JP2019038175A - Exterior member and window frame using the same - Google Patents

Abstract

To provide an exterior member having a material containing a vinyl chloride resin as a main component, which suppresses deformation by heat due to sunlight while having a sufficient dark color degree.SOLUTION: An exterior member is formed by laminating a decorative sheet having a dark color layer on a colored base material and a resin adherend containing a vinyl chloride resin as a main component so that a surface of a colored base material side and a resin adherend face each other with reference to the dark color layer of the decorative sheet, where in the exterior member, an L*value of an Labcolor system of CIE (Commission Internationale de l'Eclairage) measured according to JIS Z8781-4:2013 on a surface of a decorative sheet side is 35 or less, and a surface temperature when being irradiated with reference sunlight satisfies a specific condition.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an exterior member and a window frame using the same.

For exteriors of buildings such as walls and windows, a decorative member (exterior member) is proposed in which a metal member such as a steel plate, a resin member, and a wooden member are used as adherends, and a decorative sheet is bonded thereto.
In particular, many exterior members made of a molded product such as a window frame have been proposed which are mainly composed of a vinyl chloride resin such as polyvinyl chloride resin (Patent Documents 1 and 2).

However, the upper limit temperature of the heat resistance of the vinyl chloride resin is about 70 ° C. For this reason, the exterior member mainly composed of a vinyl chloride resin may be deformed due to solar heat. In particular, the exterior member of the window frame is easily deformed because it is easily irradiated with sunlight. Furthermore, the dark-colored exterior member tends to be deformed because it tends to have a high heat storage property.
For the purpose of solving the above problems, for example, the technique of Patent Document 3 has been proposed.

JP 2002-3675 A JP 2002-194160 A Japanese Patent No. 4741364

  Patent Document 3 is a laminate including a layer having a woodgrain pattern on a base material, the laminate including 0.5 to 13% by mass of an inorganic pigment having infrared reflection characteristics in the layer having a woodgrain pattern. Is disclosed.

The laminated body of Patent Document 3 uses an inorganic pigment having infrared reflection characteristics in order to reduce heat storage and to impart a color and woodgrain pattern similar to wood. However, the exterior member may be required to give a high-grade feeling by increasing the darkness, and with the addition amount of the inorganic pigment of Patent Document 3, the darkness cannot be sufficiently increased and a high-grade feeling is given. Can not.
On the other hand, Patent Document 3 also describes that carbon black is added to adjust the dark color, but carbon black (carbon particles) has high near-infrared absorptance contained in sunlight and is absorbed. Near-infrared rays are converted into heat. Therefore, when carbon black is added, the effect which suppresses the deformation | transformation resulting from sunlight of an exterior member will be impaired significantly.

  The present invention has been made under such circumstances, and in an exterior member provided with a material mainly composed of a vinyl chloride resin, it has sufficient darkness and is due to heat caused by sunlight. It is an object of the present invention to provide an exterior member that suppresses deformation and a window frame using the exterior member.

In order to solve the above problems, the present invention provides the following [1] to [2].
[1] A decorative sheet having a dark color layer on a colored base material, and a resin adherend comprising a vinyl chloride resin as a main component, and the surface of the colored base material side with respect to the dark color layer of the decorative sheet; An exterior member formed by laminating so as to face the resin adherend,
The exterior member has a CIE (International Lighting Commission) L ^* a ^* b ^* color system L ^* value of 35 or less as measured in accordance with JIS Z8781-4: 2013 on the surface of the decorative sheet side. An exterior member that satisfies the following condition (1).
<Condition (1)>
A sample in which a heat insulating material having a thermal conductivity of 0.028 W / (m · K) or less, a heat shielding material having an average spectral reflectance of a wavelength of 780 to 2500 nm of 75% or more, and the exterior member are prepared in this order. . In the sample, the exterior member is disposed such that the surface on the adherend side faces the heat shield material.
Solar simulator that irradiates AM1.5G standard sunlight for temperate areas specified in IEC-60904-3 (IEC-60904-9 spectrum matching degree “A”, time variation rate “A”, irradiance unevenness of location Using “A”), the reference sunlight is irradiated from 300 mm above the sample to the surface on the exterior member side of the sample so that the integrated energy value per hour becomes 4.05 MJ / m ^2. To do. The surface temperature on the exterior member side of the sample at the start of irradiation of the reference sunlight is 25 ° C. The surface temperature within 90 minutes after irradiation with the reference sunlight always shows 70 ° C. or lower.
[2] A window frame formed from the exterior member according to [1].

  ADVANTAGE OF THE INVENTION According to this invention, the exterior member provided with the material which has a vinyl chloride resin as a main component can suppress the deformation | transformation by the heat | fever which causes sunlight, having sufficient darkness.

It is sectional drawing which shows one Embodiment of the member for exterior | packing of this invention. It is sectional drawing which shows other embodiment of the member for exterior | packing of this invention. It is an example of the schematic diagram explaining the state which measures the surface temperature of the member for exteriors of conditions (1). It is a graph which shows the surface temperature of the exterior member for every time when the reference sunlight is irradiated to the sample produced from the exterior member of Example 1. It is a graph which shows the surface temperature of the exterior member for every time when the reference sunlight is irradiated to the sample produced from the exterior member of Example 2. It is a graph which shows the surface temperature of the exterior member for every time when the reference sunlight is irradiated to the sample produced from the exterior member of Example 3. It is a graph which shows the surface temperature of the exterior member for every time when the reference sunlight is irradiated to the sample produced from the exterior member of Example 4. It is a graph which shows the surface temperature of the exterior member for every time when the reference sunlight is irradiated to the sample produced from the exterior member of Comparative Examples 1-2.

[Decorative sheet]
The exterior member of the present invention includes a decorative sheet having a dark color layer on a colored substrate, and a resin adherend mainly composed of a vinyl chloride resin, wherein the colored group is based on the dark color layer of the decorative sheet. It is an exterior member formed by laminating the material side surface and the resin adherend so as to face each other,
The exterior member has a CIE (International Lighting Commission) L ^* a ^* b ^* color system L ^* value of 35 or less as measured in accordance with JIS Z8781-4: 2013 on the surface of the decorative sheet side. In addition, the following condition (1) is satisfied.
<Condition (1)>
A sample in which a heat insulating material having a thermal conductivity of 0.028 W / (m · K) or less, a heat shielding material having an average spectral reflectance of a wavelength of 780 to 2500 nm of 75% or more, and the exterior member are prepared in this order. . In the sample, the exterior member is disposed such that the surface on the adherend side faces the heat shield material.
Solar simulator that irradiates AM1.5G standard sunlight for temperate areas specified in IEC-60904-3 (IEC-60904-9 spectrum matching degree “A”, time variation rate “A”, irradiance unevenness of location Using “A”), the reference sunlight is irradiated from 300 mm above the sample to the surface on the exterior member side of the sample so that the integrated energy value per hour becomes 4.05 MJ / m ^2. To do. The surface temperature on the exterior member side of the sample at the start of irradiation of the reference sunlight is 25 ° C. The surface temperature within 90 minutes after irradiation with the reference sunlight always shows 70 ° C. or lower.

