JP5049195B2 - Colored sheet-like material having light reflection performance in the near infrared region - Google Patents

Description

  The present invention relates to vehicle interior materials such as vehicle instrument panels, door trims, and glove boxes, furniture surface materials such as benches for stations, bus stops, airfields, baseball fields, soccer fields, etc., or tents. The present invention relates to a colored sheet-like material having near-infrared region light reflection performance useful as a sheet-like material such as awning and track tarp.

  Since interior materials for vehicles such as automobiles, particularly instrument panels (instrument panels), are arranged on the front of the driver, it is not preferable that the driver feels dazzled by reflecting light in the visible light region. From such a viewpoint, a member provided with a color such as black is generally used for an instrument panel of an automobile. However, these commonly used colored materials absorb light in the near-infrared region other than the visible light region at the same time, so when exposed to sunlight, the surface is heated and the temperature inside the vehicle rises. Invite. Further, as the vehicle interior temperature rises, the use of air conditioning equipment results in a deterioration in fuel consumption. Such an increase in the temperature inside the vehicle due to sunlight has been a problem that occurs not only in the instrument panel but also in all the colored matters of the vehicle interior material.

  Also, in ball game fields such as baseball stadiums and soccer fields, it is not desirable that the color of the bench seat surface reflects light in the visible light region, and for sheet-like objects such as tents, awnings and track tarps. However, in some cases, a material that reflects light in the visible light region is not preferable because it is dazzling to human eyes. For this reason, colored materials are used for these materials, but there is a problem that the surface temperature increases as described above.

In order to solve these problems, a technique for forming a heat-shielding film or sheet on the surface of the structure as described above has been studied, for example, in Japanese Patent Application Laid-Open No. 2004-314596 (Patent Document 1). Is a sheet comprising at least a reflective layer and a colored layer, and the colored layer is laminated on the side exposed to light of the reflective layer, and the reflective layer is 60% or more in a wavelength region of 780 to 1350 nm. And the colored layer has a light transmittance of 30% or more in a wavelength region of 780 to 1350 nm and a solar absorptance of 10 to 80% in a wavelength region of 380 to 780 nm. A colored sheet having a shielding effect is disclosed. However, although the sheet described in Patent Document 1 has a heat shielding property, it is not always sufficient in terms of its heat shielding performance.
JP 2004-314596 A

  The present invention has been made in view of the above-described problems of the prior art. A colored sheet-like material having a solar radiation absorption rate of 80% or more in the visible light region of 380 to 780 nm and having excellent heat shielding properties is provided. The purpose is to provide.

  As a result of intensive studies to achieve the above object, the inventors of the present invention have made a reflective layer foamed at a specific foaming ratio in a synthetic resin sheet-like material having a colored surface layer and a reflective layer that receive sunlight. Surprisingly, it is possible to drastically improve the solar reflectance in the near infrared region of 780 to 1600 nm of the reflective layer, and to have excellent heat shielding properties. The inventors have found that a colored sheet can be obtained, and have completed the present invention.

That is, the colored sheet-like material of the present invention is a synthetic resin sheet-like material comprising a surface layer (A) that receives solar radiation and a reflective layer (B),
The surface layer (A) has a solar absorptivity of less than 30% in the near infrared region of 780 to 1600 nm, a solar transmittance of 50% or more in the near infrared region of 780 to 1600 nm, and 380 to 780 nm. A colored layer having a solar absorptance of 80% or more in the visible light region, and
The reflective layer (B) is a layer made of a foamed resin composition having a solar reflectance of 85% or more in the near infrared region of 780 to 1600 nm and a foaming ratio of 1.2 to 5.0 times.
It has the near-infrared region light reflection performance characterized by this.

  Moreover, in the colored sheet-like material of the present invention, it is preferable that the reflective layer (B) has a thickness of 70 to 400 μm.

  Furthermore, in the colored sheet material of the present invention, the foamed resin composition contains 3 to 100 parts by weight of titanium oxide having a weight average particle diameter of 300 to 500 nm with respect to 100 parts by weight of the synthetic resin. Preferably there is.

  In addition, according to this invention, it has a solar radiation absorptivity of 80% or more in a visible light region of 380 to 780 nm, and also provides a colored sheet-like material having a near-infrared region light reflection performance of having excellent heat shielding properties. It becomes possible. And the colored sheet-like material having the near-infrared region light reflecting performance of the present invention is a colored sheet-like material that absorbs light in the visible light region and has a dark color on the surface, but has a light color such as white. Demonstrate the same thermal insulation performance as a sheet. Although the reason for this is not necessarily clear, the present inventors speculate as follows. That is, the wavelength region of 380 to 780 nm is expressed as a visible light region and is light that can be felt by the human eye. Further, if the absorption rate of light in the visible light region is high (for example, the absorption rate is 90% or more), a dark color is exhibited. Furthermore, it is generally said that light in the near infrared region is easily converted into heat. Therefore, if the absorption of only light in the near-infrared region of sunlight is suppressed and transmitted or reflected, heat generation on the surface can be suppressed while being a colored sheet.

