JP5227576B2 - Dark-colored composite molded article having light reflection performance in near infrared region - Google Patents

Description

  INDUSTRIAL APPLICABILITY The present invention can be used as a structure such as a vehicle interior material such as an instrument panel for a vehicle, a door trim, a glove box, and furniture such as a seat of a bench in a station, a bus stop, an airfield, a baseball field, a soccer field, etc. The present invention relates to a dark composite molded article having a near-infrared region light reflection performance.

  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 having a dark color such as black is generally used for an instrument panel of an automobile. However, these commonly used dark-colored objects 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 a rise in the temperature of the vehicle due to sunlight is a problem that occurs not only in the instrument panel but also in all dark objects of the vehicle interior material.

  Also, in a ball game field such as a baseball field or a soccer field, it is not desirable that the color of the bench seat surface reflects light in the visible light region. For this reason, dark 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 film or sheet having a heat-shielding property on the surface of the structure as described above has been studied. For example, Japanese Patent Laid-Open No. 2002-12679 (Patent Document 1) Discloses a heat-shielding color film formed by mixing two or more pigments having heat-shielding properties to a thermoplastic resin film. However, the film as described in Patent Document 1 can give a color to the structure, but it also causes solar reflectivity in the visible light region as well as the near infrared region, There has been a problem that it is difficult to sufficiently secure the heat shielding property of the film, sufficiently suppress the increase in the surface temperature of the structure when exposed to sunlight, and make the structure dark.

In Japanese Patent Application Publication No. 2004-505808 (Patent Document 2), the reflectance in the visible light region of 380 to 720 nm is less than 50%, and the reflectance in the near infrared region of 720 to 1500 nm exceeds 60%. A structure comprising a substrate having properties and a coating film containing two kinds of pigments having specific properties provided on the substrate is disclosed. However, the structure as described in Patent Document 2 has a problem that it is difficult to sufficiently suppress an increase in surface temperature when exposed to sunlight.
JP 2002-12679 A Special table 2004-505808 gazette

  The present invention has been made in view of the above-described problems of the prior art, has a solar absorptance of 90% or more in the visible light region of 380 to 720 nm, and has a surface temperature when exposed to sunlight. An object is to provide a dark composite molded product capable of sufficiently suppressing the rise.

  The wavelength region of 720 to 1500 nm is generally expressed as a near infrared region, and light in this wavelength region is generally said to be easily converted into heat. By suppressing the absorption of light in this wavelength region, the heat rays are not absorbed, and therefore heat generation on the surface is suppressed. Therefore, the present inventors examined reflection without absorbing light in this wavelength region, but had high solar absorption in the visible light region and high solar reflectance in the near infrared region. It has been found that it is difficult to find such a material, and it is difficult to obtain a structure that is dark and suppresses absorption of light in the near infrared region. Therefore, as a result of intensive studies to solve the above problems, the present inventors have found that the surface of the reflective molded body having an extremely high solar reflectance of 85% or more in the wavelength region of 380 to 1500 nm is 380 to 1500 nm. By providing a surface layer having a solar absorptance of 90% or more in the visible light region of 720 nm and a solar transmittance of 50% or more in the near infrared region of 720 to 1500 nm, when exposed to sunlight The inventors have found that the increase in the surface temperature of the dark composite molded article can be sufficiently suppressed, and have completed the present invention.

That is, the dark composite molded article having near-infrared region light reflection performance of the present invention is a synthetic resin composite molded article comprising a surface layer (A) that receives solar radiation and a reflective molded article (B),
The surface layer (A) contains 100 parts by weight of a synthetic resin and 1 to 5 parts by weight of at least one pigment selected from the group consisting of an azo pigment, an azomethine azo pigment, and a perylene pigment, It has a solar absorptance of 90% or more in the wavelength region of 720 nm, a solar absorptivity of less than 30% in the near infrared region of 720 to 1500 nm, and a solar transmittance of 50% or more in the near infrared region of 720 to 1500 nm. A synthetic resin layer exhibiting a dark color
The reflection molded body (B) is a synthetic resin molded body having a solar reflectance of 90% or more in a wavelength region of 380 to 1500 nm, and
The solar reflectance in the near infrared region of 720 to 1500 nm of the composite molded body in which the surface layer (A) is laminated on the surface of the reflective molded body (B) is 70% or more.

  In the dark composite molded article of the present invention, the surface layer (A) is made of at least one synthetic resin selected from the group consisting of a polyvinyl chloride resin, a polyurethane resin and a thermoplastic elastomer resin. Is preferred.

  In the dark composite molded article of the present invention, the reflective molded article (B) preferably contains 100 parts by weight of a synthetic resin and 5 to 70 parts by weight of a titanium oxide white pigment.

