Decorative sheets and decorative components

Abstract

To provide decorative sheets and decorative components with higher humidity and heat resistance. [Solution] The material comprises a colored thermoplastic resin layer 2, a pattern layer 3, and a transparent thermoplastic resin layer 5, which are laminated in order, and an adhesive layer 7 and a release paper layer 8 laminated on the side of the colored thermoplastic resin layer 2 opposite to the pattern layer 3. The pattern layer 3 contains a urethane resin as a binder resin, which includes polycaprolactone polyol, polyalkylene glycol, and polyisocyanate as constituent elements, and furthermore, the maximum point stress after a 192-hour pressure cooker test is 15 N / mm 2 The decorative sheet 1 is formed such that the adhesive strength to the polypropylene board is 5N / 25mm or more.

Description

[Technical Field]

[0001] This invention relates to decorative sheets and decorative components. [Background technology]

[0002] Conventionally, in decorative sheets in which a base layer, a pattern layer, and a transparent resin layer are laminated in this order, a decorative sheet has been proposed in which an adhesive layer is provided on the side of the base layer opposite to the transparent resin layer (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2021-142744 [Overview of the project] [Problems that the invention aims to solve]

[0004] Decorative sheets with an adhesive layer are used on the surfaces of various items such as building walls, building materials, furniture, and electrical appliances. However, decorative sheets used for the exterior of buildings and other structures require particularly high resistance to humidity and heat.

[0005] This invention has been made in view of these points, and aims to provide decorative sheets and decorative components that have higher humidity and heat resistance. [Means for solving the problem]

[0006] To solve the above problems, one aspect of the present invention comprises a colored thermoplastic resin layer, a pattern layer, and a transparent thermoplastic resin layer laminated in order, and an adhesive layer and a release paper layer laminated on the side of the colored thermoplastic resin layer opposite to the pattern layer, wherein the pattern layer contains a urethane resin containing polycaprolactone polyol, polyalkylene glycol, and polyisocyanate as components as a binder resin, and the maximum point stress after a 192-hour pressure cooker test is 15 N / mm2 The above is provided, and the decorative sheet is provided having an adhesive strength of 5N / 25mm or more to a polypropylene board. Another aspect of the present invention provides a decorative member comprising an exterior material and a decorative sheet according to the above aspect provided on at least a portion of the surface of the exterior material. [Effects of the Invention]

[0007] According to one aspect of the present invention, decorative sheets and decorative members having higher moisture and heat resistance can be easily obtained. [Brief explanation of the drawing]

[0008] [Figure 1] This is a schematic cross-sectional view showing an example of a decorative sheet according to one embodiment of the present invention. [Figure 2] This is a schematic cross-sectional view showing an example of a decorative component according to one embodiment of the present invention. [Modes for carrying out the invention]

[0009] Embodiments of this technology will be described below with reference to the drawings. In these embodiments, decorative sheets and decorative materials for floors or joinery will be used as examples, but decorative sheets for use in other parts may also be used. Here, the drawings are schematic, and the relationship between thickness and planar dimensions, the ratio of the thickness of each layer, etc., may differ from reality. Furthermore, the embodiments shown below illustrate configurations for realizing the technical idea of ​​the present invention, and the technical idea of ​​the present invention is not limited to the materials, shapes, and structures of the components described below. The technical idea of ​​the present invention can be modified in various ways within the technical scope defined by the claims described in the patent claims.

[0010] [Composition of decorative sheet] As shown in Figure 1, the decorative sheet 1 according to one embodiment of the present invention has a colored thermoplastic resin layer 2, a pattern layer 3, an adhesive resin layer 4, a transparent thermoplastic resin layer 5, and a surface protection layer 6 laminated in this order. On the side of the colored thermoplastic resin layer 2 opposite to the pattern layer 3, a release paper layer 8 is laminated via an adhesive layer 7.

[0011] [Colored thermoplastic resin layer] The main component of the resin constituting the colored thermoplastic resin layer 2, which serves as the base layer, is preferably polyolefin. If the main component of the resin constituting the colored thermoplastic resin layer 2 is polyolefin, the adhesion to the pattern layer 3 can be improved.

[0012] The thickness of the colored thermoplastic resin layer 2 is preferably 30 μm to 100 μm. If the thickness of the colored thermoplastic resin layer 2 is less than 30 μm, it is too thin, making film formation difficult, and the printability will be reduced due to the effect of thickness deviation. If the thickness of the colored thermoplastic resin layer 2 is greater than 100 μm, it is too thick, making it difficult to handle as a final product (decorative sheet), and reducing workability. In addition, when applying the decorative sheet to small areas, there is a possibility that the decorative sheet may bounce back or otherwise malfunction. The colored thermoplastic resin layer 2 may be subjected to surface treatments such as corona treatment, plasma treatment, ozone treatment, electron beam treatment, ultraviolet treatment, or dichromate treatment in order to improve adhesion with adjacent layers.