  In the colored sheet-like material having near-infrared region light reflection performance of the present invention, by making the reflective layer a layer made of a foamed resin composition obtained by foaming at a foaming ratio of 1.2 to 5.0 times, The reflection layer has an extremely high solar reflectance of 85% or more in the near infrared region of 780 to 1600 nm. The colored sheet-like material having the near-infrared region light reflection performance of the present invention has a visible layer of 380 to 780 nm on the surface of the reflective layer having an extremely high solar reflectance of 85% or more in the near infrared region of 780 to 1600 nm. It is a sheet-like material in which a surface layer having a solar absorptance of 80% or more in the light region and a solar transmittance of 50% or more in the near infrared region of 780 to 1600 nm is laminated. When sunlight is incident on such a sheet-like material, light in the visible light region of sunlight is absorbed at a high rate in the surface layer (A), and light transmitted through the surface layer (A) is Reflected by the reflective layer (B), the reflected light is absorbed at a high rate in the surface layer (A). Therefore, the sheet-like material of the present invention is provided with a dark color. Further, even if such light in the visible light region is absorbed, it is hardly converted into thermal energy, so that the heat shielding property of the sheet-like material is hardly affected. On the other hand, light in the near-infrared region, which is easily converted into thermal energy when it hits an object in sunlight, is transmitted almost unabsorbed in the surface layer (A), and light transmitted through the surface layer (A) is reflected layer Reflected by (B), the reflected light is transmitted through the surface layer (A) with almost no absorption, and is emitted to the outside. Therefore, the sheet-like material of the present invention has an excellent heat-shielding property, and has a heat-shielding performance equivalent to that of a light-colored sheet-like material such as white while having a dark color on the surface. The present inventors speculate.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the colored sheet-like thing which has the solar radiation absorptivity of 80% or more in the visible light region of 380-780 nm, and also has the outstanding heat-shielding property.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

The colored sheet-like material of the present invention is a synthetic resin sheet-like material comprising a surface layer (A) that receives solar radiation and a reflective layer (B),
The surface layer (A) has a solar absorptivity of less than 30% in the near infrared region of 780 to 1600 nm, a solar transmittance of 50% or more in the near infrared region of 780 to 1600 nm, and 380 to 780 nm. A colored layer having a solar absorptance of 80% or more in the visible light region, and
The reflective layer (B) is a layer made of a foamed resin composition having a solar reflectance of 85% or more in the near infrared region of 780 to 1600 nm and a foaming ratio of 1.2 to 5.0 times. is there.

<Surface layer (A)>
The surface layer (A) according to the present invention has a solar absorptivity of less than 30% in the near infrared region of 780-1600 nm, a solar transmittance of 50% or more in the near infrared region of 780-1600 nm, and It is a colored layer having a solar absorptance of 80% or more in a visible light region of 380 to 780 nm. The synthetic resin used for the surface layer (A) according to the present invention is not particularly limited. For example, a polyvinyl chloride resin, a polyolefin resin, an acrylic resin, a polyurethane resin, and a thermoplastic elastomer system composed of these resins. Resin. Among these synthetic resins, polyvinyl chloride resins, polyurethane resins, and thermoplastic elastomer resins are preferable from the viewpoints of texture, light resistance, and processability. Moreover, it is preferable that such a surface layer (A) consists of the synthetic resin of the same system as the synthetic resin which comprises the reflection layer (B) mentioned later from a viewpoint of adhesiveness and recyclability. Thus, when a surface layer (A) and a reflection layer (B) are comprised from the same type synthetic resin, what was excellent in adhesiveness can be obtained even if it does not provide an adhesive bond layer. Further, when the surface layer (A) and the reflective layer (B) are made of the same synthetic resin, it is advantageous in that the laminated layers can be recycled without being separated.

  And the surface layer (A) concerning this invention can be formed using the resin composition containing the said synthetic resin, for example.

  When a polyvinyl chloride resin is used as the synthetic resin, the polyvinyl chloride resin can be copolymerized with a vinyl chloride monomer homopolymer, vinyl chloride monomer and vinyl acetate monomer, acrylonitrile monomer or other vinyl chloride monomer. Copolymers with monomers can be used. The polymerization method of these polyvinyl chloride resins is not particularly limited, but an emulsion polymerization method (emulsion polymerization method) that exhibits a paste-like plastisol state when a plasticizer is blended is particularly preferably used. In addition, a micro suspension polymerization method, a soap-free emulsion polymerization method, a suspension polymerization method (suspension polymerization method), or the like can be used.

  Moreover, when using a polyvinyl chloride resin as the synthetic resin, a plasticizer may be further added to the resin composition. As the plasticizer, compounds used in ordinary polyvinyl chloride resins can be used. For example, di-2-ethylhexyl phthalate (DEHP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), dibutyl Phthalate plasticizers such as phthalate (DBP), diundecyl phthalate (DUP), butylbenzyl phthalate (BBP); Trimellitic ester plasticizers such as trioctyl trimellitate (TOTM); Dioctyl adipate (DOA) Fatty acid ester plasticizers such as dioctyl sebacate (DOS) and dioctyl azelate (DOZ); polyester plasticizers such as polypropylene adipate can be used.

  Further, the amount of the plasticizer added is not particularly limited, but is preferably in the range of 25 to 150 parts by weight, preferably 60 to 100 parts by weight with respect to 100 parts by weight of the polyvinyl chloride resin. It is more preferable that If the amount of the plasticizer is too small, the sol viscosity of the paste plastisol is high, it is difficult to flow, and a good cured film tends to be difficult to obtain. On the other hand, if the plasticizer is too much, the cured film itself becomes too soft and softens during use, and the heat resistance tends to deteriorate.

