Laminated material for exterior use, and resin sash using the same.

Abstract

To provide an exterior laminate that can be used as an exterior component and has excellent crack prevention properties. [Solution] An exterior laminate 10 is disclosed, having, in order from the surface side, a) a transparent film layer 1 containing an acrylic resin and b) a colored film layer 3 containing a polyvinyl chloride resin, wherein the transparent film layer 1 of a) contains a triazine-based ultraviolet absorber and the colored film layer 3 of b) contains a polyester-based plasticizer having a weight-average molecular weight of 3500 or more. The exterior laminate 10 may have, in order from the surface side, a) a transparent film layer 1 containing an acrylic resin, c) a printed layer 2, and b) a colored film layer 3 containing a polyvinyl chloride resin. Preferably, the printed layer 2 of c) does not contain carbon black.

Description

Technical Field

[0001] The present invention relates to a laminate for exterior use, an exterior member using the laminate for exterior use, and a resin sash using the laminate for exterior use. More specifically, the present invention relates to a laminate for exterior use having excellent crack generation prevention properties, and an exterior member and a resin sash using the same.

Background Art

[0002] Various members used for the exterior that constitutes the appearance of structures such as buildings and automobiles are desired to have high weather resistance, heat insulation properties, and heat shielding properties that can withstand long-term continuous use in addition to having desired designability and design characteristics. A sash, which is an exterior member attached to an opening of a structure, usually consists of a "frame" that serves to attach a window to the structure and a "kamachi" for fitting glass into the frame. Conventionally, metal sashes such as aluminum sashes (so-called aluminum sashes) have been widely spread. In particular, in recent years, resin sashes having a resin frame formed of resin as shown in Patent Document 1 and Patent Document 2, for example, have attracted attention. Resin sashes include not only sashes in which all of the shoji frames and frames are made of resin, but also composite sashes in which resin parts are attached only to the indoor side of metal shoji and frames made of aluminum or the like. Any type of resin sash can ensure higher dew condensation prevention properties and heat insulation properties because its heat conductivity is lower than that of a sash formed only of a metal such as aluminum. Therefore, resin sashes are effective for improving the efficiency of air conditioning and can contribute to energy saving, and thus have high utility value in both warm regions and cold regions.

[0003] To ensure good thermal insulation, weather resistance, and impact resistance, resin window frames are generally manufactured by forming a laminate on a resin base material, which includes a colored film layer containing a semi-rigid polyvinyl chloride resin as a decorative surface, and a layer of acrylic resin on the surface. The polyvinyl chloride resin contributes to high thermal insulation, while the acrylic resin contributes to high weather resistance and impact resistance. Furthermore, the laminate constituting the resin window frame often includes a printed layer to provide design elements such as desired patterns, including coloring.

[0004] As described above, resin sashes typically have a layer of acrylic resin on their surface that provides high weather resistance, and a colored film layer containing polyvinyl chloride resin as a base layer. The colored film layer of polyvinyl chloride resin generally contains a plasticizer that provides flexibility. While resin sashes offer the advantages described above, they also have the disadvantage that when exposed to sunlight (solar radiation) for a long period of time, the plasticizer contained in the colored film layer of polyvinyl chloride resin tends to migrate to the acrylic resin layer, and this migration of plasticizers increases the frequency of crack formation in the acrylic resin layer.

[0005] Therefore, there is a continuous need to develop resin sashes composed of laminates that overcome the shortcomings of conventional resin sashes, specifically those that can sufficiently suppress the migration of plasticizers from the colored film layer of polyvinyl chloride resin to the acrylic resin layer on the surface, and the resulting crack formation in the acrylic resin layer, when exposed to sunlight (solar radiation) over a long period of time. Furthermore, laminates having a decorative surface that can effectively suppress the migration of plasticizers from the colored film layer of polyvinyl chloride resin to the acrylic resin layer on the surface when exposed to sunlight (solar radiation) over a long period of time, and the resulting crack formation in the acrylic resin layer, are not limited to sashes such as resin sashes, but are also widely required for various other exterior components. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 10-238245 [Patent Document 2] Japanese Patent Publication No. 2012-202186 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] Research is still ongoing to overcome the aforementioned shortcomings of laminates that make up exterior components such as resin window frames, but an effective solution has yet to be found. Therefore, the object of the present invention is to provide an exterior laminate that can constitute exterior components such as resin sashes, and that can prevent the migration of plasticizers from the colored film layer of vinyl chloride resin to the acrylic resin layer on the surface side when exposed to sunlight (solar radiation) for a long period of time, and the resulting crack formation in the acrylic resin layer. [Means for solving the problem]

[0008] As a result of diligent research, the inventors have discovered that in an exterior laminate having a transparent film layer containing an acrylic resin and a colored film layer containing a polyvinyl chloride resin, arranged in order from the surface, it is possible to sufficiently suppress the migration of the plasticizer from the colored film layer to the transparent film layer on the surface side, and the resulting crack formation in the transparent film layer, by incorporating a polyester plasticizer having a predetermined weight-average molecular weight range that makes migration to the transparent film layer difficult in the colored film layer containing the polyvinyl chloride resin, and simultaneously incorporating a specific type of ultraviolet absorber capable of suppressing crack formation in the transparent film layer containing the acrylic resin. This has led to the completion of the present invention.

[0009] Accordingly, various aspects and embodiments of the present invention for solving the above problems can be summarized as follows. [1]. Starting from the surface side, a) A transparent film layer containing an acrylic resin, and b) Colored film layer containing polyvinyl chloride resin An exterior laminate having, The transparent film layer in a) contains a triazine-based ultraviolet absorber, The colored film layer of (b) above contains a polyester-based plasticizer having a weight-average molecular weight of 3500 or more. Laminated material for exterior use. [2]. Starting from the surface side, a) A transparent film layer containing acrylic resin, c) Printed layer, and b) Colored film layer containing polyvinyl chloride resin An exterior laminate as described in item [1] above, having the following: [3]. The exterior laminate according to item [2] above, wherein the printed layer in c) does not contain carbon black. [4]. An exterior component using an exterior laminate as described in any one of the above items [1] to [3]. [5]. A resin sash using an exterior laminate as described in any one of the above items [1] to [3]. [Effects of the Invention]

[0010] The exterior laminate of the present invention contains a polyester plasticizer having a weight-average molecular weight within a predetermined range that makes migration from the colored film layer containing a polyvinyl chloride resin to the transparent film layer containing an acrylic resin difficult, and also contains a specific type of ultraviolet absorber that can suppress crack formation in the transparent film layer. As a result, even when exposed to sunlight (solar radiation) for a long period of time, the migration of the plasticizer from the colored film layer to the transparent film layer on the surface side, and the resulting crack formation in the transparent film layer, can be sufficiently suppressed. In addition, the exterior laminate of the present invention can sufficiently suppress crack generation in the transparent film layer, thereby having high weather resistance and enabling high preservation of design and aesthetic properties. Therefore, exterior members such as resin sashes on which the laminate forms the surface can withstand long-term continuous use including large temperature fluctuations.

Brief Description of the Drawings

[0011] [Figure 1] FIG. 1 shows a schematic view of an exterior laminate according to an embodiment of the present invention.