1 and 2 are sectional views showing an embodiment of the exterior member 100.
1-2, the exterior member 100 includes a decorative sheet 10 having a dark color layer 12 on a colored substrate 11, and a resin adherend 20 mainly composed of a vinyl chloride resin, and the dark color layer of the decorative sheet 10. With reference to 12, the surface of the colored substrate 11 and the resin adherend 20 are laminated so as to face each other.
Further, the decorative sheet 10 of FIG. 2 has a transparent resin layer 13 and a surface protective layer 14 on the dark color layer 12.

<Physical properties of exterior members>
<< L ^* value >>
The exterior member of the present invention has a CIE (International Lighting Commission) L ^* a ^* b ^* color system L ^* value of 35 or less, measured in accordance with JIS Z8781-4: 2013 on the surface on the decorative sheet side. It is necessary to be.
When the L ^* value exceeds 35, the dark color is not sufficient, and a high-class feeling cannot be imparted to the exterior member. The L ^* value is preferably 32 or less, and more preferably 30 or less.
L ^* lower limit value is not particularly limited, the L ^* value is too low, when the irregularities given to the surface of the exterior member, there is a tendency that the unevenness becomes difficult to recognize. For this reason, the L ^* value is preferably 18 or more, and more preferably 20 or more.

The L ^* value is measured from the surface of the exterior member on the decorative sheet side. That is, when the exterior member 100 has the structure of FIG. 1, the measurement is performed on the surface of the dark color layer 12, and when the exterior member 100 has the structure of FIG. 2, the measurement is performed on the surface of the surface protective layer 14.
In addition, the light incident angle at the time of measurement shall be 5 degree | times (The perpendicular with respect to the surface at the side of the decorative sheet of an exterior member is set to 0 degree, and the light inclined 5 degree | times from this perpendicular is made into incident light.).

<< Condition (1) >>
The exterior member of the present invention is required to satisfy the above condition (1). When the condition (1) is not satisfied, deformation due to heat caused by sunlight of the exterior member including the vinyl chloride resin cannot be suppressed.

FIG. 3 is a schematic diagram for explaining a state in which the surface temperature of the exterior member (100) is measured. Specifically, the surface temperature of the exterior member under the condition (1) can be measured as follows.
In measuring the surface temperature of the exterior member in the condition (1), first, the heat insulating material (200) having a thermal conductivity of 0.028 W / (m · K) or less, the average of the spectral reflectances at wavelengths of 780 to 2500 nm is calculated. A sample (500) in which 75% or more of the heat shielding material (300) and the exterior member (100) are laminated in this order is produced. In addition, in the sample (500), it arrange | positions so that the surface by the side of the resin adherend (20) of the exterior member (100) may face the heat shield (300) side. The heat insulating material (200), the heat shielding material (300), and the exterior member (100) may be in close contact with each other through an adhesive or the like, but may simply be overlapped.
As shown in FIG. 3, when the area of the exterior member 100 is smaller than the area of the heat shield 300, the reflector 400 is placed on the surface of the heat shield 300 that is not covered by the exterior member 100. It is preferable that the heat shield 300 is not directly exposed to the reference sunlight.
Next, using the solar simulator (600), the integrated energy value per hour is 4.05 MJ / m ² from 300 mm above the sample (500) to the surface on the exterior member (100) side of the sample. Irradiate standard sunlight. As the solar simulator (500), a solar simulator that irradiates AM1.5G standard sunlight for the temperate region defined by IEC-60904-3 (IEC-60904-9 spectrum match degree “A”, time variation rate “ A ”, irradiance location unevenness“ A ”). In addition, the surface temperature of the sample (500) on the exterior member (100) side at the start of reference sunlight irradiation is set to 25 ° C.
Next, the surface temperature on the exterior member (100) side of the sample (500) is measured for 90 minutes after irradiation with the reference sunlight. If the surface temperature is always 70 ° C. or lower for 90 minutes, the condition (1) is satisfied.
The energy integrated value of 4.05 MJ / m ² per hour is based on the annual maximum illuminance per hour in Minamidaito Island, Okinawa Prefecture.

  In condition (1), it is preferable that the surface temperature of the exterior member within 90 minutes after irradiation with the reference sunlight always shows 65 ° C. or lower.

  As the heat insulating material and the heat shielding material, those having an area equal to or larger than the area of the exterior member are used in order to cover the entire back surface of the exterior member. Further, in order to prevent the exterior member from being heated from the surroundings, the heat insulating material and the heat shielding material are of a size that covers the entire effective irradiation area of the solar simulator.

As the heat insulating material, one having a thermal conductivity of 0.028 W / (m · K) or less is used. Moreover, it is preferable that a heat insulating material is the A class extrusion method polystyrene foam heat insulating board which satisfy | fills the specification of 3 types b of JIS A9511: 2009.
The thickness of a heat insulating material is not specifically limited, It is about 20-100 mm.

As the heat shielding material, a material having an average spectral reflectance of 75% or more at a wavelength of 780 to 2500 nm is used. The average spectral reflectance of the heat shielding material at a wavelength of 780 to 2500 nm is preferably 78% or more, and more preferably 80% or more.
The structure of the heat shield is not particularly limited, but is preferably a structure having metal films on both surfaces, and more preferably a structure having an intermediate layer containing air between the metal films on both surfaces. The metal constituting the metal film of the heat shielding material is not particularly limited, but it is preferable to use aluminum which is inexpensive.
The light incident angle at the time of measuring the spectral reflectance of the heat shield is 5 degrees (the perpendicular to the surface of the heat shield is 0 degrees, and the light inclined by 5 degrees from the perpendicular is the incident light). The spectral reflectance of the heat shielding material shall be measured according to JIS K5602: 2008. The measurement of the spectral reflectance of the reflective material described later is based on the measurement of the spectral reflectance of the heat shielding material.

As for the reflective material installed as needed, it is preferable that the average of the spectral reflectance of wavelength 780-2500 nm is 70% or more. The average of the spectral reflectance of the reflective material having a wavelength of 780 to 2500 nm is more preferably 75% or more, and further preferably 80% or more.
The configuration of the reflecting material is not particularly limited, but a configuration having a metal film on the surface is preferable. Although the metal which comprises the metal film of a reflecting material is not specifically limited, It is preferable to use the low price aluminum.

Moreover, when measuring condition (1), it shall carry out by the open system which is the conditions equivalent to the outdoors. The room temperature during measurement is 25 ° C.
In addition, in order to prevent the reference sunlight reflected on the surface of the sample from being reflected by members around the measurement environment and re-entering the sample, the inside of the space connecting the solar simulator 600 and the sample 500 (one point in FIG. 3). It is preferable not to install anything other than temperature measurement equipment (for example, a thermocouple or a member for fixing the thermocouple) in the chain line). Moreover, it is preferable not to install anything other than the device for temperature measurement also in the area | region within 3 cm of the front and back of the said space, and right and left.

<< Spectral reflectance >>
For the exterior member, in order to easily satisfy the condition (1), when the light incident surface is on the decorative sheet side, the average spectral reflectance of wavelengths 780 to 2500 nm measured in accordance with JIS K5602: 2008 is 65. % Or more is preferable, and 67% or more is more preferable.

<Coating sheet>
A decorative sheet consists of a structure which has a dark color layer on a coloring base material.