  Further, when a polyvinyl chloride resin is used as the synthetic resin, it is preferable to add a stabilizer used in an ordinary polyvinyl chloride resin to the resin composition as necessary. A metal stabilizer such as Ba—Zn, Ca—Zn, and zinc oxide can be used in a wide range. Further, an ultraviolet absorber such as a hindered amine compound, a benzotriazole compound, a benzothiazole compound, or an antioxidant may be added to the resin composition. Various additives such as a thickener and a thickener may be added.

  When a polyurethane-based resin is used as the synthetic resin, a resin having a so-called urethane bond of a polymer of a polyol component and an isocyanate component can be used as the polyurethane-based resin. For example, polyester-based polyurethane, polyether-based polyurethane Polycaprolactone-based polyurethane, polyester / polyether copolymer-based polyurethane, polyamino acid / polyurethane copolymer resin, or a mixture thereof can be used.

  In the case of using a polyurethane-based resin as the synthetic resin, it is particularly preferable to use a polyurethane-based resin having particularly good light resistance, particularly from the viewpoint of being used for exposure to direct sunlight. A non-yellowing polycarbonate-based polyurethane obtained by reacting a diol component, a non-yellowing diisocyanate component, a low molecular chain extender and the like is preferably used. As the polycarbonate diol component, for example, an aliphatic diisocyanate, an alicyclic diisocyanate, an aliphatic diisocyanate having a cyclic group, and the like can be used. It is preferable to use a mixture of

Moreover, as a low molecular chain extender, the compound which has 2 or more of active hydrogen atoms, such as aliphatic diol, alicyclic diol, aliphatic diamine, a hydrazine derivative, is used, for example. The polyurethane resin thus polymerized is a common organic solvent, specifically, methanol, ethanol, isopropanol, butanol, toluene, xylene, methyl ethyl ketone, methyl / n-propyl ketone, methyl isobutyl ketone, diethyl ketone. , Tetrahydrofuran, methyl cellosolve, butyl cellosolve, cellosolve acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, dioxane, cyclohexanone, or a mixture thereof, and used as a polyurethane solution.

Furthermore, when a polyurethane resin is used as the synthetic resin, various additives such as an antioxidant, a light stabilizer, an antistatic agent, and a flame retardant may be further added to the resin composition as necessary. Good.

  When a thermoplastic elastomer-based resin is used as the synthetic resin, an olefin-based thermoplastic elastomer (so-called TPO) is particularly preferably used as the thermoplastic elastomer-based resin. Specifically, polyolefin resin, ethylene-α-olefin copolymer rubber and / or ethylene-α-olefin / non-conjugated polyene copolymer rubber, and propylene / ethylene copolymer and / or propylene / 1-butene copolymer More specifically, a olefin resin mainly composed of polypropylene, polyethylene, EPDM (ethylene propylene terpolymer) and a rubber component are mixed and dynamically crosslinked. is there.

  In addition, when a thermoplastic elastomer resin is used as the synthetic resin, various additives such as an antioxidant, a light stabilizer, an antistatic agent, and a flame retardant are further added to the resin composition as necessary. May be.

  The surface layer (A) according to the present invention is a colored layer that transmits light in the near infrared region at a high rate and absorbs light in the visible light region. That is, such a surface layer (A) needs to have a solar radiation absorption rate of 80% or more in a visible light region of 380 to 780 nm. Thus, when the surface layer (A) has a solar radiation absorption rate of 80% or more in the visible light region of 380 to 780 nm, the colored sheet-like material of the present invention can substantially absorb light that can be sensed by humans. .

  Moreover, the solar radiation absorptivity of such a surface layer (A) needs to be less than 30% (preferably less than 10%) in the near infrared region of 780-1600 nm. When the solar absorptance is 30% or more, the surface layer (A) absorbs incident light before reaching the reflective layer (B), and the reflected light reflected by the reflective layer (B) is reflected on the surface layer. Since the surface layer (A) absorbs before reaching the outside of (A), as a result, the colored sheet-like material stores heat.

  Furthermore, the solar radiation transmittance of such a surface layer (A) needs to be 50% or more in the near infrared region of 780-1600 nm. That is, in order to maintain a solar radiation absorption rate of less than 30% in the near infrared region of 780 to 1600 nm, it is necessary to reflect or transmit light in the near infrared region, but when trying to reflect light in the near infrared region. In addition, since some of the visible light region of 380 to 780 nm also exhibits reflectivity, it is difficult to obtain a product with a dark color. Therefore, in the present invention, the solar radiation transmittance of such a surface layer (A) needs to be 50% or more in the near infrared region of 780 to 1600 nm.