Modes for Carrying Out the Invention

[0012] The exterior laminate according to the present invention has, in order from the surface side, a) a transparent film layer containing an acrylic resin, and b) a colored film layer containing a polyvinyl chloride resin. In one embodiment, the exterior laminate according to the present invention has, in order from the surface side, a) a transparent film layer containing an acrylic resin, c) an optionally provided printing layer, and b) a colored film layer containing a polyvinyl chloride resin. In a further embodiment, the exterior laminate according to the present invention has, in order from the surface side, a) a transparent film layer containing an acrylic resin, c) an optionally provided printing layer, b) a colored film layer containing a polyvinyl chloride resin, and further optionally includes d) a substrate. Hereinafter, each component of the exterior laminate will be described. In this specification, the transparent film layer containing a) an acrylic resin may be simply referred to as the "transparent film layer", and the colored film layer containing b) a polyvinyl chloride resin may be simply referred to as the "colored film layer".

[0013] a) Transparent film layer containing acrylic resin In exterior laminates, the transparent film layer containing acrylic resin provides the laminate with high weather resistance and impact resistance. In exterior laminates, the transparent film layer containing acrylic resin is positioned on the surface side of either the colored film layer containing polyvinyl chloride resin (b) described below, or the printed layer (c) described below. The transparent film layer containing acrylic resin can form the outermost surface of the exterior laminate. In this specification, "surface side" refers to one side of an exterior laminate that is directly exposed to sunlight (radiant heat) when the exterior laminate is actually used for exterior purposes. In this specification, "acrylic resin" refers to both acrylic resin and methacrylic resin. Furthermore, in this specification, "transparent" in a transparent film layer refers to a state in which light from substantially the entire wavelength range of visible light, or light from a portion of the wavelength range of visible light, is transmitted through the transparent film layer, making it possible to see from one side of the transparent film layer to the other. "Transparent" in relation to a transparent film layer includes not only being colorless and transparent, but also being colored and translucent. Therefore, the transparent film layer is not limited to containing colorants or fillers, as long as it satisfies the above definition of "transparent" and does not hinder the desired effects of the present invention. Note that in this specification, when "transparent" is referred to in relation to layers other than the transparent film, it has the same meaning as described herein.

[0014] In one embodiment, the transparent film layer containing the acrylic resin may have a total light transmittance (a value measured using the "NDH2000" turbidimeter from Nippon Denshoku Industries Co., Ltd., in accordance with JIS K7361-1:1997) of preferably 85% or more, more preferably 88% or more, and even more preferably 90% or more.

[0015] Examples of acrylic resins used as materials for transparent film layers are not particularly limited, but include (meth)acrylic acid ester (co)polymers, copolymers mainly containing structural units derived from (meth)acrylic acid esters (usually 50 mol% or more, preferably 65 mol% or more, more preferably 70 mol% or more), and modified versions thereof. (Meth)acrylic means acrylic or methacrylic. (Co)polymer means polymer or copolymer. As acrylic resins used as materials for transparent film layers, one of these resins can be used alone or in the form of any mixture of two or more types.

[0016] Examples of (meth)acrylic acid ester (co)polymers include polymethyl (meth)acrylate, polyethyl (meth)acrylate, polypropyl (meth)acrylate, polybutyl (meth)acrylate, (methyl)acrylate-butyl (meth)acrylate copolymer, and (ethyl)acrylate-butyl (meth)acrylate copolymer. These resins can be used individually or in the form of any mixture of two or more.

[0017] Among (meth)acrylic acid ester (co)polymers used as materials for transparent film layers, methyl (meth)acrylate / butyl (meth)acrylate copolymers are preferred from the viewpoint of providing high weather resistance and impact resistance to the laminate, as well as enhancing the function of suppressing crack generation in the transparent film layer caused by the migration of plasticizer from the colored film layer to the transparent film layer on the surface side. Among methyl (meth)acrylate / butyl (meth)acrylate copolymers, methyl methacrylate / butyl acrylate copolymers are particularly preferred from the above viewpoint.

[0018] Copolymers primarily containing structural units derived from (meth)acrylic acid esters include, for example, ethylene-(meth)acrylate copolymer, styrene-(meth)acrylate copolymer, vinylcyclohexane-(meth)acrylate copolymer, maleic anhydride-(meth)acrylate copolymer, and N-substituted maleimide-(meth)acrylate copolymer. These resins can be used individually or in any mixture of two or more types.

[0019] Examples of the modified polymers mentioned above include polymers in which a lactone ring structure has been introduced by an intramolecular cyclization reaction; polymers in which glutaric acid anhydride has been introduced by an intramolecular cyclization reaction; and polymers in which an imide structure has been introduced by reaction with an imidizing agent (e.g., methylamine, cyclohexylamine, and ammonia, etc.) (referred to as poly(meth)acrylimide resins). These resins can be used individually or in any mixture of two or more types.

[0020] In one embodiment, the acrylic resin used as the material for the transparent film layer may be a vinylcyclohexane-(meth)methyl acrylate copolymer, from the viewpoint of impact resistance, scratch resistance, transparency, moisture resistance, etc. The content of structural units derived from (meth)acrylate in the vinylcyclohexane-(meth)methyl acrylate copolymer may be typically 50 to 95 mol%, preferably 65 to 90 mol%, and more preferably 70 to 85 mol%, with the total amount of structural units derived from the totally polymerizable monomer being 100 mol%. Here, "polymerizable monomer" means (meth)methyl acrylate, vinylcyclohexane, and monomers copolymerizable with these. The copolymerizable monomer is usually a compound having a carbon-carbon double bond, and is typically a compound having an ethylenic double bond. In another embodiment, the acrylic resin used as the material for the transparent film layer may be a poly(meth)acrylimide resin film, from the viewpoint of impact resistance, scratch resistance, transparency, heat resistance, etc.

[0021] The acrylic resin used as the material for the transparent film layer may further contain other resins commonly used in acrylic resin compositions. The proportion of other resins used (if used) is not particularly limited as long as it does not contradict the purpose of the present invention, but the total of the acrylic resin and other resins is typically 0% by mass and 50% by mass or less, preferably 0% by mass and 40% by mass or less, 1% by mass or more and 30% by mass or less, 2% by mass or more and 20% by mass or less, 3% by mass or more and 15% by mass or less, or 3% by mass or more and 10% by mass or less, with the total of the acrylic resin and other resins being 100% by mass.

[0022] In one preferred embodiment, the content of (meth)acrylic acid ester (co)polymers such as methyl (meth)acrylate / butyl (meth)acrylate copolymer in the acrylic resin used as a material for the transparent film layer may be 50% by mass or more, more preferably 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or substantially 100% by mass, based on the total mass of the acrylic resin, from the viewpoint of further improving crack prevention.

[0023] In one embodiment, the acrylic resin used as the material for the transparent film layer may contain a core-shell rubber as another resin. Examples of core-shell rubbers include methacrylate ester / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / ethylene / propylene rubber graft copolymer, acrylonitrile / styrene / acrylic acid ester graft copolymer, methacrylate ester / acrylic acid ester rubber graft copolymer, and methacrylate ester / acrylonitrile / acrylic acid ester rubber graft copolymer. One or more of these can be used as the core-shell rubber. Further examples of resins other than acrylic resins that can be used as materials for transparent film layers include ethylene vinyl acetate copolymers.