<< Colored substrate >>
What is used as a base material of a decorative sheet can be employ | adopted as a coloring base material without a restriction | limiting. Examples of such a colored substrate include those containing a binder resin and a colorant.

As the binder resin, polyolefin resins such as polypropylene and polyethylene, polyester resins, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter also referred to as “ABS resins”), thermoplastic resins such as acrylic resins and vinyl chloride resins are suitable. Used for.
Among these, polyolefin resins, polyester resins, polycarbonate resins, and ABS resins are preferable from the viewpoint of obtaining superior surface characteristics such as weather resistance and scratch resistance. In this invention, these resin can be used individually or in combination of multiple types.

  The polyolefin resin is not particularly limited. For example, polyethylene (low density, medium density, high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate. Examples thereof include a copolymer, an ethylene-acrylic acid copolymer, an ethylene-propylene-butene copolymer, and a polyolefin-based thermoplastic elastomer. Among these, polyethylene (low density, medium density, high density), polypropylene, ethylene-propylene copolymer, and propylene-butene copolymer are preferable from the viewpoint of obtaining superior surface properties such as weather resistance and scratch resistance.

  The colored substrate may be transparent or opaque, but is preferably opaque in order to prevent sunlight from reaching the resin adherend comprising a vinyl chloride resin as a main component. .

Examples of the colorant used for the coloring substrate include white pigments such as titanium oxide, inorganic pigments such as iron black, yellow lead, petal, cadmium red, ultramarine, and cobalt blue; quinacridone red, isoindolinone yellow, and phthalocyanine. Organic pigments or dyes such as blue; metal pigments composed of scaly foils such as aluminum, silver, and brass; coloring of pearlescent pigments composed of scaly foils such as titanium dioxide-coated mica and basic lead carbonate Agents.
Among these, when the surface hue of the resin adherend to which the decorative sheet is stuck varies, white pigments and metal pigments that are easy to conceal the surface hue and have excellent sunlight reflection characteristics are preferable. Among white pigments and metal pigments, titanium oxide and aluminum are preferable in that they have excellent near-infrared (light with a wavelength of 780 to 2500 nm) reflection characteristics and can easily satisfy the condition (1). In particular, titanium oxide is preferable in that it hardly damages the hue of the dark color layer. That is, the colored substrate is preferably a substrate containing a white pigment and / or a metal pigment, more preferably a substrate containing titanium oxide and / or aluminum, and a substrate containing titanium oxide. Is more preferable.

  The content of the colorant in the colored substrate is preferably 1 part by mass or more with respect to 100 parts by mass of the resin constituting the colored substrate from the viewpoint of improving the concealment degree and from the viewpoint of sunlight reflection characteristics. More preferably, it is 3 mass parts or more, More preferably, it is 5 mass parts or more. Further, from the viewpoint of moldability of the exterior member, the upper limit is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, still more preferably 30 parts by mass or less, and still more preferably 20 parts by mass or less.

  An additive may be mix | blended with the coloring base material as needed. Examples of the additive include flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, antioxidants, ultraviolet absorbers, and light stabilizers. There is no restriction | limiting in particular in the compounding quantity of an additive, According to a required characteristic etc., it can set suitably.

  When the colored base material is an exterior member, it is a layer located between the dark color layer and the resin adherend, so that the weather resistance decreases due to bleeding out of weathering agents such as ultraviolet absorbers and light stabilizers. It can be said that the influence on is small compared to other layers. For this reason, it is useful to include a weathering agent such as an ultraviolet absorber or a light stabilizer in the colored substrate.

There is no restriction | limiting in particular as an ultraviolet absorber used for a coloring base material, For example, a benzotriazole type ultraviolet absorber, a benzophenone type ultraviolet absorber, a triazine type ultraviolet absorber, etc. are mentioned.
As the light stabilizer, for example, a hindered amine light stabilizer is preferable, and among them, a reactive group-containing hindered amine light stabilizer having a functional group that is an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, or an allyl group. Is preferred.

  The content of the ultraviolet absorber in the colored substrate is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and still more preferably 0.8 parts by mass with respect to 100 parts by mass of the resin constituting the colored substrate. The upper limit is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and still more preferably 2 parts by mass or less. The content of the light stabilizer in the colored substrate is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and further preferably 3 parts by mass with respect to 100 parts by mass of the resin constituting the colored substrate. The upper limit is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and still more preferably 6 parts by mass or less. When the content of the ultraviolet absorber and the light stabilizer in the substrate is within the above range, bleeding out is difficult and an excellent additive effect is obtained.

The colored substrate may have a single layer structure or a multilayer structure having two or more of the same or different layers.
The thickness of the colored substrate is preferably 20 μm or more, more preferably 30 μm or more, and even more preferably 40 μm or more, from the viewpoint of the balance between handleability and strength. As an upper limit, 200 micrometers or less are preferable, 160 micrometers or less are more preferable, and 100 micrometers or less are further more preferable.

The colored substrate is oxidized on one or both sides for the purpose of improving the adhesion with other layers constituting the decorative sheet such as a dark color layer or for enhancing the adhesion to the resin adherend. A surface treatment such as a physical surface treatment such as a method or a roughening method, or a chemical surface treatment can be performed.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment method, and the like. Examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected according to the type of the colored substrate, but generally, a corona discharge treatment method is preferably used from the viewpoint of the effect of surface treatment and operability.
In addition, in order to improve interlayer adhesion between the colored substrate and other layers, and to enhance adhesion to the resin adherend, a treatment such as forming a primer layer and a back primer layer on the colored substrate is performed. May be. These primer layers will be described later.

<< dark color layer >>
The dark color layer is formed on the colored substrate. In the present invention, the dark color means a chromatic color or an achromatic color having an L ^* value of the L ^* a ^* b ^* color system defined by the CIE of 35 or less. For example, dark gray, dark green, dark blue, black, dark It is a low-lightness, low-colored, dark-colored color such as purple, red oil, or brown.
The dark color layer may be composed of a single layer or may be composed of two or more layers of the same kind or different kinds.

As long as the L ^* value of the exterior member can be 35 or less, the dark color layer may be, for example, a colored layer (so-called solid colored layer) covering the entire surface, or a pattern layer having various patterns. It may be a combination thereof.
As a preferred embodiment of the present invention, as described later, an azomethine azo pigment, a perylene pigment, or manganese described in International Publication WO2016 / 125906A1 is essential as a colorant for the dark layer, and titanium, calcium, and By including a composite oxide containing at least one kind of total two or more metal elements selected from bismuth, it is possible to obtain a form that has good near-infrared reflection characteristics as a member for an outer casing while being a dark color system. is there. In order to easily obtain an effect based on such a form, the dark color layer preferably has at least a solid colored layer.

As the dark colorant, one that can be used alone or in combination of two or more to make the L ^* value of the exterior member 35 or less is selected as the first condition. However, even if the colorant can reduce the L ^* value of the exterior member to 35 or less, for example, carbon black, which is a typical example of a dark colorant, absorbs near-infrared rays and uses a vinyl chloride resin. Some of them make it easier to deform the exterior member.
For this reason, as the dark colorant, one satisfying the condition (1) by mixing two or more kinds alone is selected as the second condition. That is, the dark colorant in the present invention preferably includes those having a low near-infrared absorptivity and having near-infrared reflection characteristics or near-infrared transmission characteristics.