In addition, the solar radiation absorptivity, solar radiation transmittance, and solar reflectance of the colored sheet-like material, the surface layer (A) and the reflective layer (B) (hereinafter, these are collectively referred to as solar radiation characteristics) are measured by the following methods. can do. That is, first, a single-layer sheet composed of a surface layer (A) or a reflective layer (B) or a sheet-like material (multi-layer sheet) provided with a surface layer (A) and a reflective layer (B) is used as a sample, and the spectrophotometricity is recorded. Using a meter, the reflectance of the alumina white substrate is set to 100%, and the reflectance (spectral reflectance) at each wavelength is measured. Then, using JIS A5759 Attached Table 3, the sum of values obtained by multiplying the spectral reflectance by the weight coefficient at each wavelength can be calculated to derive the solar reflectance (spectral solar reflectance test method). Further, for the sample, the transmittance (spectral transmittance) at each wavelength is measured using a self-recording spectrophotometer with the transmittance in a state where the sample is not inserted as 100%. Then, by using JIS A5759 Appendix Table 3, the sum of values obtained by multiplying the spectral transmittance by the weight coefficient at each wavelength can be calculated to derive the solar transmittance. Furthermore, from the values of the obtained solar reflectance and solar transmittance, the following mathematical formula:
(Solar radiation absorption rate) = 100%-(Solar radiation reflectance)-(Solar radiation transmittance)
The solar radiation absorption rate can be derived by calculating using.

  The thickness of the surface layer (A) according to the present invention is preferably in the range of 30 to 250 μm, and more preferably in the range of 50 to 200 μm. If the thickness of the surface layer (A) is less than the lower limit, light in the visible light region cannot be sufficiently absorbed, and it tends to be difficult to impart a dark color. On the other hand, when the thickness of the surface layer (A) exceeds the above upper limit, it tends to be difficult to ensure the solar absorption rate in the near infrared region to be less than 30% and to maintain the solar transmittance at 50% or more. This is not preferable because heat storage in the layer (A) tends to occur and the heat reflection performance of the colored sheet tends to be hindered.

  The surface layer (A) according to the present invention can be formed using the resin composition containing the synthetic resin. The resin composition for forming such a surface layer (A) may contain, in addition to the synthetic resin and various additives, a special pigment that transmits light in the near infrared region as described below. Good. Examples of such special pigments that transmit light in the near infrared region include azo pigments, anthraquinone pigments, phthalocyanine pigments, perinone / perylene pigments, indigo / thioindigo pigments, dioxane pigments, and quinacridone pigments. , Isoinnoridone pigments, isoindoline pigments, diketopyrrolopyrrole pigments, azomethine pigments, and azomethine azo pigments. Among these special pigments, azo pigments and perylene pigments are particularly preferable from the viewpoint of a balance of light absorption in the visible light region and light transmission in the near infrared region.

  Moreover, it is preferable that it is the range of 1-5 weight part with respect to 100 weight part of said synthetic resins as addition amount of these special pigments. If the addition amount is less than 1 part by weight, it tends to be difficult to darken in the visible light region. On the other hand, if it exceeds 5 parts by weight, the near infrared ray of the colored sheet-like product obtained by increasing the solar absorptance in the near infrared region. The area light reflection performance tends to be easily impaired.

  In addition, the resin composition for forming the surface layer (A) according to the present invention is obtained by weighing and mixing the above-described components with a mixing stirrer such as a dissolver mixer. Furthermore, such a resin composition may be filtered for the purpose of removing undispersed materials, or may be degassed under reduced pressure to remove bubbles, if necessary.

<Reflective layer (B)>
The reflective layer (B) according to the present invention is a layer made of a foamed resin composition having an expansion ratio of 1.2 to 5.0 times. And in such a reflection layer (B), the solar reflectance in the near infrared region of 780-1600 nm needs to be 85% or more. As described above, the reflection layer (B) has a solar reflectance of 85% or more in the near infrared region of 780 to 1600 nm, thereby reflecting the near infrared region light transmitted through the surface layer (A) at a high rate. As a result, near-infrared region light reflection performance can be imparted to the sheet-like material. Therefore, according to the present invention, a sheet-like material having excellent heat shielding properties can be obtained. Further, from the viewpoint of further improving the near-infrared region light reflection performance, the solar reflectance is preferably 90% or more. Conventionally, it is difficult to obtain a reflective layer having an extremely high solar reflectance of 85% or more in the near infrared region of 780 to 1600 nm, particularly when the thickness of the reflective layer is thin (for example, 250 μm or less). In this case, it was not possible to obtain a reflective layer having an extremely high solar reflectance. However, in the present invention, the reflection layer (B) is formed by foaming a resin composition described later at a foaming ratio of 1.2 to 5.0 times (more preferably 1.4 to 3.0 times). As a result, the solar reflectance in the near-infrared region can be dramatically improved, and thus a reflective layer (B) having an extremely high solar reflectance can be obtained. The expansion ratio refers to the volume ratio (magnification) of the foamed resin composition to the resin composition before foaming. When the expansion ratio is less than 1.2, the solar reflectance in the near infrared region of the reflective layer (B). Cannot be improved sufficiently. On the other hand, when the expansion ratio exceeds 5.0 times, the mechanical properties such as the tensile strength of the obtained sheet-like material are lowered.

  The thickness of the reflective layer (B) according to the present invention is preferably in the range of 70 to 400 μm, more preferably in the range of 70 to 250 μm, and particularly preferably in the range of 100 to 150 μm. If the thickness of the reflective layer (B) is less than the lower limit, sufficient solar reflectance tends to be difficult to ensure. On the other hand, exceeding the upper limit not only increases the manufacturing cost but also increases the weight of the entire sheet. Problems tend to occur.