[0024] The transparent film layer containing the acrylic resin preferably contains a triazine-based ultraviolet absorber. By including such a triazine-based UV absorber in the transparent film layer, crack formation in the transparent film layer caused by the migration of plasticizer from the colored film layer to the transparent film layer on the surface can be effectively prevented.

[0025] The transparent film layer containing the acrylic resin may preferably contain 0.1% by mass or more of a triazine-based ultraviolet absorber relative to the total mass of the layer. By ensuring that the amount of triazine-based ultraviolet absorber contained in the transparent film layer containing the acrylic resin is above the above lower limit, a sufficient effect can be achieved to prevent crack formation in the transparent film layer caused by the migration of plasticizer from the colored film layer to the transparent film layer on the surface side. From this viewpoint, the content of the triazine-based ultraviolet absorber in the transparent film layer may more preferably be 0.3% by mass or more, 0.5% by mass or more, 1.0% by mass or more, or 1.5% by mass or more, relative to the total mass of the layer. The upper limit of the content of triazine-based ultraviolet absorbers in a transparent film layer containing acrylic resin is not particularly limited, but from the viewpoint of film formation and manufacturing costs, it may be, for example, 5% by mass or less relative to the total mass of the layer.

[0026] The transparent film layer may optionally contain other components besides resin components such as acrylic resins and triazine-based ultraviolet absorbers, to the extent that it does not contradict the objectives of the present invention. Examples of such optional components include light stabilizers, flame retardants, photopolymerization initiators, antistatic agents, surfactants, leveling agents, thixotropic agents, antifouling agents, printability improvers, antioxidants, weather-resistant stabilizers, heat stabilizers, pigments, and fillers. The amount of the optional components (if used) is not particularly limited, but is usually about 0.01 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the total amount of the acrylic resin forming the transparent film layer and the other resins. It is permissible to include small amounts of pigments or colorants in the transparent film layer, but these should not hinder transparency or the desired effects of the present invention, and it is desirable to avoid the use of pigments such as carbon black, which have high heat absorption and heat storage properties.

[0027] As a light stabilizer, for example, hindered amine-based light stabilizers are preferably used. Among these, radical polymerizable light stabilizers having a radically polymerizable double bond in the molecule are preferred. Using a triazine-based UV absorber in combination with a light stabilizer is a preferred embodiment because it can improve the weather resistance of an exterior laminate containing a transparent film layer.

[0028] The transparent film layer containing the acrylic resin may be a single layer or a laminate of multiple layers. If the transparent film layer containing the acrylic resin is a laminate of multiple layers, it may consist of multiple layers having the same composition, or it may consist of multiple layers, some of which have different compositions. Furthermore, the transparent film layer containing the acrylic resin may be an unoriented film, a uniaxially oriented film, or a biaxially oriented film. If the transparent film layer containing the acrylic resin is a laminate of multiple layers, it may be formed from a combination of two or more of the unoriented film, uniaxially oriented film, and biaxially oriented film.

[0029] The method for manufacturing a transparent film layer containing an acrylic resin using the materials described above is not particularly limited. Examples of methods for obtaining a transparent film layer include using an apparatus equipped with a calender roll rolling machine and a winding machine, and using an apparatus equipped with an extruder, a T-die, and a winding machine. Examples of calender roll rolling machines include upright 3-roll, upright 4-roll, L-type 4-roll, inverted L-type 4-roll, and Z-type roll. Examples of extruders include single-screw extruders, co-rotating twin-screw extruders, and opposite-rotating twin-screw extruders. Examples of T-dies include manifold dies, fishtail dies, and coat hanger dies.

[0030] The thickness of the transparent film layer containing the acrylic resin (total thickness if it consists of multiple layers) is not particularly limited, but from the viewpoint of balancing the provision of high weather resistance, impact resistance, and crack prevention with manufacturing costs and ease of handling, it may be, for example, 5 μm or more and 1000 μm or less. This thickness is preferably 8 μm or more, 10 μm or more, 20 μm or more, 30 μm or more, or 40 μm or more, and / or 800 μm or less, 600 μm or less, 500 μm or less, 400 μm or less, 300 μm or less, 200 μm or less, 100 μm or less, or 80 μm or less.

[0031] b) Colored film layer containing polyvinyl chloride resin In exterior laminates, the colored film layer containing polyvinyl chloride resin has the function of providing high heat insulation to the laminate. The colored film layer containing polyvinyl chloride resin forms the base for the transparent film layer containing acrylic resin, which is positioned closer to the surface in the exterior laminate. Furthermore, if the printed layer described in c) below is provided, the colored film layer containing polyvinyl chloride resin forms the base for the printed layer, which is positioned closer to the surface in the exterior laminate. The coloring of the colored film layer is primarily achieved through the use of pigments and colorants.

[0032] Examples of polyvinyl chloride resins used as materials for colored film layers containing polyvinyl chloride resins include polyvinyl chloride (polyvinyl chloride homopolymer); vinyl chloride-vinyl acetate copolymer, vinyl chloride-(meth)acrylic acid copolymer, vinyl chloride-methyl (meth)acrylate copolymer, vinyl chloride-(meth)acrylate copolymer, polyvinyl chloride-ethyl (meth)acrylate copolymer, vinyl chloride-maleic acid copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile terpolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-various vinyl ether copolymers, and other vinyl chloride copolymers of vinyl chloride and other monomers copolymerizable with vinyl chloride; and modified (chlorinated, etc.) polyvinyl chloride or vinyl chloride copolymers such as post-chlorinated vinyl copolymers. Furthermore, chlorinated polyolefins, such as chlorinated polyethylene, which have a chemical structure similar to polyvinyl chloride, may also be used. Such chlorinated polyolefins with a chemical structure similar to polyvinyl chloride are also considered to fall under the category of "polyvinyl chloride resins" that constitute the colored film layer containing the polyvinyl chloride resin. One or more of these can be used as the polyvinyl chloride resin.

[0033] The polyvinyl chloride resin used as a material for a colored film layer containing a polyvinyl chloride resin may further contain other resins commonly used in polyvinyl chloride resin compositions. The proportion of other resins used (if used) is not particularly limited as long as it does not contradict the purpose of the present invention, but the total of the polyvinyl chloride resin and other resins is taken as 100% by mass, and is usually greater than 0% by mass and 40% by mass or less, preferably greater than 0% by mass and 30% by mass or less, 1% by mass or more and 25% by mass or less, 2% by mass or more and 20% by mass or less, 3% by mass or more and 15% by mass or less, or 3% by mass or more and 10% by mass or less.

[0034] Other resins besides polyvinyl chloride resins that can be used as materials for the colored film layer include, for example, ethylene-vinyl acetate copolymer; ethylene-(meth)acrylic acid copolymer; ethylene-methyl (meth)acrylate copolymer; ethylene-ethyl (meth)acrylate copolymer; (meth)acrylic acid ester-alkyl acrylate copolymer; methacrylic acid ester-styrene / butadiene rubber graft copolymer; acrylonitrile-styrene / butadiene rubber graft copolymer; acrylonitrile-styrene / ethylene-propylene rubber graft copolymer; acrylonitrile-styrene / acrylic acid ester graft copolymer; methacrylic acid ester / acrylic acid ester rubber graft copolymer; methacrylic acid ester-acrylonitrile / acrylic acid ester rubber graft copolymer, and other core-shell rubbers. As for other resins, one or more of these can be used.