  Furthermore, in the dark composite molded article of the present invention, the reflective molded article (B) preferably has a foamed structure.

  According to such a dark composite molded article of the present invention, it has a solar absorptance of 90% or more in the visible light region of 380 to 720 nm, and has a sufficient reflection performance for light in the near infrared region, It becomes possible to provide a dark color composite molded article in which an increase in surface temperature when exposed to is sufficiently suppressed. The dark composite molded product having near-infrared region light reflection performance of the present invention is a structure that absorbs light in the visible light region and exhibits a dark color on the surface, but has a heat reflection equivalent to a light-colored structure such as white. Demonstrate performance. The reason why the surface exhibits a heat reflection performance equivalent to that of a light-colored structure such as white while the surface is a structure having a dark color is not necessarily clear, but the present inventors infer as follows. . That is, first, a wavelength region of 380 to 720 nm is expressed as a visible light region, which is light that humans can feel with the naked eye, and has a high light absorption rate in the visible light region (for example, the absorption rate is 90% or more). There is a dark color). Furthermore, it is generally said that light in the near infrared region is easily converted into heat. Therefore, if absorption of only light in the near-infrared region of sunlight is suppressed and transmitted or reflected, heat absorption on the surface is suppressed while being a dark-colored structure. The dark color composite molded article having near-infrared region light reflection performance of the present invention has a visible wavelength of 380 to 720 nm on the surface of the reflective molded article having an extremely high solar reflectance of 85% or more in the wavelength range of 380 to 1500 nm. It is a composite molded body in which a surface layer having a solar absorptance of 90% or more in the light beam region and a solar radiation transmittance of 50% or more in the near infrared region of 720 to 1500 nm is laminated. When such a composite molded body is exposed to sunlight, the light in the visible light region of the sunlight is absorbed at a high rate in the surface layer (A) and transmitted through the surface layer (A). Is reflected by the reflection molded body (B), and the reflected light is absorbed at a high rate in the surface layer (A). Therefore, the composite molded body of the present invention is dark. Further, even if such light in the visible light region is absorbed, it is hardly converted into thermal energy, so that the surface temperature of the composite molded body 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 reflection-molded The light is reflected by the body (B), and the reflected light passes through the surface layer (A) with almost no absorption and is emitted to the outside. Therefore, in the composite molded body of the present invention, the rise in the surface temperature when exposed to sunlight is sufficiently suppressed, and the heat reflection performance equivalent to a light-colored structure such as white while the surface is dark. The present inventors speculate that they have

  According to the present invention, a dark composite molding having a solar absorptance of 90% or more in a visible light region of 380 to 720 nm and capable of sufficiently suppressing an increase in surface temperature when exposed to sunlight. The body can be provided.

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

The dark-colored composite molded article having near-infrared region light reflection performance of the present invention is a synthetic resin composite molded article comprising a surface layer (A) that receives solar radiation and a reflective molded article (B),
The surface layer (A) has a solar absorptivity of 90% or more in a wavelength region of 380 to 720 nm, a solar absorptivity of less than 30% in a near infrared region of 720 to 1500 nm, and a near 720 to 1500 nm. A synthetic resin layer having a dark color with a solar transmittance of 50% or more in the infrared region,
The reflection molded body (B) is a synthetic resin molded body having a solar reflectance of 85% or more in a wavelength range of 380 to 1500 nm, and
The solar reflectance in the near infrared region of 720 to 1500 nm of the composite molded body in which the surface layer (A) is laminated on the surface of the reflective molded body (B) is 70% or more.

<Surface layer (A)>
The surface layer (A) according to the present invention has a solar absorptance of 90% or more in the wavelength region of 380 to 720 nm, a solar absorptivity of less than 30% in the near infrared region of 720 to 1500 nm, and 720 It is a synthetic resin layer exhibiting a dark color having a solar transmittance of 50% or more in a near infrared region of ˜1500 nm. The synthetic resin used in the present invention is not particularly limited, and examples thereof include polyvinyl chloride resins, polyolefin resins, acrylic resins, polyurethane resins, and thermoplastic elastomer resins made of these resins. 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 reflective molded object (B) mentioned later from a viewpoint of adhesiveness and recyclability. As described above, when the surface layer (A) and the reflection molded body (B) are made of the same synthetic resin, those having excellent adhesion can be obtained without providing an adhesive layer. Moreover, when the surface layer (A) and the reflection molded body (B) are made of the same synthetic resin as described above, it is advantageous in that recycling can be performed without separating the laminated ones.