  As the synthetic resin used for the reflective layer (B) according to the present invention, the same resin as the synthetic resin used for the surface layer (A) is used. And the reflection layer (B) concerning this invention can be formed by foaming the resin composition containing the said synthetic resin by 1.2 to 5.0 times expansion ratio. Examples of the method of foaming the resin composition as described above include, for example, (i) a method of adding a chemical foaming agent to the resin composition and foaming the synthetic resin with the chemical foaming agent, and (ii) a high-pressure inert gas. Below, the method of mixing in a resin composition, (iii) The method of mixing an inert gas by mechanically stirring a resin composition is employable. Among these methods, from the viewpoint of forming a reflective layer having a uniform and fine foam structure, a method of foaming a synthetic resin with a chemical foaming agent is preferable.

  As such a chemical foaming agent, a known chemical foaming agent can be appropriately used, and is not particularly limited. For example, ADCA (azodicarboxylic acid amide), OBSH (4,4′-oxybisbenzenesulfonylhydrazide) And organic decomposition type chemical foaming agents such as DPT (N, N′-dinitrosopentamethylenetetramine).

  The resin composition for forming the reflective layer (B) according to the present invention may contain a pigment as described below in addition to the synthetic resin and various additives. An example of such a pigment is a titanium oxide white pigment. As the titanium oxide-based white pigment, rutile type and anatase type titanium oxides can be used, but rutile type titanium oxide is preferable. Furthermore, the weight average particle diameter of such titanium oxide is preferably in the range of 300 to 500 nm. By using titanium oxide having a weight average particle diameter within the above range, the solar reflectance in the near infrared region of the reflective layer (B) can be further improved. The reason for this is not necessarily clear, but it is due to the fact that Mie scattering, which is a light scattering phenomenon by particles having the same wavelength as the light wavelength, increases the scattering efficiency when using particles having a particle diameter of about half the wavelength. Inferred.

  Further, the amount of such titanium oxide added is preferably in the range of 3 to 100 parts by weight, more preferably in the range of 10 to 30 parts by weight with respect to 100 parts by weight of the synthetic resin. When the addition amount is less than the lower limit, the solar reflectance of the reflective layer tends to decrease. On the other hand, even if the upper limit is added, the solar reflectance is not improved so much. Problems with physical properties may occur. In addition, you may mix | blend such a titanium oxide type white pigment in the toner state previously disperse | distributed to the plasticizer etc.

  In addition to the synthetic resin, various additives and pigments, the resin composition for forming the reflective layer (B) according to the present invention includes glass beads, hollow glass balloons, microcapsules, etc., as necessary. It may contain a filler.

  Moreover, the resin composition for forming the reflective layer (B) according to the present invention is obtained by weighing and mixing the above-mentioned components homogeneously with a mixing stirrer such as a dissolver mixer. Furthermore, such a resin composition may be filtered for the purpose of removing undispersed materials, or may be degassed under reduced pressure to remove bubbles, if necessary.

<Colored sheet-like material>
The colored sheet-like material of the present invention includes the surface layer (A) and the reflective layer (B), and is a colored sheet-like material having near-infrared region light reflecting performance. And the colored sheet-like material of this invention can be obtained by laminating | stacking the said surface layer (A) and the said reflection layer (B).

  As described above, various methods can be selected as a method of laminating the reflective layer (B) and the surface layer (A). For example, it is possible to form a multilayer structure by first forming the reflective layer (B) into a sheet and forming the surface layer (A) directly on one surface thereof. Conversely, the surface layer (A) can be formed first, and the reflective layer (B) can be laminated on one surface thereof. Further, both layers can be formed in a sheet form in advance and laminated by an adhesive or heat, and further, a third layer such as another base material may be interposed between both layers.

  Also, for example, when both layers are directly laminated on both the surface layer (A) and the reflective layer (B) using a polyvinyl chloride resin paste plastisol, the paper (release paper) or film having releasability After coating the surface layer (A) (or the reflective layer (B)) to the specified thickness by an appropriate method and solidifying by heating, the reflective layer (B) (or the surface layer (A)) is again applied to the specified thickness by an appropriate method. It is possible to form a laminated sheet-like product by coating the film and heating and solidifying it, followed by peeling from the release paper or film. In addition, not only a polyvinyl chloride resin but the layer structure where both layers are laminated | stacked directly is the most preferable from a viewpoint of functionality and manufacture.

  By laminating the surface layer (A) and the reflective layer (B) by these methods, it has a high reflectance in the near-infrared region contributing to heat generation among the wavelengths constituting the entire sunlight, and in the visible light region. When the surface layer (A) has an absorptance, a sheet-like product having a dark color and not dazzling for humans is obtained.

  In the colored sheet-like material of the present invention, an antifouling layer may be provided on the outermost surface as necessary. The antifouling layer should be applied with an antifouling paint composed of a solvent-based, water-based or ultraviolet curable paint in consideration of not adversely affecting the visible light absorption performance or near-infrared reflection performance of the present application. Can be formed.

  Among such antifouling paints, as solvent-based paints, for example, acrylic resin-based, vinyl chloride resin-based, cellulose resin-based, fluororesin-based, polyamide resin-based, urethane resin-based, epoxy resin-based, silicone resin-based, etc. Paint can be used.