[0035] The colored film layer containing polyvinyl chloride resin contains a polyester-based plasticizer having a weight-average molecular weight of 3500 or more. By including a polyester-based plasticizer having a weight-average molecular weight above the lower limit mentioned above in the colored film layer, the migration of the plasticizer from the colored film layer to the transparent film layer on the surface side is effectively suppressed. Consequently, in combination with the effect brought about by the inclusion of a triazine-based ultraviolet absorber in the transparent film layer, crack formation in the transparent film layer can be more effectively prevented. Such polyester-based plasticizers having a weight-average molecular weight within a specific range may be used alone or in a mixture of two or more types.

[0036] From the viewpoint of enhancing the above effects, the weight-average molecular weight of the polyester plasticizer contained in the colored film layer containing polyvinyl chloride resin is preferably 3600 or more, more preferably 3700 or more, 3800 or more, 3900 or more, 4000 or more, or 5000 or more. The upper limit of the weight-average molecular weight of the polyester plasticizer is not particularly limited, but may be 10000 or less.

[0037] In this specification, the weight-average molecular weight (Mw) of polyester plasticizers can be measured as the weight-average molecular weight in terms of polystyrene using gel permeation chromatography (hereinafter sometimes abbreviated as "GPC") by the following method. GPC measurements are performed using Tosoh Corporation's high-performance liquid chromatography system "HLC-8320" (product name) (a system including a degasser, liquid transfer pump, autosampler, column oven, and RI (differential refractive index) detector); four GPC columns in total: two Shodex GPC columns "KF-806L" (product name), one "KF-802" (product name), and one "KF-801" (product name), connected in the order of KF-806L, KF-806L, KF-802, and KF-801 from upstream; and tetrahydrofuran for high-performance liquid chromatography (without stabilizers) from Fujifilm Wako Pure Chemical Industries, Ltd. as the mobile phase; under the conditions of a flow rate of 1.0 ml / min, column temperature of 40°C, sample concentration of 1 ml / ml, and sample injection volume of 100 microliters. The elution amount at each retention volume can be determined from the detection amount of the RI detector, assuming that there is no molecular weight dependence of the refractive index of the sample being measured. Furthermore, calibration curves from retention capacity to polystyrene-equivalent molecular weight can be created using Agilent Technologies, Inc.'s standard polystyrene "EasiCal PS-1" (product name) (Plain A molecular weights: 6,375,000, 573,000, 117,000, 31,500, 3480; Plain B molecular weights: 2,517,000, 270,600, 71,800, 10,750, 705). The analysis program can be the "TOSOH HLC-8320GPC EcoSEC" (product name) from Tosoh Corporation. For the theory and practical aspects of GPC, reference books such as "Size Exclusion Chromatography: High-Performance Liquid Chromatography of Polymers" by Kyoritsu Shuppan Co., Ltd., author: Sadao Mori, 1st edition, 1st printing, December 10, 1991, can be consulted.

[0038] Examples of polyester-based plasticizer structures are not particularly limited, but include those using polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, and neopentyl glycol, and polyhydric carboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, trimellitic acid, pimelic acid, suberic acid, maleic acid, azelaic acid, sebacic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid, and using monohydric alcohols and monocarboxylic acids as stoppers as needed. Among these, a preferred example is a polyester-based plasticizer which is a polymer of 1,4-butanediol and 2,2-dimethyl-1,3-propanediol with adipic acid.

[0039] Furthermore, the colored film layer containing the polyvinyl chloride resin may further contain plasticizers other than polyester plasticizers having the weight-average molecular weight within the specified range, which are commonly used in polyvinyl chloride resin compositions, in an amount that does not interfere with the desired effects achieved by the exterior laminate according to the present invention.

[0040] Examples of other plasticizers include phthalate ester plasticizers, trimellitic acid ester plasticizers, pyromellitic acid ester plasticizers, adipic acid ester plasticizers, itaconic acid ester plasticizers, citrate ester plasticizers, cyclohexane dicarboxylate plasticizers, and epoxy plasticizers. Alternatively, one or more of these plasticizers can be used.

[0041] Examples of phthalate ester plasticizers include dibutyl phthalate, butylhexyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, ditridecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate.

[0042] Examples of trimellitic acid ester plasticizers include tri(2-ethylhexyl) trimellitate, tri(n-octyl) trimellitate, and tri(isononyl) trimellitate.

[0043] Examples of adipic acid ester plasticizers include bis(2-ethylhexyl) adipate, dioctyl adipate, diisononyl adipate, and diisodecyl adipate.

[0044] Examples of epoxy plasticizers include epoxidized soybean oil, epoxidized linseed oil, epoxidized fatty acid octyl esters, and epoxidized fatty acid alkyl esters.

[0045] Other examples of plasticizers include tetrahydrophthalate diester plasticizers, glycerin ester plasticizers, epoxyhexahydrophthalate diester plasticizers, isosorbide diester plasticizers, phosphate plasticizers, azelaic acid plasticizers, sebaciate plasticizers, stearic acid plasticizers, biphenyltetracarboxylic acid ester plasticizers, polyester plasticizers having a weight-average molecular weight outside the specified range, and chlorine-based plasticizers.

[0046] The total amount of plasticizer (polyester-based plasticizer having the weight-average molecular weight within the specified range and other plasticizers) in the colored film layer containing polyvinyl chloride resin is usually greater than 0 parts by mass and less than or equal to 80 parts by mass, preferably 5 parts by mass or more and 50 parts by mass, 10 parts by mass or more and 40 parts by mass or less, or 15 parts by mass or more and 30 parts by mass or less, based on a total of 100 parts by mass of the polyvinyl chloride resin and the other resins. The mass percentage of polyester-based plasticizers having a weight-average molecular weight within the above-mentioned specific range in the total amount of plasticizers contained in the colored film layer is preferably 80% by mass or more, more preferably 90% by mass or more, or substantially 100% by mass, from the viewpoint of sufficiently exhibiting the effect of suppressing the migration of plasticizers from the colored film layer to the transparent film layer on the surface side.

[0047] The colored film layer containing polyvinyl chloride resin may contain, as non-limiting examples, the following coloring pigments or colorants. Inorganic pigments such as iron black, antimony white, lead yellow, titanium yellow, red iron oxide, cadmium red, ultramarine, and cobalt blue; Complex oxides such as Cu-Fe-Mn, Cu-Cr, Cu-Cr-Mn, Cu-Cr-Mn-Ni, Cu-Cr-Fe, Co-Cr-Fe; Organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue; Metallic pigments consisting of flaky foil pieces of aluminum, brass, etc. Pearlescent pigments consisting of titanium dioxide particle-coated mica, basic lead carbonate, and other flaky foil fragments; Iron oxide, carbon black, titanium dioxide particles, phthalocyanine blue, isoindolinone, diketopyrrolopyrrole, azo pigments, disazo pigments, dark azo pigments; Titanium black, titanium nitride, titanium oxynitride, perinone-perylene pigments, perylene black pigment, aniline black pigment.