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

  When a polyvinyl chloride resin is used as such a synthetic resin, such a polyvinyl chloride resin may be a vinyl chloride monomer homopolymer, a vinyl chloride monomer such as a vinyl chloride monomer and a vinyl acetate monomer, or an acrylonitrile monomer. Copolymers with monomers copolymerizable with 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-type resin as such a synthetic resin, you may add a plasticizer to the said compounding composition further. As such a 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 (DBP), diundecyl phthalate (DUP), butyl benzyl phthalate (BBP), etc .; phthalate ester plasticizers such as trioctyl trimellitate (TOTM); dioctyl adipate Fatty acid ester plasticizers such as (DOA), 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.

  In addition, when using a polyvinyl chloride resin as such a synthetic resin, it is preferable to add a stabilizer used in an ordinary polyvinyl chloride resin as necessary to the blended composition. Specifically, metal stabilizers such as Ba—Zn, Ca—Zn, and zinc oxide can be used in a wide range. Furthermore, UV absorbers and antioxidants such as hindered amine compounds, benzotriazole compounds, benzothiazole compounds, etc. may be added to the above blended composition, and in order to improve processability, it is reduced. Various additives such as a thickener and a thickener may be added.

  When a polyurethane resin is used as such a 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 such a polyurethane resin. For example, a polyester polyurethane Polyether polyurethane, polycaprolactone polyurethane, polyester / polyether copolymer polyurethane, polyamino acid / polyurethane copolymer resin, or a mixture thereof can be used.

  In addition, when using a polyurethane-based resin as such a synthetic resin, it is preferable to use a polyurethane-based resin with particularly good light resistance, particularly from the viewpoint that it is used for exposure to direct sunlight, In particular, a non-yellowing polycarbonate-based polyurethane obtained by reacting a polycarbonate 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, aliphatic diisocyanate, alicyclic diisocyanate, 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 polymerized in this way is a normal 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, dimethylsulfoxide, N-methylpyrrolidone, dioxane, cyclohexanone, or a mixture thereof, and used as a polyurethane solution.

Furthermore, when using a polyurethane-based resin as such a synthetic resin, various additives such as an antioxidant, a light stabilizer, an antistatic agent and a flame retardant are further added to the blended composition as necessary. May be.

  When a thermoplastic elastomer resin is used as such a synthetic resin, an olefin thermoplastic elastomer (so-called TPO) is particularly preferably used as such a thermoplastic elastomer 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.

  Moreover, when using a thermoplastic elastomer-based resin as such a synthetic resin, various additives such as an antioxidant, a light stabilizer, an antistatic agent, a flame retardant and the like are further added to the blended composition as necessary. It may be added.

  The surface layer (A) according to the present invention is a layer that absorbs light in the visible light region to exhibit a dark color and transmits light in the near infrared region at a high rate. That is, such a surface layer (A) needs to have a solar absorptivity of 90% or more in a visible light region of 380 to 720 nm. Thus, since the surface layer (A) has a solar absorptance of 90% or more in the visible light range of 380 to 720 nm, the composite molded body of the present invention can substantially absorb light that can be sensed by humans. It is dark and does not feel dazzling.

  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 720 to 1500 nm. When the solar absorptance is 30% or more, the surface layer (A) absorbs the incident light before reaching the reflection molded body (B), and the reflected light reflected by the reflection molded body (B) is reflected. Since the surface layer (A) absorbs before reaching the outside of the surface layer (A), the composite molded body will eventually store heat.

  Furthermore, the solar radiation transmittance of such a surface layer (A) needs to be 50% or more in the near infrared region of 720 to 1500 nm. That is, in order to maintain the solar radiation absorption rate of less than 30% in the near infrared region of 720 to 1500 nm, it is necessary to reflect or transmit the light in the near infrared region, but when trying to reflect the light in the near infrared region. In addition, since some of the visible light region of 380 to 720 nm also exhibits reflectivity, it is difficult to obtain a dark color. Therefore, in the present invention, it is necessary that the solar radiation transmittance of such a surface layer (A) be 50% or more in the near infrared region of 720 to 1500 nm.

In addition, the solar radiation absorptivity, solar radiation transmittance, and solar radiation reflectance (hereinafter, these are collectively referred to as solar radiation characteristics) of the surface layer (A) can be measured by the following method. That is, first, a single-layer sheet composed of the surface layer (A) is used as a sample, and using a self-recording spectrophotometer, the alumina white substrate is set to 100% reflectance, 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 0.05 to 0.5 mm, and more preferably in the range of 0.1 to 0.5 mm. When 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 exhibit 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 composite molded body tends to be hindered.