Examples of the dark colorant having near infrared transmission characteristics include azomethine azo pigments and perylene pigments. In addition, when using the dark colorant which has a near-infrared transmission characteristic, it is preferable to use the coloring base material (coloring base material which is excellent in the reflection characteristic of a near infrared ray) containing a titanium oxide and / or aluminum.
On the other hand, as a dark colorant having near-infrared reflection characteristics, manganese described in WO2016 / 125906A1 is essential, and a composite oxide containing at least one metal element other than manganese is included therein. .
Among dark colorants having near-infrared reflection characteristics or near-infrared transmission characteristics, azomethine azo pigments and perylene pigments that have a low near-infrared absorptivity and easily satisfy the condition (1) even when used in a large amount are preferable. The azomethine azo pigments and perylene pigments are excellent in the balance between realizing darkening and satisfying the condition (1). That is, the dark color layer preferably contains at least one selected from azomethine azo pigments and perylene pigments.

The azomethine azo pigment has a diazonium group which is a reaction compound of tetrachlorophthalimide and aminoaniline.
The perylene pigment is a pigment having a structure in which two oxygen atoms constituting the six-membered ring of perylenetetracarboxylic dianhydride are removed, and examples include perylene black.

The specific composite oxide is an oxide containing at least two kinds of metal elements. The composite oxide is preferably a composite oxide containing at least manganese, that is, an oxide containing manganese and at least one metal element other than manganese. The metal elements other than manganese contained in the composite oxide are not particularly limited, and can be appropriately selected from the viewpoint of obtaining a calm design with lower brightness, the viewpoint of obtaining heat shielding performance, and the like.
One kind of metal element other than manganese contained in the composite oxide may be used alone, or a combination of two or more kinds may be used. Examples of metal elements other than manganese contained in the composite oxide include Group 2 elements such as calcium and barium; Group 3 elements such as yttrium, lanthanum, and praseodymium; Group 3 elements such as neodymium; and Group 4 elements such as titanium and zirconium; Examples include Group 13 elements such as boron, aluminum, gallium, and indium; and metal elements such as Group 15 elements such as antimony and bismuth. Among these, a Group 2 element, a Group 4 element, and a Group 15 element are preferable, calcium, titanium, and bismuth are more preferable, and calcium and titanium are more preferable. As a particularly preferable specific example of the composite oxide, a composite oxide containing manganese, calcium, and titanium can be given.
The structure of the complex oxide is not particularly limited, but from the viewpoint of being stable as a structure, obtaining excellent heat shielding performance and design, etc., a perovskite structure, an orthorhombic structure, a hexagonal structure, etc. And a perovskite structure is more preferable.

The average particle diameter of the colorant is preferably 0.1 μm or more, and more preferably 0.2 μm or more, from the viewpoint of increasing the absorbability in the visible light region. The upper limit of the average particle size of the colorant is not particularly limited, but is preferably 3.0 μm or less, more preferably 2.0 μm or less, from the viewpoint of making the design of the dark color layer delicate. More preferably, it is 1.0 μm or less.
In addition, in this specification, an average particle diameter is a value which can be calculated | required as the mass average value D50 in the particle size distribution measurement by a laser beam diffraction method.

The content of the dark colorant is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and more preferably 20 to 40% by mass based on the total solids constituting the dark color layer. Further preferred. The colorant is preferably at least one selected from azomethine azo pigments and perylene pigments.
By setting the content of the dark colorant to 10% by mass or more, the reflectance of near-infrared rays (light having a wavelength of 780 to 2500 nm) can be increased and the condition (1) can be easily satisfied. Moreover, the fall of the coating strength of a dark color layer can be suppressed by making content of the coloring agent in a dark color layer 50 mass% or less, and the moldability of the exterior member can be made favorable.
As the colorant in the dark color layer, it may contain a colorant other than the dark colorant having near-infrared reflection characteristics and near-infrared transmission characteristics, but from the viewpoint of easily exerting the effects of the present invention, The ratio of the dark colorant having the near-infrared reflection property and the near-infrared transmission property in the total amount of the colorant in the dark color layer is preferably 25% by mass or more, more preferably 50% by mass or more, and 75% by mass. % Or more, more preferably 95% by mass or more.

  The binder resin for the dark color layer is not particularly limited. For example, urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, polycarbonate urethane-acrylic copolymer. A polymer (a urethane-acrylic copolymer derived from a polymer having a carbonate bond in the polymer main chain and having two or more hydroxyl groups in the terminal and side chains (polycarbonate polyol)), vinyl chloride-vinyl acetate copolymer resin, Preferred examples include resins such as vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin, and cellulose acetate resin, and these can be used alone or in combination. In addition to the one-component curing type, for example, curing of isocyanate compounds such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPID), xylylene diisocyanate (XDI), etc. Various types of resins, such as a two-component curable type with an agent, can be used.

The dark color layer may contain weathering agents such as an ultraviolet absorber and a light stabilizer from the viewpoint of improving the weather resistance.
As an ultraviolet absorber and a light stabilizer, the ultraviolet absorber and the light stabilizer which were illustrated as what may be contained in a coloring base material can be mentioned. The content of the ultraviolet absorber and the light stabilizer can be exemplified by the same range as the content in the surface protective layer described later from the viewpoint of improving the weather resistance.

The thickness of the dark color layer is preferably 0.5 μm or more, more preferably 1 μm or more, and even more preferably 2 μm or more in order to easily make the L ^* value 35 or less and to easily satisfy the condition (1). Moreover, as an upper limit of a dark color layer, 20 micrometers or less are preferable, 10 micrometers or less are more preferable, and 8 micrometers or less are further more preferable.
It is preferable to have at least one of a transparent resin layer and a protective layer described later on the dark color layer.

<< Adhesive layer >>
The decorative sheet can have an adhesive layer as necessary.
In particular, when the decorative sheet has a transparent resin layer to be described later, it is effective to provide an adhesive layer when improving the interlayer adhesion between the dark color layer and the transparent resin layer. As an adhesive constituting the adhesive layer, an adhesive usually used in a decorative sheet can be used without limitation.

  Examples of the adhesive include urethane adhesives, acrylic adhesives, epoxy adhesives, rubber adhesives, etc. Among them, urethane adhesives are preferable in terms of adhesive strength. As the urethane adhesive, for example, a two-component curable urethane resin containing various polyol compounds such as polyether polyol, polyester polyol, acrylic polyol, and polycarbonate diol, and curing agents such as the above various isocyanate compounds is used. Adhesives. Acrylic-polyester-vinyl acetate resins and the like are also suitable adhesives that can easily exhibit adhesiveness by heating and maintain adhesive strength even when used at high temperatures.

  The thickness of the adhesive layer is preferably 0.1 μm or more, more preferably 1 μm or more, further preferably 2 μm or more, and the upper limit is preferably 20 μm or less, more preferably 10 μm, from the viewpoint of obtaining sufficient adhesiveness. It is as follows.

<< Transparent resin layer >>
In the decorative sheet, it is preferable to laminate a transparent resin layer directly on the dark color layer or via another layer from the viewpoint of protecting the dark color layer and improving surface properties such as weather resistance and scratch resistance.