[0048] In one embodiment, the colored film layer containing polyvinyl chloride resin may contain titanium dioxide (TiO2: titanium dioxide / titania) particles as a white pigment. By having the colored film layer containing polyvinyl chloride resin, which forms the base of the transparent film layer containing acrylic resin, contain titanium dioxide particles in an amount greater than a predetermined lower limit, the reflectivity of sunlight (solar radiation) within the colored film layer can be increased. Consequently, heat accumulation due to radiant heat by the exterior laminate including the colored film layer can be sufficiently suppressed, resulting in high heat shielding performance.

[0049] The titanium dioxide particles that may be contained in the colored film layer containing polyvinyl chloride resin are not particularly limited, and any of the crystalline forms of rutile, anatase, or brookite can be used. Among these, rutile titanium dioxide particles are preferred. The titanium dioxide particles may be surface-treated with a coating agent. Examples of coating agents include inorganic oxides such as silicon dioxide, alumina, and zinc oxide. The average particle diameter (primary particle diameter) of the titanium dioxide particles is not particularly limited, but is usually between 10 nm and 1000 nm, preferably between 15 nm and 800 nm, between 20 nm and 500 nm, or between 30 nm and 300 nm. The average particle diameter here refers to the median diameter, which can be measured using a laser diffraction / scattering particle size distribution analyzer (d50).

[0050] The content of coloring pigments or colorants in the colored film layer containing polyvinyl chloride resin is not particularly limited, but may be, for example, 0.1% to 20% by mass, 0.3% to 15% by mass, 0.8% to 10% by mass, or 1% to 8% by mass, relative to the total mass of the colored film layer.

[0051] In a preferred embodiment, the amount of carbon black in the colored film layer containing polyvinyl chloride resin may be 0% to 0.1% by mass or 0% to 0.05% by mass relative to the total mass of the colored film layer. In a more preferred embodiment, the colored film layer containing polyvinyl chloride resin does not contain carbon black. While there is no intention to completely eliminate the use of carbon black in the colored film layer containing polyvinyl chloride resin, it is preferable to use less carbon black, which has high heat absorption (high heat storage) properties, in the colored film layer, and more preferably to use none at all. Furthermore, the statement that "the colored film layer containing polyvinyl chloride resin does not contain carbon black" includes not only cases where the colored film layer contains no carbon black at all, but also cases where the colored film layer contains substantially no carbon black, that is, the amount of carbon black in the colored film layer is so small that it does not affect the heat storage suppression performance of the layer (for example, the amount of carbon black relative to the total mass of the colored film layer is 0.1% by mass or less or 0.01% by mass or less).

[0052] Furthermore, the polyvinyl chloride resin used as a material for the colored film layer containing the polyvinyl chloride resin may contain, in addition to the components described and illustrated above, substances commonly used in polyvinyl chloride resin compositions, to the extent that they do not contradict the objectives of the present invention. Examples of such optional components that may be included include inorganic fillers other than titanium dioxide particles and pigments, organic fillers, resin fillers; lubricants, antioxidants, weather stabilizers, heat stabilizers, processing aids, reinforcing agents, nucleating agents, mold release agents, antistatic agents, urea-formaldehyde wax, and surfactants. The amount of these optional components blended may typically be about 0.01 parts by mass or more and 50 parts by mass or less, based on a total of 100 parts by mass of the polyvinyl chloride resin and the other resins mentioned above.

[0053] The colored film layer containing polyvinyl chloride resin may be a single layer or a laminate of multiple layers. If the colored film layer containing polyvinyl chloride resin is a laminate of multiple layers, it may consist of multiple layers having the same composition, or it may consist of multiple layers, some of which have different compositions. Furthermore, the colored film layer containing polyvinyl chloride resin may be an unoriented film, a uniaxially oriented film, or a biaxially oriented film. If the colored film layer containing polyvinyl chloride resin is a laminate of multiple layers, it may be formed from a combination of two or more of the unoriented film, uniaxially oriented film, and biaxially oriented film.

[0054] The method for manufacturing a colored film layer containing polyvinyl chloride resin using the above-mentioned materials is not particularly limited. Examples of methods for obtaining a colored film layer include a calendering method using an apparatus equipped with a calender roll rolling machine and a winding machine, an extrusion method using an apparatus equipped with an extruder, a T-die and a winding machine, and an inflation molding method. Examples of calender roll rolling machines include upright 3-roll, upright 4-roll, L-type 4-roll, inverted L-type 4-roll, and Z-type roll. Examples of extruders include single-screw extruders, co-rotating twin-screw extruders, and opposite-rotating twin-screw extruders. Examples of T-dies include manifold dies, fishtail dies, and coat hanger dies.

[0055] The thickness of the colored film layer containing polyvinyl chloride resin (total thickness if it consists of multiple layers) is not particularly limited, but from the viewpoint of balancing the impartment of desired properties such as high heat insulation with manufacturing costs and ease of handling, it may be, for example, 5 μm or more and 1000 μm or less. This thickness is preferably 8 μm or more, 10 μm or more, 20 μm or more, 30 μm or more or 40 μm or more, and / or 800 μm or less, 600 μm or less, 500 μm or less, 400 μm or less, 300 μm or less, 200 μm or less, 100 μm or less or 80 μm or less.

[0056] c) Printing layer In exterior laminates, optionally provided printed layers have the function of providing a high level of design and aesthetic appeal, such as patterns and designs, to those who view the exterior laminate. If provided, the printed layer may serve as a base for the transparent film layer containing an acrylic resin, which is positioned closer to the surface in the exterior laminate, and may also be positioned on the surface side of the colored film layer containing a polyvinyl chloride resin. In other words, the printed layer may be positioned between the transparent film layer containing the acrylic resin and the colored film layer containing the polyvinyl chloride resin.

[0057] The printed layer can be formed by printing any pattern using any ink and any printing press. For example, such a printed layer can be applied entirely or partially to the surface of a colored film layer containing a polyvinyl chloride resin, either directly or via any anchor coat. The printing may be carried out by any known method, such as gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, or inkjet printing. Examples of patterns include metallic patterns such as hairline patterns, wood grain patterns, stone patterns that mimic the surface of rocks such as marble, fabric patterns that mimic the texture of cloth or fabric, tile patterns, brick patterns, parquet patterns, and patchwork.

[0058] The printed layer may preferably have a solar transmittance of 70% or more. More preferably, the printed layer may have a solar transmittance of 73% or more, or 75% or more. The printed layer may preferably have a solar absorptance of 20% or less. More preferably, the printed layer may have a solar absorptance of 17% or less, or 15% or less. The printed layer may preferably have a solar transmittance of 70% or more and a solar absorptance of 20% or less. More preferably, the printed layer may have a solar transmittance of 73% or more and a solar absorptance of 17% or less, or a solar transmittance of 75% or more and a solar absorptance of 15% or less. In exterior laminates, by setting the solar transmittance and / or solar absorptance of the printed layer within a predetermined range, the transmittance of sunlight (solar radiation) in the printed layer can be increased, or the absorption capacity of sunlight (solar radiation) can be decreased, thereby sufficiently suppressing heat accumulation due to radiant heat and achieving high heat shielding performance. Exterior laminates having such a printed layer also have excellent weather resistance due to their even higher heat shielding performance, and combined with the crack prevention properties of the transparent film layer, the preservation of design and aesthetics can be further enhanced. Therefore, exterior components using this laminate have the advantage of being able to withstand long-term continuous use, including large temperature fluctuations.

