared with the comparative examples containing no citrate-based resin.

Claims (11)

An insulating laminate in which a hard coat layer containing a citrate resin is formed on at least one side of the heat insulating layer. The adiabatic laminate according to the first aspect of the invention, wherein the bismuth-based resin is a combination of a compound (A) having a silicon alkoxide group and the following compound (B), the compound (B) Having an alkyl alcohol group and a group selected from the group consisting of an acryl group, an epoxy group, an alkyl group, a vinyl group, a methacryl group, a thiol group, an amine group, and an isocyanate group At least one functional group. The adiabatic laminate according to item 2 of the patent application, wherein the blend ratio of the compound (A) to the compound (B) is 95:5 to 50:50 by mass ratio. The adiabatic laminate according to claim 2 or 3, wherein the compound (B) is obtained by dividing the number of alkoxide groups per molecule by the weight average molecular weight of the compound (B). (A) The amount of the alkoxy group per molecule divided by 90% or less of the value obtained by the weight average molecular weight of the compound (A). The heat insulating laminate according to any one of claims 1 to 3, wherein the hard coat layer has a thickness of 0.1 to 3 μm. The heat insulating laminate according to any one of claims 1 to 3, wherein each layer is laminated on the substrate in the order of the heat insulating layer and the hard coat layer. For example, the heat insulating laminate of claim 6 is further laminated with an adhesive layer. The heat insulating laminate according to any one of claims 1 to 3, wherein the heat insulating layer contains a metal sputtering layer. The heat insulating laminate according to any one of claims 1 to 3, wherein the hard coat layer Further, it contains a conductive polymer exhibiting a conductivity of 0.05 S/cm or more. The adiabatic laminate according to claim 9, wherein the conductive polymer exhibiting a conductivity of 0.05 S/cm or more is poly(3,4-ethylenedioxythiophene) and polystyrenesulfonic acid. Complex. A composition for forming a hard coat layer in an insulating laminate of any one of claims 1 to 10.