  Among such antifouling paints, for example, acrylic resin-based, polyester resin-based, urethane resin-based, and epoxy resin-based paints can be used as the water-based paint.

  Furthermore, among such antifouling paints, for example, acrylic resin-based, acrylic-modified urethane resin-based, acrylic-modified epoxy resin-based, mercapto derivative-based, and epoxy resin-based paints can be used.

  Moreover, in the colored sheet-like material of this invention, in order to provide the design property to the said surface layer (A), you may give uneven | corrugated embossing. Such embossing can be performed by the same technique as embossing performed when an ordinary synthetic leather is obtained, such as embossing roll processing or release paper.

  Moreover, in the colored sheet-like material of the present invention, a fibrous base material such as a woven fabric or a non-woven fabric may be provided on the back surface of the reflective layer (B). The fibrous base material may be laminated with an adhesive on the reflective layer (B) side of the sheet-like material in which the reflective layer (B) and the surface layer (A) according to the present invention are formed on the release paper. The reflective layer (B) may be formed on the fibrous base material by a method such as impregnating the fibrous base material with the resin composition forming the layer (B). In particular, when used as a seating surface material such as a bench, such a form is preferable. Moreover, you may provide another resin layer in the back surface (fiber base material layer side) of a surface layer (A), a reflection layer (B), and a fiber base material layer. In particular, when used as a sheet-like material for a membrane structure such as a tent, such a form is preferable.

  Furthermore, the colored sheet-like material of the present invention is laminated on the surface of a molded body such as polyethylene foam, polypropylene foam, and urethane foam so as to be in contact with the surface of the molded body and the back surface of the reflective layer (B). Can be used. In particular, when it is used for an application such as an instrument panel or a door panel, such a form is preferable. Thus, the method of laminating a colored sheet-like material on the molded body may be adhered to the molded body using an adhesive on the reflective layer (B) side of the colored sheet-like material, for example, laminated on a urethane foam. In some cases, urethane foam may be injected and foamed directly into the colored sheet.

  As described above, by providing a fibrous base material or molded body to the colored sheet-like material of the present invention, the shape-retaining property, tear strength, and tensile strength of the sheet-like material are increased, and durability and workability during use are increased. improves.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. In Examples and Comparative Examples, the following were used as resins, pigments, fillers, and various additives.
Polyvinyl chloride resin: “PX-QHPN” manufactured by Shin Daiichi PVC
Urethane resin: “Resamine NE-8875” manufactured by Dainichi Seika Kogyo Co., Ltd.
Acrylic resin: Solvent type acrylic resin, “Acrynal XC # 9000” manufactured by Toei Kasei Co., Ltd.
Thermoplastic elastomer resin: “Milastomer N-8030” manufactured by Mitsui Chemicals, Inc.
Olefin resin: LDPE, “Ultzex 2022L” manufactured by Prime Polymer Co., Ltd.
Plasticizer: Isononyl phthalate, Sekisui Chemical Co., Ltd. foaming agent: ADCA thermal decomposition chemical foaming agent, Otsuka Chemical Co., Ltd. “Uniform AZ”
Stabilizer 1: Ba-Zn heat stabilizer, "FL-54" manufactured by Asahi Denka Kogyo Co., Ltd.
Stabilizer 2: Antioxidant, “AO-60” manufactured by Asahi Denka Kogyo Co., Ltd.
Pigment 1: Titanium oxide fine particles, weight average particle size: 410 nm, “Titanics WP0042” manufactured by Teika
Pigment 2: Black pigment, “Paliogen Black S-0084” manufactured by BASF AG
Pigment 3: Black pigment, “DPF-T-7939B” manufactured by Resino Color Industry Co., Ltd.
Pigment 4: Black pigment, “Arctic Black 10C909” manufactured by Shepherd
Pigment 5: Black pigment, “ARCTIC Black 411” manufactured by Shepherd
Pigment 6: Black pigment, “Toka Black # 8500 / F” manufactured by Tokai Carbon Co., Ltd.

(I) Preparation of paste plastisol and molding composition Resin, pigment, filler and various additives are mixed so as to have compositions as shown in Table 1 and Table 2, respectively, and molding paste plastisol And a resin composition was prepared.

  That is, for forming the reflective layer (B1 to B9) and the surface layer (A1 to A5), an emulsion-polymerized polyvinyl chloride (PX-QHPN, manufactured by Shin Daiichi PVC Co.), a foaming agent, a pigment, and a plasticizer (diisononyl phthalate) ) And a stabilizer (heat stabilizer) so as to have compositions as shown in Tables 1 and 2, respectively, and uniformly mixed with a dissolver mixer to prepare a paste plastisol for molding.

  In addition, for molding the surface layer (A6) and the reflective layer (B10), acetic acid as a solvent is used as a solvent for polyurethane resin (Resamine NE-8875, manufactured by Dainichi Seika Kogyo Co., Ltd.), which is a polymer of polycarbonate diol and isocyanate. Ethyl was added, and then a foaming agent and a pigment were blended so as to have compositions as shown in Tables 1 and 2, respectively, and mixed uniformly with a dissolver mixer to prepare a resin composition for molding.