[0059] In this specification, solar transmittance was measured using an ultraviolet-visible-near-infrared spectrophotometer in the measurement wavelength range of 300 to 2500 nm, in accordance with JIS A5759-2016. Furthermore, the solar absorptance in this specification was calculated according to JIS A5759-2016, by measuring the solar transmittance and solar reflectance in the range of 300 to 2500 nm using an ultraviolet-visible-near-infrared spectrophotometer, and using the following formula. Solar absorptance = 100 - (solar transmittance + solar reflectance). For the measurement of solar transmittance and solar reflectance of the printed layer, a 25 μm thick PET film (Cosmoshine E5431 from Toyobo Co., Ltd.) was printed, and measurements were taken on the PET film with the printed layer laminated on top.

[0060] As the printing ink for forming the printed layer, a binder can be used which pigments, solvents, stabilizers, plasticizers, catalysts, and curing agents are appropriately mixed. As the binder, for example, resins such as polyurethane resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, polyester resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, and cellulose acetate resins, and compositions thereof, can be used. Furthermore, in order to apply a metallic design, aluminum, tin, titanium, indium, and oxides thereof may be deposited directly or via an optional anchor coat onto the entire or partial surface of the colored film layer containing polyvinyl chloride resin by known methods.

[0061] The pigments contained in the printing ink for forming the printed layer are not particularly limited, and any known pigments may be used. Any of the pigments exemplified above for use in a colored film layer containing polyvinyl chloride resin can be used as pigments for printing inks. However, it is desirable that the type and amount of pigment contained in the printing ink be adjusted so that the solar transmittance and solar absorptance of the printed layer satisfy the preferred ranges described above. In one preferred embodiment, the amount of carbon black in the printed layer may be 0% by mass or more and 0.1% by mass or less, or 0% by mass or more and 0.05% by mass or less, relative to the total mass of the printed layer. In one more preferred embodiment, the printed layer does not contain carbon black. While there is no intention to completely eliminate the use of carbon black in the printed layer, it is preferable to use as little carbon black as possible, as carbon black has high heat absorption (high heat storage) properties, and it is even more preferable to use none at all. Furthermore, the statement "the printed layer does not contain carbon black" includes not only the case where the printed layer contains no carbon black at all, but also the case where the printed layer contains substantially no carbon black, that is, the amount of carbon black in the printed layer is so small that it does not affect the heat storage suppression performance of the layer (for example, the amount of carbon black relative to the total mass of the printed layer is 0.1% by mass or less or 0.01% by mass or less).

[0062] d) Base material The substrate optionally included in the exterior laminate serves as a base for a) a transparent film layer containing an acrylic resin, an optionally provided c) printed layer, and b) a colored film layer containing a polyvinyl chloride resin, supporting the laminated structure of these layers and constituting the main body of the exterior laminate or the main body of an exterior component. That is, when the exterior laminate includes a substrate, this substrate may be positioned on the side opposite to the surface of the colored film layer containing the polyvinyl chloride resin.

[0063] The materials and shapes constituting the base material are not particularly limited, as long as they do not hinder the desired effects achieved by the exterior laminate according to the present invention and can constitute the main body portion of the desired exterior member. Examples of the main constituent materials of the base material include any known type of resin, metal, wood, glass, ceramic, rubber, concrete, or a composite of two or more of these. Furthermore, the substrate may be in a two-dimensional shape such as a film, sheet, or plate, or it may be in any three-dimensional shape.

[0064] Any resin can be used as the resin constituting the base material. Examples of resins include polyvinyl chloride resins; polyvinylidene chloride resins; polyester resins such as aromatic polyesters and aliphatic polyesters; acrylic resins; polycarbonate resins; poly(meth)acrylimide resins; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; cellulose resins such as cellophane, triacetylcellulose, diacetylcellulose, and acetylcellulose butyrate; styrene resins such as polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), styrene-ethylene-butadiene-styrene copolymer, styrene-ethylene-propylene-styrene copolymer, and styrene-ethylene-ethylene-propylene-styrene copolymer; fluorine-containing resins such as polyvinylidene fluoride; and others such as polyvinyl alcohol, ethylene vinyl alcohol, polyetheretherketone, nylon, polyamide, polyimide, polyurethane, polyetherimide, polysulfone, and polyethersulfone. Furthermore, these resins may be transparent, translucent, or opaque, and may be colorless or colored. When the substrate is formed from a film of these resins, the film includes unoriented films, uniaxially oriented films, and biaxially oriented films. Furthermore, the resin film includes laminated films formed by laminating two or more layers of one or more of these types.

[0065] Any metal can be used as the metal constituting the base material. Examples of metals include aluminum, iron, nickel, titanium, molybdenum, magnesium, manganese, copper, silver, lead, tin, chromium, beryllium, tungsten, cobalt, metal compounds, alloys of any two or more metals, or mixtures of any two or more of these.

[0066] The substrate may optionally contain additional components other than those exemplified above as the main constituent materials of the substrate, to the extent that it does not contradict the objectives of the present invention. Examples of such optional components include additives such as ultraviolet absorbers, light stabilizers, flame retardants, photopolymerization initiators, antistatic agents, surfactants, leveling agents, thixotropic agents, antifouling agents, printability improvers, antioxidants, weather-resistant stabilizers, heat stabilizers, pigments, and fillers. The amount of the above optional components (if used) is not particularly limited, but is usually about 0.01 parts by mass or more and 10 parts by mass or less, relative to 100 parts by mass of the amount of the main constituent materials. Pigments and colorants may be included for coloring the substrate, but it is desirable to avoid the use of pigments such as carbon black, which have high heat absorption and heat storage properties. The substrate may contain titanium dioxide particles as a white pigment, which can enhance the reflectivity of sunlight (solar radiation) and prevent deformation of the laminate due to heat storage.

[0067] Laminate for exterior use The exterior laminate may consist, in order from the surface side, only a) a transparent film layer containing an acrylic resin and b) a colored film layer containing a polyvinyl chloride resin; or, in order from the surface side, only a) a transparent film layer containing an acrylic resin, an optionally provided c) printed layer, and b) a colored film layer containing a polyvinyl chloride resin; or, in order from the surface side, only a) a transparent film layer containing an acrylic resin, an optionally provided c) printed layer, b) a colored film layer containing a polyvinyl chloride resin, and optionally included d) a substrate. Furthermore, the exterior laminate may have any layer other than a) a transparent film layer containing an acrylic resin, c) a printed layer, b) a colored film layer containing a polyvinyl chloride resin, and d) a substrate, as long as it does not contradict the objectives of the present invention. Examples of such arbitrary layers include resin film layers other than the transparent film layer and the colored film layer, printing ink-containing layers other than the printed layer, anchor coats, adhesive layers, surface protection layers, transparent conductive layers, high refractive index layers, low refractive index layers, and anti-reflective functional layers. The position in which such arbitrary layers are arranged may be between any two adjacent layers of layers a), c), b), and d), or on the outer surface side of these laminates. Any surface protection layer may be formed on the outer surface (i.e., the outermost surface) of the transparent film layer containing an acrylic resin arranged on the surface side of the exterior laminate.