  Preferred examples of the resin constituting the transparent resin layer include polyolefin resin, polyester resin, acrylic resin, polycarbonate resin, polyurethane resin, polystyrene resin, vinyl chloride resin, vinyl acetate resin, and the like. Among these, from the viewpoint of improving surface properties such as weather resistance and scratch resistance, polyolefin resins and polyester resins are preferable, and polyolefin resins are more preferable. Examples of the polyolefin resin include resins exemplified as those capable of constituting a colored substrate, and a polypropylene resin is particularly preferable.

An additive may be mix | blended with the transparent resin layer as needed, For example, what was illustrated as an additive which can be mix | blended in the said colored base material can be used. Among various additives, it is preferable to use weathering agents such as ultraviolet absorbers and light stabilizers.
As an ultraviolet absorber and a light stabilizer, the ultraviolet absorber and the light stabilizer which were illustrated as what can be used for a coloring base material can be mentioned. Content of these weathering agents can illustrate the same range as content in a colored base material from a viewpoint of an improvement of a weather resistance.

  The thickness of the transparent resin layer is preferably 10 μm or more, more preferably 30 μm or more, and even more preferably 50 μm or more from the viewpoint of improving the surface properties such as protection of the dark color layer, scratch resistance and weather resistance. Further, from the viewpoint of handleability of the exterior member, the upper limit is preferably 150 μm or less, more preferably 120 μm or less, and even more preferably 100 μm or less. Moreover, it is preferable to set it as the thickness more than a base material from a viewpoint of protecting a decoration layer and obtaining the outstanding scratch resistance.

For improving the interlayer adhesion between the transparent resin layer and the other layer, the transparent resin layer has a physical surface treatment such as an oxidation method and a concavo-convex method, or a chemical surface treatment on one or both sides thereof. Etc. can be subjected to surface treatment. As these physical or chemical surface treatments, the same method as the surface treatment of the colored substrate is preferably exemplified.
Moreover, in order to improve the interlayer adhesion between the transparent resin layer and other layers, a treatment such as forming a primer layer on one or both sides of the transparent resin layer may be performed. This primer layer will be described later.

<< surface protective layer >>
From the viewpoint of mainly imparting surface characteristics such as scratch resistance and weather resistance, the decorative sheet is directly on the dark color layer or other layers, for example, an adhesive layer provided as necessary, a transparent resin layer, Or it is preferable to provide a surface protective layer on the primer layer etc. for improving the interlayer adhesiveness of a dark color layer and a surface protective layer.

A surface protective layer is a layer comprised with the hardened | cured material of the resin composition containing curable resin.
As the curable resin used for forming the surface protective layer, an ionizing radiation curable resin or the like is preferably used in addition to a thermosetting resin such as a two-component curable resin. For example, ionization is combined. A so-called hybrid type may be used in which a radiation curable resin and a thermosetting resin are used in combination, or a curable resin and a thermoplastic resin are used in combination.
The curable resin is preferably an ionizing radiation curable resin from the viewpoint of increasing the crosslink density of the resin constituting the surface protective layer and obtaining better surface properties such as scratch resistance and weather resistance, and is easy to handle. From the viewpoint of the above, an electron beam curable resin is more preferable.

(Ionizing radiation curable resin)
The ionizing radiation curable resin is a resin that crosslinks and cures when irradiated with ionizing radiation, and has an ionizing radiation curable functional group. Here, the ionizing radiation curable functional group is a group that crosslinks and cures upon irradiation with ionizing radiation, and preferably includes a functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group. It is done. The ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. Also included are electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams.
Specifically, the ionizing radiation curable resin can be appropriately selected from polymerizable monomers and polymerizable oligomers conventionally used as ionizing radiation curable resins.

As the polymerizable monomer, a (meth) acrylate monomer having a radical polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable. Here, “(meth) acrylate” means “acrylate or methacrylate”.
Examples of the polyfunctional (meth) acrylate monomer include a (meth) acrylate monomer having two or more ionizing radiation-curable functional groups in the molecule and having at least a (meth) acryloyl group as the functional group. From the viewpoint of obtaining superior surface properties such as scratch resistance and weather resistance, an acrylate monomer having an acryloyl group is preferred.
From the viewpoint of obtaining superior surface properties such as scratch resistance and weather resistance, the number of functional groups is preferably 2 or more, and the upper limit is preferably 8 or less, more preferably 6 or less, still more preferably 4 or less, and particularly preferably 3 It is as follows. These polyfunctional (meth) acrylates may be used alone or in combination.

Examples of the polymerizable oligomer include a (meth) acrylate oligomer having two or more ionizing radiation-curable functional groups in the molecule and having at least a (meth) acryloyl group as the functional group. Examples include urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, polyether (meth) acrylate oligomers, polycarbonate (meth) acrylate oligomers, acrylic (meth) acrylate oligomers, and the like.
Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. In a molecule such as an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule, or a novolak epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group.

  These polymerizable oligomers may be used alone or in combination of two or more. From the viewpoint of obtaining better surface properties such as scratch resistance and weather resistance, urethane (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, polyester (meth) acrylate oligomer, polyether (meth) acrylate oligomer, polycarbonate (meth) An acrylate oligomer and an acrylic (meth) acrylate oligomer are preferable, and a urethane (meth) acrylate oligomer and a polycarbonate (meth) acrylate oligomer are more preferable.

  From the viewpoint of obtaining superior surface properties such as scratch resistance and weather resistance, the number of functional groups of these polymerizable oligomers is preferably 2 or more, and preferably 8 or less, more preferably 6 or less, and even more preferably as the upper limit. 4 or less, more preferably 3 or less.

  The weight average molecular weight of these polymerizable oligomers is preferably 2,500 or more, more preferably 3,000 or more, and further preferably 3,500 or more, from the viewpoint of obtaining more excellent surface properties such as scratch resistance and weather resistance. . Moreover, as an upper limit, 15,000 or less are preferable, 12,500 or less are more preferable, and 11,000 or less are still more preferable. Here, the weight average molecular weight is an average molecular weight measured by GPC analysis and converted to standard polystyrene.

  In the ionizing radiation curable resin, a monofunctional (meth) acrylate can be used in combination with the above-mentioned polyfunctional (meth) acrylate and the like for the purpose of reducing the viscosity. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

  The ionizing radiation curable resin preferably contains a polymerizable oligomer from the viewpoint of improving surface properties such as scratch resistance and weather resistance. The content of the polymerizable oligomer in the ionizing radiation curable resin is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and further preferably 100% by mass.

The curable resin composition constituting the surface protective layer preferably contains an ultraviolet absorber. Since the surface protective layer contains the ultraviolet absorber, the ultraviolet absorber is stably held in the surface protective layer, so that excellent weather resistance can be obtained even in a severe environment.
Examples of the UV absorber include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, and triazine-based UV absorbers exemplified as UV absorbers that can be contained in the colored substrate, and triazine-based UV absorbers are preferred. .

  Moreover, it is preferable that the curable resin composition which comprises a surface protective layer contains a light stabilizer from a viewpoint of improving a weather resistance. As the light stabilizer, a hindered amine light stabilizer is preferable, and the hindered amine light stabilizer exemplified as the light stabilizer that can be used for the colored substrate can be used. From the viewpoint of weather resistance, decanedioic acid (sebacic acid) Derived hindered amine light stabilizers are preferred.