  The surface layer (A) according to the present invention may contain, in addition to the above-described synthetic resin and various additives, a special pigment that transmits light in the near infrared region as described below. As such special pigments that transmit light in the near infrared region, for example, azo, anthraquinone, phthalocyanine, perinone / perylene, indigo / thioindigo, dioxane, quinacridone, isoinnoridone, isoindoline , Diketopyrrolopyrrole, azomethine, and azomethine azo pigments. Among these special pigments, azo-based, azomethine azo-based, and perylene-based pigments are particularly preferable from the viewpoint of a balance between 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 not to be dark in the visible light region, whereas if it exceeds 5 parts by weight, the near infrared region of the composite molded product obtained by increasing the amount of solar radiation in the near infrared region. Light reflection performance tends to be impaired.

  In addition, the compounding composition for forming such a surface layer (A) is obtained by mixing each component mentioned above homogeneously with a mixing stirrer, such as a dissolver mixer, after measuring. Further, such a blended composition may be filtered for the purpose of removing undispersed materials, or may be degassed under reduced pressure to remove bubbles, if necessary.

<Reflection molding (B)>
The reflection molded body (B) according to the present invention is a synthetic resin molded body having a solar reflectance of 85% or more in a wavelength region of 380 to 1500 nm. The synthetic resin used in the present invention is not particularly limited, and examples thereof include polyvinyl chloride resins, polyolefin resins, acrylic resins, polyurethane resins, and thermoplastic elastomer resins made of these resins. Among these synthetic resins, polyolefin resins, polyvinyl chloride resins, polyurethane resins, and thermoplastic elastomer resins are preferable from the viewpoint of light resistance and moldability.

  When a polyolefin-based resin is used as such a synthetic resin, such a polyolefin-based resin includes low-density polyethylene such as linear linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, ethylene-propylene copolymer. Polyolefins such as copolymers; Ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers and esterified products thereof, ethylene-vinyl acetate copolymers, olefin-vinyl compound copolymers such as ethylene-vinyl alcohol copolymers These graft copolymers, block copolymers, and random copolymers can also be used. These resins can be used singly or in combination of two or more.

  When a polyvinyl chloride resin, a polyurethane resin, or a thermoplastic elastomer resin is used as such a synthetic resin, the same resin as that constituting the surface layer (A) is used.

  And the reflective molded object (B) concerning this invention can be formed using the compounding composition containing such a synthetic resin, for example. The compounding composition for molding such a reflective molded body (B) contains the synthetic resin and can be molded by a molding method such as injection molding, blow molding, compression molding, rotational molding, spray molding or the like. I just need it. Moreover, in such a compounding composition, a plasticizer, a stabilizer, a thinning agent, a thickener, and a compounding composition used for forming the surface layer (A) described above, if necessary, Various additives such as antioxidants, light stabilizers, anti-static agents, flame retardants and the like may be added.

  In the reflection molded body (B) according to the present invention, the solar reflectance in the wavelength region of 380 to 1500 nm is required to be 85% or more. Such a reflection molded body (B) has a solar reflectance of 85% or more in the wavelength range of 380 to 1500 nm, so that the light transmitted through the surface layer (A) is reflected at a high rate. A near-infrared light reflection performance can be imparted to the body. Therefore, according to the present invention, a composite molded body having excellent heat reflection performance 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. In order to improve the near-infrared region light reflection performance, it is necessary that not only the near-infrared region but also the solar reflectance in the wavelength region of 380 to 720 nm is high. For example, when the solar reflectance in the wavelength region of 380 to 720 nm is low (for example, less than 50%), the solar radiation absorption rate in the near infrared region of 720 to 1500 nm is increased (for example, 85% or more). It is difficult. Further, when such a reflection molded body (B) has a high solar reflectance in the wavelength range of 380 to 720 nm, the reflection molded body reflects light in the visible light region that could not be absorbed by the surface layer (A). And can be absorbed again by the surface layer (A), so that a composite molded body exhibiting a hue with a very dark color can be obtained. In addition, the solar radiation characteristic of such a reflective molded object (B) can be measured by the method similar to the measuring method of the solar radiation characteristic of the surface layer (A) mentioned above.

  The reflection molded body (B) according to the present invention may contain a pigment described below in addition to the above-described synthetic resin and various additives. An example of such a pigment is a titanium oxide white pigment. As such a titanium oxide-based white pigment, any of rutile type and anatase type titanium oxides can be used, but rutile type titanium oxide is preferred. Furthermore, the primary particle diameter of such titanium oxide is preferably in the range of 200 nm to 1000 nm. Further, the amount of such white pigment added is preferably in the range of 5 to 70 parts by weight, more preferably in the range of 10 to 20 parts by weight with respect to 100 parts by weight of the synthetic resin. If the addition amount is less than the lower limit, the solar reflection performance may be insufficient. On the other hand, if the addition amount exceeds the upper limit, the increase in the solar reflection effect is not recognized so much. Problems may occur in physical properties. In addition, you may mix | blend such a titanium oxide type white pigment in the toner state previously disperse | distributed to the plasticizer etc.