[0068] Figure 1 shows a schematic diagram of an exterior laminate according to one embodiment of the present invention. In Figure 1, from the surface side outwards, 1 refers to a) a transparent film layer containing acrylic resin, 2 refers to an optional c) printed layer, 3 refers to b) a colored film layer containing polyvinyl chloride resin, 4 refers to an optional d) substrate, and 10 refers to the entire exterior laminate.

[0069] Manufacturing method for exterior laminates In the manufacture of exterior laminates, the method for laminating a) a transparent film layer containing an acrylic resin and b) a colored film layer containing a polyvinyl chloride resin is not particularly limited, and any known method may be employed. Examples of lamination methods include: a method of directly heat-laminating the transparent film layer containing an acrylic resin and the colored film layer containing a polyvinyl chloride resin; a method of forming a transparent film layer containing an acrylic resin by melt-extruding a resin composition containing an acrylic resin onto the surface of the colored film layer containing a polyvinyl chloride resin; and a method of laminating the transparent film layer containing an acrylic resin and the colored film layer containing a polyvinyl chloride resin via any known adhesive. The temperature, time, and other conditions for heat lamination and melt extrusion can be appropriately selected from suitable conditions known in the industry. Examples of adhesives for interlayer bonding include acrylic resins, polyurethane resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, styrene-acrylic copolymer resins, polyester resins, and polyamide resins. Two-component polyurethane or polyester adhesives that use isocyanates or the like as a curing agent may also be used. Alternatively, if the exterior laminate does not include a printed layer, lamination can be performed by co-extruding two layers: a resin composition containing an acrylic resin for forming a transparent film layer and a resin composition containing a polyvinyl chloride resin for forming a colored film layer. The temperature, time, and other conditions for this two-layer co-extrusion can be appropriately selected from suitable conditions known in the industry.

[0070] When a printed layer (c) is optionally provided on the exterior laminate, the method for forming the printed layer is not particularly limited, and any known method can be used. Examples of methods for forming the printed layer include gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, and inkjet printing. Furthermore, when forming a solid printed layer over an entire surface, in addition to the methods exemplified above, other methods such as roll coating, knife coating, air knife coating, die coating, lip coating, comma coating, kiss coating, flow coating, and dip coating can also be used, as well as hand-painting, suminagashi (marbling), photography, laser beam lithography, electron beam lithography, partial deposition of metals, etching, or combinations thereof.

[0071] c) When an exterior laminate includes a printed layer, lamination methods include, for example, a method in which a printed layer is formed on the surface side of a colored film layer containing a polyvinyl chloride resin, and then the transparent film layer containing an acrylic resin and the printed layer are directly heat-laminated; a method in which a transparent film layer containing an acrylic resin is formed on the printed surface by melt-extruding a resin composition containing an acrylic resin for forming the transparent film layer onto the surface side of the printed layer; and a method in which the transparent film layer containing an acrylic resin and the printed layer are laminated via any known adhesive. The temperature, time, and other conditions for heat lamination and melt extrusion can be appropriately selected from suitable conditions known in the industry. Examples of adhesives for interlayer bonding include acrylic resins, polyurethane resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, styrene-acrylic copolymer resins, polyester resins, and polyamide resins. Two-component curing type polyurethane adhesives or polyester adhesives using isocyanates as a curing agent can also be used.

[0072] In the form in which the exterior laminate includes d) a substrate, the method for laminating d) the substrate with a multilayer structure of a) a transparent film layer containing an acrylic resin, an optionally provided c) printed layer, and b) a colored film layer containing a polyvinyl chloride resin is not particularly limited, and any known method may be employed. For example, a method of directly heat-laminating the substrate with a multilayer structure of a transparent film layer containing an acrylic resin, an optionally provided printed layer, and a colored film layer containing a polyvinyl chloride resin; a method of forming a colored film layer containing a polyvinyl chloride resin on one surface of the substrate by melt-extruding a resin composition containing a polyvinyl chloride resin to form the colored film layer, and then forming other layers thereon; and a method of laminating the substrate with a multilayer structure of a transparent film layer containing an acrylic resin, an optionally provided printed layer, and a colored film layer containing a polyvinyl chloride resin via any known adhesive or tack. The temperature, time, and other conditions for heat lamination and melt extrusion can be appropriately selected from suitable conditions known in the industry, as described above. Examples of adhesives for interlayer bonding include acrylic resins, polyurethane resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, styrene-acrylic copolymer resins, polyester resins, and polyamide resins. Two-component curing polyurethane or polyester adhesives using isocyanates as a curing agent may also be used. For bonding the substrate to the colored film layer containing polyvinyl chloride resin, a tackant may be used instead of an adhesive. Such a tackant is not particularly limited, but any known tackant may be used. Examples of tackants include acrylic, urethane, silicone, and rubber-based tacks. Alternatively, if the exterior laminate does not include a printed layer, lamination can be performed by co-extruding three layers (for example, by morph extrusion to have an arbitrary cross-sectional shape) a resin composition containing an acrylic resin for forming a transparent film layer, a resin composition containing a polyvinyl chloride resin for forming a colored film layer, and a substrate forming material. The temperature, time, and other conditions for this three-layer co-extrusion or morph extrusion can be appropriately selected from suitable conditions known in the industry.

[0073] Exterior components The exterior laminate according to the present invention can be used as an exterior component in a variety of applications. The applications of the exterior component using the exterior laminate according to the present invention are not particularly limited, as long as it can constitute the appearance of a structure such as a building or an automobile. The exterior component can be suitably used in applications that are directly exposed to sunlight (solar radiation). Examples of applications for the exterior component include the following: Materials involved in the exterior appearance of buildings include sashes, window frames, doors, flooring, balconies, verandas, jointing materials, handrails, moldings, table edge materials, bathtubs, signs, lighting covers, aquariums, stair wainscoting, carports, highway sound barriers, multi-wall sheets, steel wire cladding, lighting globes, etc. Components involved in the exterior appearance of transport structures such as automobiles include sashes, window frames, meter covers, body panels, door handles, rear panels, wheel caps, visors, roof rails, sunroofs, instrument panels, panels, control cable sheathing, airbag covers, mudguards, bumpers, boots, air hoses, various moldings such as window moldings, side shields, weatherstrips, and glass run channels.

[0074] sash The exterior laminate according to the present invention can be used in applications such as aluminum sashes, which are sashes based on aluminum that have been widely used in the past, and resin sashes, which are based on resins that have attracted attention in recent years. Any known structure of these sashes, and any type or composition of the aluminum or resin used as the base material, can be adopted (for example, for known sash structures, refer to the above-mentioned Patent Documents 1 and 2). The type of resin used as the base material for the exterior laminate in resin sashes is not particularly limited, but is typically a polyvinyl chloride resin. When the exterior laminate according to the present invention is used for exterior components such as window frames, the migration of plasticizers from the colored film layer to the transparent film layer on the surface, and the resulting crack formation in the transparent film layer, can be sufficiently suppressed even when exposed to sunlight (solar radiation) for a long period of time. As a result, it has high weather resistance and can also enhance the preservation of its design and aesthetic appeal. Therefore, exterior components such as resin window frames on which the laminate forms the surface can withstand continuous use over a long period of time, including large temperature fluctuations. [Examples]

[0075] The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0076] Measurement method (1) Loading test • Weight change rate of transparent film containing acrylic resin a) A transparent film containing acrylic resin and b) a colored film containing polyvinyl chloride resin were each cut to a size of 25 mm x 50 mm, and the weight of a) the transparent film containing acrylic resin was measured. b) A transparent film containing acrylic resin (a) was placed on top of a colored film containing polyvinyl chloride resin to create a test sample. The test sample was sandwiched between two aluminum plates and placed in a gear oven at 70°C. A load of 1 kgf was applied from above. After 4 weeks, the test sample was removed and allowed to return to room temperature. The weight of the transparent film containing acrylic resin (a) was measured, and the percentage change in weight before and after the test was calculated. When the weight of the transparent film containing acrylic resin increases before and after this test, it is thought that this is due to the migration of the plasticizer contained in the colored film to the transparent film. Therefore, a lower weight increase rate in this test result is understood to mean less plasticizer migration.