  In addition, for molding the surface layer (A7), a pigment is blended into an acrylic resin (Acrynal XC # 9000, manufactured by Toei Kasei Co., Ltd.) so as to have the composition shown in Table 2, and mixed uniformly with a dissolver mixer. Thus, a resin composition for molding was prepared.

  For molding the surface layer (A8) and the reflective layer (B11), a thermoplastic elastomer (Miralastomer N8030, manufactured by Mitsui Chemicals Co., Ltd.) is added with a foaming agent, a stabilizer (antioxidant) and a pigment, respectively, in Table 1 and A resin composition for molding was prepared by dry blending to have a composition as shown in Table 2.

  Further, for molding the surface layer (A9) and the reflective layer (B12), a foaming agent, a stabilizer (antioxidant) and a pigment are added to the olefin resin (Ultzex 2022L, manufactured by Prime Polymer Co., Ltd.), respectively. The resin composition for molding was prepared by blending and dry blending so as to have the composition as described in 1.

(II) Preparation of single layer sheet In order to evaluate the solar radiation characteristics of the surface layer and the reflective layer, single layer sheets of the surface layer (A1 to A9) and the reflective layer (B1 to B12) were prepared as follows. .

  That is, the paste-like plastisol for forming the reflective layer (B1 to B9) and the surface layer (A1 to A5) is formed on the release paper by a knife coating method so as to have a thickness as shown in Table 1 and Table 2, respectively. Coated and heated at 140 ° C. for 2 minutes, then heated at 195 ° C. for 3 minutes. Then, it cooled and peeled the release paper and produced the single-layer sheet of the reflection layer (B1-B9) and the surface layer (A1-A5), respectively.

  Moreover, the resin composition for molding the surface layers (A6, A7) and the reflective layer (B10) is coated on the release paper by a knife coating method so as to have thicknesses as shown in Tables 1 and 2, respectively. And dried with hot air at 80 ° C. Thereafter, the release paper was peeled off by cooling, and single layer sheets of the surface layer (A6, A7) and the reflective layer (B10) were produced.

  Further, the resin composition for molding the surface layer (A8, A9) and the reflective layer (B11, B12) was extruded with a T-die extruder so as to have the thicknesses shown in Table 1 and Table 2, respectively, Single-layer sheets of layers (A8, A9) and reflective layers (B11, B12) were produced.

  In addition, Table 1 shows the thickness and the expansion ratio of the single-layer sheet of the obtained reflective layers (B1 to B12). In addition, Table 2 shows the hue and thickness of the single-layer sheet of the obtained surface layers (A1 to A9).

(III) Evaluation of solar radiation characteristics The solar radiation characteristics (solar absorption rate, solar transmittance, solar reflectance) of the single layer sheets of the reflective layers (B1 to B12) and the surface layers (A1 to A9) were evaluated by the following methods. . That is, first, using a single layer sheet of the reflective layer (B1 to B12) and the surface layer (A1 to A9) as a sample, a self-recording spectrophotometer U-4000 (manufactured by Hitachi, Ltd.) was used to reflect the alumina white substrate. The reflectance (spectral reflectance) at each wavelength was measured at 100%. Then, using JIS A5759 Attached Table 3, the sum of the values obtained by multiplying the spectral reflectance by the weight coefficient at each wavelength was calculated to derive the solar reflectance (spectral solar reflectance test method).

  Next, using the single-layer sheet as a sample and using a self-recording spectrophotometer U-4000 (manufactured by Hitachi, Ltd.), the transmittance without any sample is 100%, and the transmittance at each wavelength (spectral) Transmittance) was measured. Then, using Table 3 of JIS A5759, the sum of values obtained by multiplying the spectral transmittance by the weight coefficient at each wavelength was calculated, and the solar transmittance was derived.

Next, from the obtained values of solar reflectance and solar transmittance, the following mathematical formula:
(Solar radiation absorption rate) = 100%-(Solar radiation reflectance)-(Solar radiation transmittance)
The solar absorptance was derived by calculating using.

  In addition, about the single layer sheet | seat of the reflection layer (B1-B12), the solar reflectance in the 780-1600 nm near-infrared area | region was evaluated. The obtained results are shown in Table 1. Moreover, about the single layer sheet | seat of the surface layer (A1-A9), the solar radiation absorptivity in the visible light region of 380-780 nm and the solar radiation absorptivity and solar transmittance in the near infrared region of 780-1600 nm were evaluated. The obtained results are shown in Table 2.

(IV) Examples 1 to 10 and Comparative Examples 1 to 7
The paste layer plastisol for molding the surface layers (A1 to A5) was coated on a release paper by a knife coating method so as to have a layer configuration and thickness as shown in Tables 3 and 4, respectively, at 2O <0> C at 2O <0> C. Heated for minutes. Thereafter, a paste-like plastisol for forming the reflective layer (B1 to B9) is coated on the surface layer by a knife coating method so as to have the layer constitution and thickness as shown in Table 3 and Table 4, respectively. And heated at 195 ° C. for 3 minutes. And after cooling, the release paper was peeled and the colored sheet-like thing (multilayer sheet) was produced, respectively (Examples 1-6, Comparative Examples 1-7).