  Moreover, it is preferable that the reflective molded object (B) concerning this invention has a foam structure. When the reflection molded body (B) has a foamed structure as described above, the refractive index of light becomes large, the reflectance can be further improved, and impact resistance performance can be imparted or reduced in weight. Is also possible. As a method of developing such a foam structure, a method of containing a filler such as a hollow glass balloon or a microcapsule, a method of foaming a synthetic resin with a chemical foaming agent, a method of mechanically mixing bubbles in the resin ( Mechanical foaming) can be employed.

  Thus, when adopting a method of containing a filler such as a hollow glass balloon or a microcapsule as a method of developing a foamed structure, the particle diameter of such a filler is preferably in the range of 1 to 150 μm. The range of 5 to 100 μm is more preferable, and the range of 8 to 80 μm is particularly preferable. When the particle diameter exceeds 150 μm, the workability during preparation of the composition or molding tends to deteriorate. On the other hand, even when a composition of less than 1 μm is used, a desired solar reflection effect is obtained by addition of a filler. Tend to be difficult.

  Furthermore, the addition amount of such a filler is preferably in the range of 3 to 20 parts by weight, and more preferably in the range of 5 to 15 parts by weight with respect to 100 parts by weight of the synthetic resin. If the addition amount is less than the lower limit, it tends to be difficult to ensure a sufficient solar reflection effect. On the other hand, even if the addition exceeds the upper limit, the increase in the solar reflection effect is not recognized so much. Problems tend to occur in the mechanical properties of Moreover, when using a hollow glass balloon as a filler, a glass composition, specific gravity (hollow rate), etc. are not restrict | limited in particular, In order to improve close_contact | adherence with a resin component, you may perform various coupling processes. Furthermore, when microcapsules are used as the filler, there is no particular limitation on the shell composition, and heat expandable or already expanded types can be used, and hollow or bead type can be used. You can also.

  As described above, when a method of foaming a synthetic resin with a chemical foaming agent or a method of mechanically mixing bubbles in the resin is adopted as a method of developing a foam structure, the foaming ratio is in the range of 2 to 30 times. It is preferable to do.

  Furthermore, the reflection molded body (B) according to the present invention may further have a woven fabric, a nonwoven fabric or a resin layer on the surface thereof. These woven fabrics, non-woven fabrics, or resin layers may be any material that does not adversely affect the visible light absorption performance or near-infrared region light reflection performance of the reflective molded body (B), and the material is not particularly limited. Furthermore, the reflection molded body (B) according to the present invention may further have a core material. The material of such a core material is not particularly limited, and examples thereof include metals such as aluminum, iron, gold, silver, and copper; and plastics such as ABS, polyethylene, and polypropylene. Such a core material may be hollow.

<Dark color composite molding>
The dark composite molded product of the present invention is a composite molded product in which the surface layer (A) described above is laminated on the surface of the reflective molded product (B) described above.

  As described above, various methods can be selected as a method of laminating the surface layer (A) on the surface of the reflective molded body (B). For example, (i) after forming a sheet-like material composed of the surface layer (A), the sheet-like material is brought into close contact with the mold, and then the raw material of the reflective molded body (B) is injected into the mold. A method using so-called sheet-in-mold molding, (ii) First, a blended composition for forming the surface layer (A) is put into a heated mold having the shape of a reflective molded body (B), and the mold A method of injecting the raw material of the reflection molded body (B) into the mold after the surface layer (A) formed in a specific shape is formed on the surface of the mold, and the surface layer (A) is then placed on the mold. ) After applying the compounding composition for forming the surface layer (A) to the mold coated with the release agent, the so-called integral skin is used in which the raw material of the reflective molded body (B) is injected into the mold. (Iv) after heating the reflective molded body (B), the raw material of the surface layer (A) (V) A method of forming a cured film on the surface of the reflective molded body (B), (v) Curing after applying the composition for forming the surface layer (A) on the surface of the reflective molded body (B) Caulking, a method of forming a cured film on the surface of the reflective molded body (B), (vi) forming a sheet-like material comprising the surface layer (A), and forming the sheet-like material into the shape of the reflective molded body (B). It is possible to employ a method of sewing and covering so as to fit. Moreover, in laminating the surface layer (A) on the surface of the reflection molded body (B) as described above, an adhesive may be used as necessary. Such an adhesive is not particularly limited as long as it does not adversely affect the visible light absorption performance or near infrared region light reflection performance of the composite molded body. Further, the thickness of the layer made of such an adhesive is not particularly limited as long as it does not adversely affect the visible light absorption performance or the near infrared region light reflection performance of the composite molded body.