[0013] [Picture layer] The pattern layer 3 is formed by printing a pattern ink onto the colored thermoplastic resin layer 2 using a binder resin containing at least specific components, namely polycaprolactone polyol, polyalkylene glycol, and polyisocyanate. Preferably, the pattern ink further contains neopentyl glycol. Including neopentyl glycol in the pattern ink improves its resistance to moisture and heat.

[0014] The urethane resin of this embodiment can be synthesized by a known technique, that is, an addition polymerization reaction between a polyol and a polyisocyanate. The terminal of the urethane resin is usually an isocyanate group blocked with a hydroxyl group or an amine. When the terminal of the urethane resin is a hydroxyl group, the pattern layer 3 can be cured by blending a curing agent such as isocyanate into the pattern ink.

[0015] The polycaprolactone polyol constituting the urethane resin of this embodiment is a material obtained by ring-opening polymerization of ε-caprolactone and has an ester bond inside. Therefore, the adhesion to the base material 11, that is, the base material adhesion is improved. The polycaprolactone polyol generally has excellent hydrolysis resistance compared to a general-purpose polyester polyol obtained by polycondensation of a dicarboxylic acid such as adipic acid and a diol.

[0016] The polyalkylene glycol constituting the urethane resin of this embodiment has a polyether structure and is excellent in hydrolysis resistance compared to the above-mentioned polycaprolactone polyol, but tends to be inferior in heat resistance and base material adhesion. In this embodiment, by using the polyalkylene glycol in combination with the polycaprolactone polyol, both the base material adhesion and the moisture and heat resistance are achieved.

[0017] As the polyalkylene glycol, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. can be used, and polytetramethylene glycol having a large hydrophobicity is suitable from the viewpoint of moisture and heat resistance.

[0018] The polycaprolactone polyol and the polyalkylene glycol of this embodiment can be appropriately selected and used from various commercially available materials in terms of molecular weight, functional group number (number of hydroxyl groups per molecule), etc. Further, as the polyisocyanate, for example, diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and hydrogenated products thereof can be used, and isophorone diisocyanate is suitable in terms of moisture and heat resistance.

[0019] Although the composition of the urethane resin of this embodiment is not particularly limited, considering the printing suitability of the pattern layer 3 formed by ordinary printing and various performances of the decorative sheet 1, when the amounts of substances of each part of the urethane resin (caprolactone unit (CL), alkylene glycol unit (AG), diisocyanate unit (I), neopentyl glycol (NPG)) shown in the following structural formula are X, Y, Z, and N respectively, it is preferable to satisfy the following relational expressions (1) to (3).

[0020]

Chem.

[0021] 3 < (X + Y + N) / Z < 50 (Equation 1) 0.1 < X / Y < 10 (Equation 2) N / (X + Y + X + N) < 0.2 (Equation 3) Within the above numerical range, the printing suitability can be easily improved.

[0022] The molecular weight of the urethane resin of this embodiment is not particularly limited. For example, considering the printing suitability of the pattern layer 3 formed by ordinary printing and various performances of the decorative sheet 1, the mass average molecular weight (MW) is preferably in the range of 5,000 or more and 100,000 or less. Within the above numerical range, the printing suitability can be easily improved.

[0023] The curing agent used for curing the urethane resin of this embodiment is not particularly limited. For example, it can be appropriately selected from commercially available curing agents including hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, xylylene diisocyanate and its hydrogenated product, or diphenylmethane diisocyanate and its hydrogenated product, etc. and used. The pattern layer 3 is usually formed by printing pattern ink using the urethane resin of this embodiment as a binder resin on the colored thermoplastic resin layer ②, but other resin components may be added as necessary.

[0024] In addition to the binder resin, the components of the pattern ink can include various additives such as colorants (pigments, dyes, etc.), extenders, solvents, and light stabilizers. Examples of pigments include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolon, cobalt, phthalocyanine, carbon, titanium dioxide, iron oxide, mica, and other pearl pigments. The method for creating the image layer 3 is not particularly limited, and conventional printing methods such as gravure printing, offset printing, screen printing, flexographic printing, and inkjet printing can be used.

[0025] [Adhesive resin layer] The adhesive resin layer 4 comprises a polyester resin and a bisphenol A type epoxy resin, the polyester resin comprising phthalic acid, linear dicarboxylic acid, and alkylenediol as constituent elements. Furthermore, the polyester resin can be produced by known techniques (e.g., polycondensation reaction of dicarboxylic acid and diol). In this embodiment, the adhesive resin layer 4 is made by blending a bisphenol A type epoxy resin with the polyester resin described above, thereby enabling the decorative sheet 1 to exhibit practically sufficient moisture and heat resistance.

[0026] From the viewpoint of achieving both moisture and heat resistance and adhesion, the amount of bisphenol A type epoxy resin blended is preferably in the mass ratio of "polyester resin / bisphenol A type epoxy resin" = 50 / 50 to 90 / 10. If the blending ratio of bisphenol A type epoxy resin is too low, moisture and heat resistance will be insufficient, while if it is too high, adhesion may be insufficient.