  In the surface protective layer, these ultraviolet absorbers and light stabilizers can be used alone or in combination of two or more. Moreover, the ultraviolet absorber and the light stabilizer may have a reactive functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, or an allyl group. Since it becomes difficult to bleed out by the interaction with the curable resin constituting the surface protective layer, it can be used in a larger amount, and more excellent weather resistance can be obtained.

The content of the ultraviolet absorber in the surface protective layer is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, relative to 100 parts by mass of the curable resin constituting the surface protective layer, and 0.3 Part by mass or more is more preferable, and 0.5 part by mass or more is more preferable. Moreover, as an upper limit, 20 mass parts or less are preferable, and 10 mass parts or less are more preferable.
The content of the light stabilizer in the surface protective layer is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the curable resin constituting the surface protective layer, and 1 part by mass. The above is more preferable, and 1.5 parts by mass or more is even more preferable. Moreover, as an upper limit, 10 mass parts or less are preferable, 8 mass parts or less are more preferable, 5 mass parts or less are further more preferable, and 3 mass parts or less are more preferable. When the contents of the ultraviolet absorber and the light stabilizer in the surface protective layer are within the above ranges, an excellent additive effect can be obtained without bleeding out.

  In the surface protective layer, as an additive, within the range that does not impair the object of the present invention, in addition to the above-mentioned ultraviolet absorber and light stabilizer, an ultraviolet shielding agent, an antiwear agent, a polymerization inhibitor, a crosslinking agent, a charge An inhibitor, an adhesion improver, a leveling agent, a thixotropic agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, an antiblocking agent, a lubricant, a solvent, and the like can be added.

  From the viewpoint of improving surface properties such as scratch resistance and weather resistance, the thickness of the surface protective layer is preferably 2 μm or more, more preferably 3 μm or more, and even more preferably 4 μm or more. Further, from the viewpoint of suppressing cracks in the surface protective layer when molding the exterior member, the thickness of the surface protective layer is preferably 15 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less.

<< Primer layer >>
The decorative sheet can be provided with a primer layer as desired. The primer layer is a layer provided mainly for obtaining an effect of improving interlayer adhesion. Further, when the primer layer is provided on the surface of the colored substrate opposite to the surface protective layer side (the primer layer in such a case is also referred to as “back surface primer layer”), the colored substrate. And interlayer adhesion between the resin adherend and the resin adherend can be improved.
The primer layer is disposed between the colored substrate and the dark color layer, between the adhesive layer and the transparent resin layer, between the transparent resin layer and the surface protective layer, and on the side opposite to the dark color layer side of the colored substrate. It can be provided at any one or more locations selected from the following.

For the formation of the primer layer, a resin composition is used in which a binder is appropriately mixed with a curing agent, a weathering agent such as an ultraviolet absorber and a light stabilizer, and an additive such as an antiblocking agent.
As the binder, for example, resins exemplified as the binder that can be used in the dark color layer are preferably exemplified, and these can be used alone or in combination. For example, a mixture of a polycarbonate urethane-acrylic copolymer and an acrylic polyol resin can be used as a binder.

  In addition to the one-component curing type, for example, curing of isocyanate compounds such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPID), xylylene diisocyanate (XDI), etc. Various types of resins, such as a two-component curable type with an agent, can be used.

The primer layer preferably contains a weathering agent such as an ultraviolet absorber and a light stabilizer from the viewpoint of improving the weather resistance. As an ultraviolet absorber and a light stabilizer, what was illustrated as what can be contained in a coloring base material can be mentioned.
The content of the ultraviolet absorber in the primer layer is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and further preferably 10 parts by mass or more with respect to 100 parts by mass of the resin constituting the primer layer. Is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 25 parts by mass or less.
The content of the light stabilizer in the primer layer is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, further preferably 1.5 parts by mass with respect to 100 parts by mass of the resin constituting the primer layer. More preferably, it is 2 parts by mass or more, and the upper limit is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less, and still more preferably 8 parts by mass or less.
When the contents of the ultraviolet absorber and the light stabilizer in the primer layer are within the above ranges, excellent weather resistance is obtained as well as excellent performance as a primer layer.

  The thickness of the primer layer is preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 3 μm or more from the viewpoint of improving the interlayer adhesion and further the effect of reducing the thermal shrinkage of each layer. Moreover, as an upper limit, 10 micrometers or less are preferable, 8 micrometers or less are more preferable, and 6 micrometers or less are further more preferable.

The decorative sheet may have an uneven surface formed by embossing or the like.
When embossing, for example, the decorative sheet is preferably heated to 80 ° C. or higher and 260 ° C. or lower, more preferably 85 ° C. or higher and 160 ° C. or lower, more preferably 100 ° C. or higher and 140 ° C. or lower, and the embossed plate is pressed on the decorative sheet. Thus, embossing can be performed. The location where the embossed plate is pressed is preferably on the dark color layer side with respect to the colored base material of the decorative sheet.

<Resin adherend>
The resin adherend is mainly composed of a vinyl chloride resin. Here, the main component means 50% by mass or more of the total resin constituting the resin adherend, preferably 70% by mass or more, and more preferably 90% by mass or more.
The resin adherend includes a vinyl chloride resin as a main component, and the dark-colored exterior member is usually easily deformed when irradiated with sunlight for a long time. However, the exterior member of the present invention can suppress deformation when it is irradiated with sunlight for a long time by satisfying the condition (1).

As vinyl chloride resin, in addition to vinyl chloride resin (vinyl chloride homopolymer), copolymer containing vinyl chloride (chloroethylene) as a monomer component constituting a copolymer such as vinyl chloride-vinyl acetate copolymer Coalescence is mentioned. However, in the case of a copolymer, a vinyl chloride resin having a vinyl chloride ratio of 50 mol% or more as a monomer component constituting the copolymer is referred to as a vinyl chloride resin.
Examples of resins other than the vinyl chloride resin constituting the resin adherend include acrylic resins, polyester resins, polystyrene resins, polyolefin resins such as polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resins, phenol resins, cellulose resins, etc. Is mentioned.

  What is necessary is just to select suitably the thickness of a resin adherend according to a use and material, 0.1 mm or more and 30 mm or less are preferable, 0.3 mm or more and 20 mm are more preferable, 0.5 mm or more and 10 mm or less are more preferable.

<Adhesive layer>
In order to obtain excellent adhesion, the resin adherend and the decorative sheet are preferably bonded together via an adhesive layer.

It does not specifically limit as an adhesive agent used for an adhesive bond layer, A well-known adhesive agent can be used, For example, adhesive agents, such as a heat sensitive adhesive and a pressure sensitive adhesive, are mentioned preferably. Examples of the resin used for the adhesive constituting the adhesive layer include acrylic resin, polyurethane resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, styrene-acryl copolymer resin, and polyester resin. , Polyamide resins, and the like, and these can be used alone or in combination. Further, a two-component curable polyurethane adhesive or polyester adhesive using an isocyanate compound or the like as a curing agent can also be applied.
An adhesive can also be used for the adhesive layer. As the pressure-sensitive adhesive, an acrylic, urethane, silicone, rubber, or other pressure-sensitive adhesive can be appropriately selected and used.