  By laminating the surface layer (A) on the reflection molded body (B) by these techniques, the solar light has a high reflectance in the near infrared region contributing to heat generation among the wavelengths constituting the entire sunlight, and the visible light region. When the surface layer (A) has a high absorptance, a composite molded article having a dark color and not dazzling for humans is obtained.

  The dark composite molded article of the present invention can be used for vehicle interior materials such as instrument panels for vehicles, door trims, glove boxes, and bench seats for stations, bus stops, airfields, baseball fields, soccer fields, etc. It can be used as a structure such as furniture.

  In the dark composite molded article of the present invention, an antifouling layer may be provided on the outermost surface as necessary. The antifouling layer is applied with an antifouling paint composed of a solvent-based, water-based or ultraviolet curable coating in consideration of not adversely affecting the visible light absorption performance or near-infrared light 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 dark color composite molded object of this invention, in order to provide the designability to the said surface layer (A), you may give uneven | corrugated embossing. Such embossing can adopt the same technique as embossing performed when obtaining synthetic leather, such as embossing roll processing or release paper.

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 1: “PSH-23” manufactured by Kaneka Corporation
Thermoplastic olefin elastomer resin 1: “Miralastomer N-8030” manufactured by Mitsui Chemicals, Inc.
Urethane resin 1: "Rezamin NE-8875" manufactured by Dainichi Seika Kogyo Co., Ltd.
Polypropylene resin 1: “Prime Polypro J105G” manufactured by Prime Polymer Co., Ltd.
Plasticizer: Diisononylphthalate, Sekisui Chemical Co., Ltd. Stabilizer 1: Asahi Denka Kogyo "AC-183"
Stabilizer 2: “AO-60” manufactured by Asahi Denka Kogyo Co., Ltd.
Filler 1: Hollow glass balloon, “Cell Star Z27” manufactured by Asahi Glass Co., Ltd.
Filler 2: Ceramic balloon, Taiheiyo Cement "E-SPHERES"
Foaming agent 1: Chemical foaming agent, “Uniform AZ” manufactured by Otsuka Chemical Co., Ltd.
Pigment 1: Titanium oxide white pigment, “JR600A” manufactured by Teika Co., Ltd.
Pigment 2: Titanium oxide white pigment, “JR1000” manufactured by Teika Co., Ltd.
Pigment 3: Brown pigment: “Brown FT-9000” manufactured by Fuji Dyeing Co., Ltd.
Pigment 4: Black pigment: “DPF-T-7939” manufactured by Resino Color Industries
Pigment 5: Black pigment: “Pariogen Black S0084” manufactured by BASF AG
Pigment 6: Black pigment: “Black FT-10” manufactured by Special Color Industries Co., Ltd.
Pigment 7: Black pigment: “ARCTIC Black 10C909” manufactured by Shepherd Japan
Pigment 8: Black pigment: “ARCTIC Black 411” manufactured by Shepherd Japan.

(Preparation examples and production examples)
(I) Preparation of paste-like plastisol and molding composition Resin, pigment, filler and various additives are mixed so as to have the compositions shown in Table 1, respectively, and paste-like plastisol and molding composition are mixed. Was made.

  That is, for surface layer (A1 to A7) molding, emulsion-polymerized polyvinyl chloride (manufactured by Kaneka Chemical Industry Co., Ltd., trade name “PSH-23”), filler, pigment, plasticizer (diisononyl phthalate) and thermal stability Each agent was blended so as to have a composition as shown in Table 1, and uniformly mixed with a dissolver mixer to prepare a pasty plastisol.

  In addition, for molding the surface layer (A8 and A9), an olefin-based thermoplastic elastomer (manufactured by Mitsui Chemicals, Inc., trade name “Miralastomer N-8030”), a stabilizer (antioxidant) and a pigment are shown in Table 1. A molding composition was prepared by dry blending so as to obtain the composition as described in 1.

  Furthermore, for molding of the surface layer (A10), a urethane resin (trade name “Rezamine NE-8875” manufactured by Dainichi Seika Kogyo Co., Ltd.), which is a polymer of polycarbonate diol and isocyanate, is used as a solvent. In addition, after that, the filler and the pigment were blended so as to have the compositions shown in Table 1, respectively, and mixed uniformly with a dissolver mixer to prepare a molding composition.

  Further, for the reflection molding (B1 to B5), a filler, a pigment, a foaming agent, and a heat stabilizer are listed in Table 2 for polypropylene resin (manufactured by Prime Polymer Co., Ltd., trade name “Prime Polypro J105G”). A molding composition was prepared by dry blending so as to obtain the composition as described above.