  Further, the resin composition for molding the surface layer (A6, A7) is coated on the release paper by the knife coating method so as to have the layer configuration and thickness as shown in Table 3, and dried with hot air at 80 ° C. did. Thereafter, the resin composition for forming the reflective layer (B10) is coated on the surface layer by a knife coating method so as to have the layer structure and thickness as shown in Table 3, and hot air at 80 ° C. And dried. And after cooling, the release paper was peeled off to produce colored sheet-like materials (Examples 7 and 8).

  Further, the resin compositions for molding the surface layers (A8, A9) and the reflective layers (B11, B12) are as shown in Table 3 using a two-type two-layer T-die extruder capable of changing the layer ratio. Coextruded so as to have the layer structure and thickness of the above to produce colored sheet-like materials (Example 9 and Example 10).

  In addition, the surface hue and thickness of the colored sheet-like material obtained in Examples 1 to 10 and the colored sheet-like material obtained in Comparative Examples 1 to 7 are shown in Table 3 and Table 4, respectively.

(V) Evaluation of solar radiation characteristics, heat shielding properties and glare of colored sheet-like material The heat shielding properties and glare of colored sheet-like materials obtained in Examples 1 to 10 and Comparative Examples 1 to 7 were evaluated by the following methods. did. Moreover, the solar radiation characteristic of the colored sheet was evaluated by the same method as the solar radiation evaluation method for the single-layer sheet. In addition, about the solar radiation characteristic, the solar radiation absorptivity in the visible light region of 380 to 780 nm, the solar radiation transmittance and the solar reflectance, and the solar radiation absorption factor, the solar radiation transmittance and the solar reflectance in the near infrared region of 780 to 1600 nm were evaluated. . The obtained results are shown in Table 3 and Table 4, respectively.

(I) Evaluation of heat insulation (Sunlight exposure temperature rise test)
A colored sheet-like material (multi-layer sheet) obtained in Examples and Comparative Examples was applied to a steel sheet having a width of 200 mm, a length of 300 mm, and a thickness of 0.3 mm to obtain the sample. In addition, a polyvinyl chloride resin sheet containing carbon black (thickness: 400 μm, composition: same as surface layer (A5)) is placed on a steel plate having a width of 200 mm, a length of 300 mm, and a thickness of 0.3 mm, the same size as the steel plate. The sample for reference was obtained by pasting. Then, these samples are placed on the bottom of a box (height 150 mm, width 240 mm, length 340 mm) made of expanded polystyrene having a thickness of 30 mm, and 1.5 mm thick soda glass on the top of the box. A plate was placed, and the temperature of the sheet surface inside the box was measured with a thermocouple, and exposed to sunlight on a clear day in August in the Kanto region. Then, observing the temperature of the sheet surface, the temperature were measured the temperature at which became constant, the difference between the surface temperature T _R of the sample for the surface temperature T and the reference of the sample (T R _-T) [Delta] T Recorded as (° C). It can be said that the larger the value of ΔT (° C.), the better the heat shielding property.

(ii) Evaluation of glare The colored sheet-like material (multi-layer sheet) obtained in Examples and Comparative Examples on the steel plate having a width of 200 mm, a length of 300 mm, and a thickness of 0.3 mm is made the same size as the steel plate. A sample was obtained by pasting. Under fine weather, the sample was tilted at an angle of 45 degrees and observed with the naked eye from a distance of 1 m, and whether or not it felt dazzling was evaluated according to the following criteria.
A: No reflection is felt and there is no glare.
B: Almost no reflection is felt, but tired when viewed for a long time.
C: The light is reflected and the glare is felt.
D: It feels very dazzling and cannot keep an eye on for a long time.

  As is clear from the results shown in Tables 3 and 4, the colored sheet-like materials (Examples 1 to 10) of the present invention are dazzling because of the large absorption of light in the visible light region of the surface layer (A). In addition, since the reflection of light in the near infrared region of the sheet was large, it was confirmed that the temperature rise on the sheet surface when exposed to sunlight was small.

  As described above, according to the present invention, it is possible to provide a colored sheet-like material having a solar radiation absorption rate of 80% or more in the visible light region of 380 to 780 nm and having excellent heat shielding properties. .

  Therefore, the colored sheet-like material of the present invention is a vehicle interior material such as an instrument panel for vehicles, a door trim, a glove box, and furniture such as a seat for a bench in a station, bus stop, airfield, baseball field, soccer field, etc. It is useful as a surface material, or a sheet-like material such as a tent, awning, or truck tarp.

Claims (3)

A synthetic resin sheet comprising a surface layer (A) that receives solar radiation and a reflective layer (B),
The surface layer (A) has a solar absorptivity of less than 30% in the near infrared region of 780 to 1600 nm, a solar transmittance of 50% or more in the near infrared region of 780 to 1600 nm, and 380 to 780 nm. A colored layer having a solar absorptance of 80% or more in the visible light region, and
The reflective layer (B) is a layer made of a foamed resin composition having a solar reflectance of 85% or more in the near infrared region of 780 to 1600 nm and a foaming ratio of 1.2 to 5.0 times.
A colored sheet-like material having a near-infrared region light reflection performance.   The colored sheet-like material according to claim 1, wherein the reflective layer (B) has a thickness of 70 to 400 μm.   3. The foamed resin composition contains 3 to 100 parts by weight of titanium oxide having a weight average particle diameter of 300 to 500 nm with respect to 100 parts by weight of a synthetic resin. The colored sheet-like material described.