[0077] (2) Weathering test • Confirmation of surface crack occurrence using a weathering tester (Metal Weather). Using the Metal Weather DMW KU R5N-A weather resistance tester from Daipla Wintes Co., Ltd., the surface crack formation after 40 cycles of treatment was visually inspected under the following conditions. Test conditions: Lighted conditions + condensation conditions, 1 cycle = 24 hours. (i) Light conditions Temperature: 53℃, Humidity: 50%, Irradiation: 70mW / cm 2 Time: 20 hours. (ii) Condensation conditions Temperature: 30℃, Humidity: 98%, Time: 4 hours, 10-second shower before and after condensation. The weather resistance was evaluated as follows: 〇: Cracks were observed on the surface after 40 cycles of treatment. ×: No cracks were observed on the surface after 40 cycles of treatment.

[0078] (3) Solar simulator test (3-1)Surface temperature Using the XES-155S1 solar simulator from Sanei Electric Works Co., Ltd., an irradiance of 1000 W / m² was measured. 2 The sample was irradiated with a light source at a distance of 30 cm, and the surface temperature of the sample was measured after 30 minutes. For surface temperature measurement, a HIKIMICRO SP60-25m thermograph was used, and the central part of the sample was measured at a distance of 58 cm from the measuring instrument. (3-2) Substrate deformation Using the XES-155S1 solar simulator from Sanei Electric Works Co., Ltd., an irradiance of 1000 W / m² was measured. 2 The sample was irradiated for 30 minutes at a distance of 30 cm from the light source, and the deformation of the substrate was observed. The same sample used for the surface temperature test described above was used. The deformation was evaluated as follows: ○: The lifting of the edges of the substrate was less than 2 mm. △: The lifting at the edges of the substrate was 2 mm or more and less than 5 mm. ×: The edge of the base material was lifted by 5 mm or more.

[0079] Raw materials used a) Transparent film layer containing acrylic resin a-1) Sanduren 101XL11T (Kaneka Corporation) Thickness 53μm A transparent film primarily composed of methyl methacrylate and containing a triazine-based UV absorber. a-2) Sanduren 001NAT (Kaneka Corporation) Thickness 53μm A transparent film primarily composed of methyl methacrylate and containing a benzotriazole-based UV absorber. b) Colored film layer containing polyvinyl chloride resin b-1) A colored film obtained by depositing a composition comprising 100 parts by mass of polyvinyl chloride resin, 19 parts by mass of polyester plasticizer, and a reinforcing agent, processing aid, stabilizer, ultraviolet absorber, and colorant to a thickness of 100 μm using a calendering machine. PN-446 (ADEKA Corporation, adipic acid-based polyester, weight-average molecular weight 5500) was used as the polyester-based plasticizer. Titanium dioxide (CR-90 (Ishihara Sangyo Co., Ltd.)) was added at a concentration of 16.5% by mass as a coloring agent. b-2) A colored film was obtained in the same manner as in b-1), except that the polyester-based plasticizer was changed to the following grade. The polyester-based plasticizer used was PN-1030 (ADEKA Corporation, adipic acid-based polyester, weight-average molecular weight 4100). b-3) A colored film was obtained in the same manner as in b-1), except that the polyester-based plasticizer was changed to the following grade. The polyester-based plasticizer used was PN-1010 (ADEKA Corporation, adipic acid-based polyester, weight-average molecular weight 3100). c) Printing layer A wood grain pattern (three-color) was printed on one side of the colored film using a gravure printing press with acrylic binder printing ink. The following black printing inks were used: c-1) DS Black (DIC Graphics Corporation, perylene-based). c-2) NH-NT Ink (Z) (DIC Graphics Co., Ltd., carbon black, contains 0.3% by mass of carbon black). d) Base material d-1) ES-5700 (Takiron CI Co., Ltd., rigid white polyvinyl chloride resin sheet, 3mm thick).

[0080] Example 1 Transparent film a-1) and colored film b-1) were heat-laminated using an embossing machine to create samples for load testing and weather resistance testing. The colored film side of the samples used for the above-mentioned load test and weather resistance test was bonded to the substrate d-1) via an acrylic adhesive to create samples for solar simulator testing. The aforementioned tests were conducted using the components of each layer and samples thereof, and the evaluation results are shown in Table 1.

[0081] Comparative Example 1 a) Samples were prepared and evaluated in the same manner as in Example 1, except that transparent film a-2) was used as the transparent film layer. The evaluation results are shown in Table 1.

[0082] Example 2, Comparative Example 2 In Example 2, samples were prepared and evaluated in the same manner as in Example 1, except that colored film b-2) was used as the colored film layer. In Comparative Example 2, samples were prepared and evaluated in the same manner as in Example 1, except that colored film b-3) was used as the colored film layer. The evaluation results are shown in Table 1.

[0083] Examples 3 and 4 c) Samples were prepared and evaluated in the same manner as in Example 1, except that a printed layer was added. The evaluation results are shown in Table 1. The printing involved applying a three-color wood grain print to one side of a colored film b-1) using a gravure printing machine, and then creating a printed layer c) In Example 3, black ink c-1) was used, while in Example 4, c-2) was used.

[0084] [Table 1]

[0085] It has been found that the exterior laminate of the present invention, by containing a polyester-based plasticizer having a predetermined weight-average molecular weight in the colored film layer and a specific type of ultraviolet absorber in the transparent film layer, can sufficiently suppress the migration of the plasticizer from the colored film layer to the transparent film layer on the surface side, and the resulting crack formation in the transparent film layer, even when exposed to sunlight (solar radiation) for a long period of time. [Explanation of symbols]

[0086] 1: Transparent film layer containing acrylic resin 2: Printing layer 3: Colored film layer containing polyvinyl chloride resin 4: Base material 10: Laminate for exterior use

Claims

1. Starting from the surface side, a) A transparent film layer containing an acrylic resin, and b) Colored film layer containing polyvinyl chloride resin An exterior laminate having, The transparent film layer in a) contains a triazine-based ultraviolet absorber, The colored film layer of (b) above contains a polyester-based plasticizer having a weight-average molecular weight of 3500 or more. Laminated material for exterior use.

2. Starting from the surface side, a) A transparent film layer containing acrylic resin, c) Printed layer, and b) Colored film layer containing polyvinyl chloride resin An exterior laminate according to claim 1, having the following characteristics.

3. The exterior laminate according to claim 2, wherein the printed layer in c) above does not contain carbon black.

4. An exterior member using the exterior laminate described in any one of claims 1 to 3.

5. A resin sash using an exterior laminate according to any one of claims 1 to 3.

Images