(II) Preparation of surface layer sheet and evaluation of solar radiation characteristics In order to evaluate the solar radiation characteristics of the surface layer (A), single layer sheets of the surface layers (A1 to A10) were prepared as follows. And the solar radiation characteristics (solar radiation absorption rate, solar radiation transmittance, solar radiation reflectance) of the obtained surface layer sheet were evaluated as shown below.

(I) Production of surface layer sheet The surface layer (A1 to A7) obtained in the preparation example was formed on a release paper by a knife coating method so that the paste-like plastisol for molding had a thickness as shown in Table 1, respectively. And heated at 140 ° C. for 2 minutes and then at 195 ° C. for 3 minutes. Then, it cooled and peeled release paper and produced each single layer sheet of the surface layer (A1-A7).

  Further, the composition for molding the surface layer (A8 and A9) obtained in the preparation example was extruded with a T-die extruder so as to have a thickness as shown in Table 1, and the surface layer (A8 and A9). Each single layer sheet was prepared.

  Further, the surface layer (A10) molding composition obtained in the preparation example was coated on the release paper by a knife coating method so as to have a thickness as shown in Table 1, and heated with hot air at 80 ° C. Dried. Then, it cooled and peeled release paper and produced the single layer sheet of the surface layer (A10). In addition, Table 3 shows the hues of the obtained single layer sheets of the surface layers (A1 to A10).

(Ii) Evaluation of solar radiation characteristics The solar radiation characteristics (solar absorption rate, solar transmittance, solar reflectance) of the single-layer sheet of the surface layers (A1 to A10) obtained in the production examples were evaluated by the method as described above. As a self-recording spectrophotometer, “U-4000” manufactured by Hitachi, Ltd. was used. Moreover, about the single layer sheet | seat of a surface layer (A1-A10), the solar radiation absorptivity in the wavelength range of 380-720 nm, the solar radiation transmittance, and the solar reflectance, and the solar radiation absorption factor in the wavelength region of 720-1500 nm, solar radiation transmittance And solar reflectance was evaluated. The obtained results are shown in Table 3.

Example 1
First, after placing the single layer sheet of the surface layer (A1) obtained in the production example in a mold, the single layer sheet was brought into close contact with the mold by evacuation. Then, using the injection molding machine (product made from Engel), the composition for reflection shaping | molding body (B1) shaping | molding obtained by the preparation example was inject | poured and shape | molded in the shaping | molding die, and the composite molding was obtained. The surface hue of the composite molded body obtained in Example 1 is shown in Table 5.

(Examples 2-4, Comparative Examples 1-8)
Except for using the single-layer sheet of the surface layer (A1) and the composition for forming the reflective molded body (B1) obtained in Preparation Examples and Preparation Examples, respectively, as shown in Table 5 and Table 6, respectively. A composite molded body was obtained in the same manner as in Example 1. The surface hues of the composite molded bodies obtained in Examples 2 to 4 and Comparative Examples 1 to 8 are shown in Table 5 and Table 6, respectively.

<Evaluation of solar radiation characteristics, heat reflection performance and glare of composite molded body>
(I) Evaluation Method The solar radiation characteristics, heat reflection performance and glare of the composite molded body and the solar radiation characteristics of the reflective molded bodies (B1 to B5) constituting the composite molded body were evaluated by the following methods.

(I) Evaluation of solar radiation characteristics The solar radiation characteristics of the reflection molded bodies (B1 to B5) were evaluated as follows. That is, the surface layer (A) was removed from the composite molded bodies obtained in Examples and Comparative Examples, and the surface of the reflective molded bodies (B1 to B5) was exposed as a sample, and the solar radiation characteristics of the single-layer sheet Evaluation was performed by the same method as the evaluation method.

  Moreover, the solar radiation characteristic of the composite molded body was evaluated by the same method as the evaluation method of the solar radiation characteristics in a single-layer sheet, using the composite molded bodies obtained in Examples and Comparative Examples as samples.

(Ii) Evaluation of heat reflection performance (sunlight exposure temperature rise test)
The composite molded bodies obtained in the examples and comparative examples were used as samples, and the rise in surface temperature when the samples were exposed to sunlight was measured. That is, a sample is placed on the bottom surface of a box (height 150 mm, width 240 mm, length 340 mm) made of expanded polystyrene having a thickness of 30 mm, and a soda glass plate having a thickness of 1.5 mm is placed on the top surface of the box. The sample was exposed to sunlight on a sunny day in August in Kanto, while measuring the temperature of the sample surface inside the box with a thermocouple. Thereafter, the temperature rise of the sample surface was observed, and the difference between the temperature at which the rise temperature became constant and the temperature in the shade at that time was recorded as ΔT (° C.).