  Although there is no restriction | limiting in particular in the thickness of an adhesive bond layer, from a viewpoint of obtaining the outstanding adhesiveness, 1 micrometer or more and 100 micrometers or less are preferable, 5 micrometers or more and 50 micrometers or less are more preferable, and 10 micrometers or more and 30 micrometers or less are still more preferable.

<Method for manufacturing exterior member>
The exterior member can be manufactured through a process of laminating a decorative sheet and a resin adherend.
This step is a step of laminating a resin adherend and a decorative sheet, and the surface on the side that requires decoration of the resin adherend and the surface on the colored substrate side facing the dark color layer of the decorative sheet are opposed to each other And stack. Examples of the method of laminating the resin adherend and the decorative sheet include a laminating method in which the decorative sheet is laminated on the plate-shaped resin adherend with a pressure roller via an adhesive layer.

  When a hot melt adhesive (heat sensitive adhesive) is used as the adhesive, the heating temperature is preferably 160 ° C. or higher and 200 ° C. or lower, although it depends on the type of resin constituting the adhesive, and 100 for the reactive hot melt adhesive. It is preferably at least 130 ° C. Moreover, in the case of a vacuum forming process, it is common to carry out with heating, 80 to 130 degreeC is preferable, More preferably, it is 90 to 120 degreeC.

  The exterior member obtained as described above can be used as an exterior member of a building such as a wall, a window, a door, or a handrail, and particularly for a window frame in which heat due to sunlight irradiation is likely to be a problem. It can be suitably used as an exterior member.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.
1. Measurement and Evaluation 1-1. Surface temperature Thermal conductivity 0.028 W / (m · K) or less heat insulating material (Class A extruded polystyrene foam insulation board that satisfies the standards of JIS A9511: 2009, type b. Kaneka Corporation's trade name “Kanelite Foam” "Super E-III" (thickness 25 mm) was cut into a size of 20 cm in length and 20 cm in width. Next, a heat-shielding material having an average spectral reflectance of 80% at wavelengths of 780 to 2500 nm (trade name “ASTROFOIL” of Prairie Homes Co., Ltd. From a configuration having an intermediate layer containing air between aluminum films on both surfaces The heat shielding material) was cut into a size of 22 cm in length and 22 cm in width. Subsequently, the exterior member produced in the example and the comparative example was cut into a length of 9 cm and a width of 4 cm.
The cut heat insulating material, the heat shielding material, and the exterior member are stacked in this order. Further, as shown in FIG. 3, the portion of the surface on the exterior member side of the heat shielding material that is not covered with the exterior member is A sample for measurement was produced by covering with a reflective material (aluminum tape, trade name Monf manufactured by Fudo Kogyo Co., Ltd.) having an average spectral reflectance of 780 to 2500 nm of 87.8%. In the sample, it arrange | positioned so that the surface by the side of the to-be-adhered body of an exterior member might face the heat-shielding material side. Moreover, when the sample was observed from the surface direction, the exterior member was arranged so that the exterior member was positioned at the center of the heat insulating material and the heat shielding material. In addition, a lead wire direct connection type thermocouple for measuring temperature (trade name “TPK-01” of Sato Corporation) was installed on the surface of the exterior member. In order to make the tip of the thermocouple in close contact with the surface of the exterior member, a polyimide tape measuring 2 cm in length and 1 cm in width from the top of the thermocouple (manufactured by ASONE, product number: KS-200055-3, thickness) 0.055 mm) was pressed, and the upper and lower short sides of the tape were fixed with aluminum tape (trade name “monf aluminum tape” by Koto Kogyo Co., Ltd.).
Next, a solar simulator that irradiates AM1.5G standard sunlight for temperate areas as defined by IEC-60904-3 (trade name “XES-155S1” of Mitsunaga Electric Co., Ltd. Spectrum conformance of IEC-60904-9 Using the degree “A”, the time variation rate “A”, and the irradiance unevenness “A”), the integrated energy value per hour is 4. Reference sunlight was irradiated so that it might become 05MJ / m < ² >, and the surface temperature of the exterior member was measured for 90 minutes. The temperature measurement interval was 5 seconds. The surface temperature on the exterior member side of the sample at the start of irradiation with the reference sunlight was set to 25 ° C.
In addition, said measurement was performed by the open system and the room temperature at the time of measurement was 25 degreeC. In addition, in order to prevent the reference sunlight reflected from the surface of the sample from being reflected by members around the measurement environment and re-entering the sample, the interior of the space connecting the solar simulator and the sample, and the front and rear of the space And in the area | region within 3 cm of right and left, nothing was installed except said thermocouple, a polyimide film, and an aluminum tape.
The measurement result of the surface temperature of the exterior member immediately after the irradiation of the reference sunlight is shown in FIGS. 4 shows the first embodiment, FIG. 5 shows the second embodiment, FIG. 6 shows the third embodiment, and FIG. 7 shows the fourth embodiment. FIG. 8 shows Comparative Examples 1 and 2, and Comparative Example 1 shows data that always shows around 75 to 85 ° C. after 30 minutes, and Comparative Example 2 shows the other. Further, Table 1 shows that the surface temperature within 90 minutes after irradiation with the reference sunlight was always 70 ° C. or less, and “C” was that the temperature exceeded 70 ° C. even once.

1-2. Measurement of L ^* value Using a spectrophotometer (trade name: CM-3500d) manufactured by Konica Minolta Holdings, Inc., in accordance with JIS Z8781-4: 2013, CIE (International Lighting Committee) L ^* a ^* b ^* L ^* value of the color system was measured. The results are shown in Table 1.
The L ^* value was measured from the surface of the exterior member on the decorative sheet side. The light incident angle during measurement was 5 degrees, and a D65 light source was used as the light source.

1-3. Spectral reflectance average of wavelengths from 780 to 2500 nm (near infrared) Using a spectrocolorimeter (trade name: CM-3500d) manufactured by Konica Minolta Holdings, Inc., in accordance with JIS K5602: 2008, Examples and Comparative Examples The spectral reflectance of the exterior member at a wavelength of 780 to 2500 nm (near infrared) was measured (measurement wavelength interval was 1 nm), and the average of the spectral reflectance was calculated.
The spectral reflectance was measured from the surface of the exterior member on the decorative sheet side. The light incident angle during measurement was 5 degrees, and a D65 light source was used as the light source.

1-4. Deformation The state of deformation of the exterior member after completion of the test of “1-1” was visually evaluated. As a result, “A” was used for the undeformed and “C” was used for the deformed one.

[Example 1]
A white polypropylene sheet (thickness: 60 μm, containing 10 parts by mass of titanium oxide with respect to 100 parts by mass of random polypropylene resin) is prepared as a coloring substrate, and a primer agent (acrylic urethane resin system) is provided on one surface of the sheet. ) Was used to provide a back primer layer (thickness: 2 μm) by a gravure coating method.