(iii) Evaluation of dazzlingness Whether the composite molded products obtained in the examples and comparative examples are installed at an angle of 45 degrees, and the composite molded products are observed with the naked eye from a distance of 1 m under fine weather, and do you feel glare? Whether or not 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.

(II) Evaluation results The solar radiation characteristics, heat reflection performance and glare of the composite molded bodies obtained in Examples 1 to 4 and Comparative Examples 1 to 8 were evaluated. In addition, about the solar radiation characteristic, the solar radiation absorptivity in the wavelength range of 380-720 nm, solar radiation transmittance, and solar reflectance, and the solar radiation absorption factor, solar radiation transmittance, and solar reflectance in the wavelength range of 720-1500 nm were evaluated. The obtained results are shown in Table 5 and Table 6, respectively. Moreover, the solar radiation characteristic of the reflective molded object (B1-B5) which comprises a composite molded object was evaluated. Table 4 shows the obtained results.

  As is apparent from the results shown in Tables 5 and 6, in the dark color composite molded bodies (Examples 1 to 4) of the present invention, the surface layer (A) has a large absorption of light in the visible light region, so it is dazzling. In addition, since the reflection of light in the near-infrared region of the composite molded body was large, it was confirmed that the surface temperature of the composite molded body was little increased when exposed to sunlight.

  On the other hand, in the composite molded bodies obtained in Comparative Examples 1 and 8, a normal carbon black black pigment is used for the surface layer (A), and the light in the near infrared region as well as the visible light region is high. It was confirmed that the surface temperature of the composite molded body would increase when exposed to sunlight.

  Moreover, in the composite molded bodies obtained in Comparative Examples 2 and 5, the surface layer (A) absorbs light in the visible light region and transmits light in the near infrared region at a high rate, but the reflective layer (B). Since the reflectance of the surface layer (A) is not sufficient, the light transmitted through the surface layer (A) cannot be effectively reflected, and as a result, the surface temperature of the composite molded body increases when exposed to sunlight. confirmed.

  Furthermore, in the composite molded body obtained in Comparative Example 3, the surface layer (A) slightly absorbs light in the visible light region, so that the glare is somewhat reduced. It was confirmed that the surface temperature of the molded body increased.

  Moreover, in the composite molded body obtained in Comparative Example 4, the surface layer (A) has a high solar reflectance, so that the temperature rise when exposed to sunlight is kept low. Since it is reflected at a high rate, it was confirmed to be dazzling.

  Furthermore, in the composite molded bodies obtained in Comparative Examples 6 and 7, the surface layer (A) reflects light in the near infrared region at a relatively high rate, but sufficiently suppresses absorption of light in the near infrared region. Therefore, it was confirmed that the surface temperature of the composite molded body would increase when exposed to sunlight.

  As described above, according to the present invention, it has a solar absorptivity of 90% or more in the visible light region of 380 to 720 nm, and sufficiently suppresses an increase in surface temperature when exposed to sunlight. It is possible to provide a dark color composite molded body capable of achieving the above.

Claims (4)

A synthetic resin composite molded body comprising a surface layer (A) that receives solar radiation and a reflective molded body (B),
The surface layer (A) contains 100 parts by weight of a synthetic resin and 1 to 5 parts by weight of at least one pigment selected from the group consisting of an azo pigment, an azomethine azo pigment, and a perylene pigment, It has a solar absorptance of 90% or more in the wavelength region of 720 nm, a solar absorptivity of less than 30% in the near infrared region of 720 to 1500 nm, and a solar transmittance of 50% or more in the near infrared region of 720 to 1500 nm. A synthetic resin layer exhibiting a dark color
The reflection molded body (B) is a synthetic resin molded body having a solar reflectance of 90% or more in a wavelength region of 380 to 1500 nm, and
Near-infrared region light reflection, wherein the composite molded body obtained by laminating the surface layer (A) on the surface of the reflective molded body (B) has a solar reflectance in the near infrared region of 720 to 1500 nm of 70% or more. A dark composite molded article having performance.   2. The dark composite according to claim 1, wherein the surface layer (A) comprises at least one synthetic resin selected from the group consisting of a polyvinyl chloride resin, a polyurethane resin, and a thermoplastic elastomer resin. Molded body. 3. The dark composite molded article according to claim 1, wherein the reflective molded article (B) contains 100 parts by weight of a synthetic resin and 5 to 70 parts by weight of a titanium oxide-based white pigment. The dark composite molded article according to any one of claims 1 to 3 , wherein the reflective molded article (B) has a foamed structure.