Next, a dark color layer-forming ink 1 having the following formulation was applied to the surface opposite to the surface provided with the back primer layer by a gravure coating method and dried to form a dark color layer having a thickness of 4 μm.
<Dark color layer forming ink 1>
-Binder resin (acrylic urethane resin) 15 parts by mass-Colorant (azomethine azo pigment) 5 parts by mass (average particle size: 0.2 μm, black pigment)
・ Solvent 80 parts by mass (mixed solvent of methyl ethyl ketone, ethyl acetate, butyl acetate and isopropyl alcohol)

Next, an adhesive layer (polyester resin, thickness: 5 μm) is formed on the dark color layer, and a transparent resin layer (transparent polypropylene resin, thickness: 80 μm) is laminated on the adhesive layer by extrusion lamination. did.
Next, the surface of the transparent resin layer was subjected to corona discharge treatment, and then a two-component curable urethane resin composition was applied to form a primer layer (thickness: 2 μm).

Next, a surface protective layer-forming ink having the following formulation was applied onto the primer layer by a roll coating method, and an electron beam was applied using an electron beam irradiation apparatus under the conditions of oxygen concentration: 200 ppm, acceleration voltage: 175 keV, irradiation amount: 5 Mrad. Was irradiated to cure the ionizing radiation curable resin composition to form a surface protective layer having a thickness of 3 μm to obtain a decorative sheet.
<Surface protective layer forming ink>
-Bifunctional urethane acrylate oligomer 80 parts by mass (mass average molecular weight: 1500, glass transition temperature: -55 ° C)
-Hexafunctional aliphatic urethane acrylate oligomer 20 parts by mass (mass average molecular weight: 1500, glass transition temperature: 200 ° C or higher-14 parts by mass of inorganic filler (silica particles, average particle size: 11 µm)

  Next, a surface of the decorative sheet on the back primer layer side and a resin adherend comprising a vinyl chloride resin having a thickness of 2 mm as a main component (white vinyl chloride plate manufactured by Unisunday, product number “EB232-5”, vinyl chloride resin Is bonded together via an adhesive layer (vinyl acetate aqueous emulsion adhesive, thickness: 7 μm) to obtain an exterior member of Example 1.

[Example 2]
An exterior member of Example 2 was obtained in the same manner as in Example 1 except that the colorant of Example 1 was changed to a perylene pigment (perylene black, black pigment).

[Example 3]
5 parts by mass of the colorant of Example 1 was mixed with an azomethine azo pigment (average particle size 0.2 μm) and a composite oxide containing manganese, calcium and titanium as metal elements (product number: MPT-370, manufactured by Ishihara Sangyo Co., Ltd.). , Black pigment, average primary particle diameter 0.8 μm) and the mixture was changed to 5 parts by mass, and the mass ratio of the azomethine azo pigment to the composite oxide was changed to 1: 0.46, the same as in Example 1. Thus, an exterior member of Example 3 was obtained.

[Example 4]
5 parts by mass of the colorant of Example 1 was mixed with 5 parts by mass of an azomethine azo pigment (average particle diameter 0.2 μm), iron oxide (Fe ₂ O ₃ , brown pigment), and copper phthalocyanine blue (blue pigment). The exterior member of Example 4 was changed in the same manner as in Example 1 except that the mass ratio of azomethine azo pigment, iron oxide and copper phthalocyanine blue was 1: 1.16: 1.16. Obtained.

[Comparative Example 1]
An exterior member of Comparative Example 1 was obtained in the same manner as in Example 1 except that the dark layer forming ink 1 was changed to the dark layer forming ink 2 having the following formulation.
<Dark color layer forming ink 2>
・ Binder resin (acrylic urethane resin) 22 parts by mass ・ Colorant (carbon black) 8 parts by mass ・ Solvent 70 parts by mass (mixed solvent of methyl ethyl ketone, ethyl acetate, butyl acetate and isopropyl alcohol)

[Comparative Example 2]
An exterior member of Comparative Example 2 was obtained in the same manner as in Example 1 except that the dark layer forming ink 1 was changed to the dark layer forming ink 3 having the following formulation.
<Dark color layer forming ink 3>
-Binder resin (acrylic urethane resin) 24 parts by mass-Colorant 9 parts by mass (complex oxide containing manganese, calcium and titanium as metal elements)
Ishihara Sangyo Co., Ltd., product number: MPT-370, black pigment)
-Solvent 67 parts by mass (mixed solvent of methyl ethyl ketone, ethyl acetate, butyl acetate and isopropyl alcohol)

From the results in Table 1, the exterior member of the example can suppress deformation due to heat caused by sunlight while lowering L ^* of the exterior member provided with a material mainly composed of vinyl chloride resin. Can be confirmed.

  Since the exterior member of the present invention has sufficient darkness and can suppress deformation due to heat caused by sunlight, it can be used as an exterior member for walls, windows, doors, handrails, fences, fences, insulators, etc. In particular, it is extremely useful as a member for a window frame that is likely to be excessively irradiated with sunlight.

10: decorative sheet 11: colored substrate 12: dark color layer 13: transparent resin layer 14: surface protective layer 20: resin adherend 100: exterior member 200: heat insulating material A
300: Heat insulation material B
400: Reflector 500: Sample 600: Solar simulator

Claims (8)

A decorative sheet having a dark color layer on a colored base material and a resin adherend comprising a vinyl chloride resin as a main component, and the surface of the colored base material side and the resin coating on the basis of the dark color layer of the decorative sheet. It is an exterior member that is laminated so as to face the kimono,
The exterior member has a CIE (International Lighting Commission) L ^* a ^* b ^* color system L ^* value of 35 or less as measured in accordance with JIS Z8781-4: 2013 on the surface of the decorative sheet side. An exterior member that satisfies the following condition (1).
<Condition (1)>
A sample in which a heat insulating material having a thermal conductivity of 0.028 W / (m · K) or less, a heat shielding material having an average spectral reflectance of a wavelength of 780 to 2500 nm of 75% or more, and the exterior member are prepared in this order. . In the sample, the exterior member is disposed such that the surface on the adherend side faces the heat shield material.
Solar simulator that irradiates AM1.5G standard sunlight for temperate areas specified in IEC-60904-3 (IEC-60904-9 spectrum matching degree “A”, time variation rate “A”, irradiance unevenness of location Using “A”), the reference sunlight is irradiated from 300 mm above the sample to the surface on the exterior member side of the sample so that the integrated energy value per hour becomes 4.05 MJ / m ^2. To do. The surface temperature on the exterior member side of the sample at the start of irradiation of the reference sunlight is 25 ° C. The surface temperature within 90 minutes after irradiation with the reference sunlight always shows 70 ° C. or lower.   The average of the spectral reflectance of the wavelength of 780 to 2500 nm of the exterior member measured in accordance with JIS K5602: 2008 when the light incident surface is the decorative sheet side is 65% or more. Exterior member.   The exterior member according to claim 1 or 2, wherein the dark color layer contains at least one selected from azomethine azo pigments and perylene pigments.   The exterior member according to claim 3, wherein the dark color layer contains 10 to 50% by mass of at least one selected from the azomethine azo pigment and the perylene pigment.   The exterior member according to any one of claims 1 to 4, comprising two or more dark color layers.   The exterior member according to claim 1, wherein the colored substrate is a white substrate.   The exterior member according to any one of claims 1 to 6, wherein the decorative sheet has at least one of a transparent resin layer and a protective layer on the dark color layer.   The window frame formed from the member for an exterior of any one of Claims 1-7.