[0027] The phthalic acid (in this embodiment, orthophthalic acid and terephthalic acid collectively refer to) which is a component of the polyester resin is used to enhance the moisture and heat resistance of the adhesive resin layer 4. The phthalic acid content is preferably in the range of (phthalic acid / linear dicarboxylic acid) = 45 / 55 to 85 / 15 in terms of molar ratio. If the phthalic acid content is too high, the adhesive resin layer 4 tends to become hard and brittle, which may adversely affect the adhesiveness. Conversely, if the content is too low, the adhesive strength may be insufficient due to insufficient cohesive force of the adhesive resin layer 4.

[0028] The linear dicarboxylic acid that is a component of the polyester resin is not particularly limited, and can be appropriately selected from, for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.

[0029] The alkylenediol component of the polyester resin can be, for example, (poly)ethylene glycol, (poly)propylene glycol, (poly)tetramethylene glycol, or (poly)hexamethylene glycol, but it is preferable to use neopentyl glycol in combination in terms of heat and humidity resistance.

[0030] The alkylenediol content is preferably within the range of {alkylenediol / (phthalic acid + linear dicarboxylic acid)} = 40 / 60 to 60 / 40 in terms of molar ratio. Polyester resins outside this numerical range have a small molecular weight, which may result in insufficient adhesion and heat resistance. The adhesive resin layer 4 can be formed using conventional coating methods such as gravure coating, microgravure coating, comma coating, knife coating, or die coating.

[0031] [Transparent thermoplastic resin layer] The transparent thermoplastic resin layer 5 is made of petroleum-derived polypropylene or chemically recycled polypropylene. A hydroxyphenyltriazine-based ultraviolet absorber is added to the transparent thermoplastic resin layer 5. The amount of the ultraviolet absorber is preferably in the range of 0.2% to 1.0% by mass relative to the resin constituting the transparent thermoplastic resin layer 5.

[0032] It is preferable that a hindered amine-based light stabilizer is added to the transparent thermoplastic resin layer 5. The content of the light stabilizer is preferably in the range of 0.2% to 1.0% by mass relative to the resin constituting the transparent thermoplastic resin layer 5. The thickness of the transparent thermoplastic resin layer 5 is preferably in the range of 10 μm to 150 μm. Furthermore, the density of the transparent thermoplastic resin layer 5 is 0.91 g / m³. 2 ~0.96g / m 2 It is preferable that it be within the range.

[0033] [Surface protective layer] The surface protection layer 6 is a layer provided to impart functions such as weather resistance, scratch resistance, stain resistance, and design properties to the decorative sheet 1. The material of the surface protection layer 6 is not particularly limited, and can be appropriately selected from resin materials such as urethane-based, acrylic-based, acrylic-silicone-based, fluorine-based, and epoxy-based materials.

[0034] The surface protective layer 6 may optionally contain various additives such as ultraviolet absorbers, heat stabilizers, light stabilizers, blocking inhibitors, catalyst scavengers, colorants, light scattering agents, and gloss modifiers. Triazine is particularly preferred as the ultraviolet absorber. The content of the ultraviolet absorber is preferably in the range of 2% to 15% by mass relative to the resin constituting the surface protective layer 6. Hindered amines are particularly preferred as the light stabilizer. The content of the light stabilizer is preferably in the range of 2% to 15% by mass relative to the resin constituting the surface protective layer 6.

[0035] The method for forming the surface protective layer 6 is not particularly limited. The aforementioned material is applied in a liquid form using conventional methods such as gravure coating, microgravure coating, comma coating, knife coating, or die coating, and then cured using a method suitable for the material, such as heat curing or ultraviolet curing, to form the surface protective layer 6. The thickness of the surface protective layer 6 should preferably be within the range of 3 μm to 20 μm. On the surface of the surface protective layer 6 opposite to the transparent thermoplastic resin layer 5, an embossed pattern 6a is formed. For example, the embossed pattern 6a can be a pattern that matches the pattern of the pattern layer 3, or a pattern that does not match the pattern. The embossed pattern 6a may be provided as needed.

[0036] [Adhesive layer] The adhesive layer 7 is a layer that provides tackiness to the colored thermoplastic resin layer 2. Multiple grooves 7a may be formed on the side of the adhesive layer 7 opposite to the colored thermoplastic resin layer 2. The groove 7a either terminates at the outer periphery of the adhesive layer 7 or communicates with other grooves 7a that terminate at the outer periphery of the adhesive layer 7. This allows air trapped between the adhesive layer 7 and the adherend to escape to the surroundings when the decorative sheet 1 is attached to the adherend. After the air has escaped to the surroundings, the bottom of the groove 7a can be made to adhere to the surface of the adherend, thereby making it disappear. Furthermore, by making the bottom of the groove 7a adhere to the surface of the adherend, impact resistance and cold resistance can be improved.

[0037] [Mizobe] The cross-sectional shape of the groove 7a can be, for example, V-shaped, U-shaped, rectangular, trapezoidal, or the like. As a method for forming the grooves 7a, for example, an adhesive can be uniformly applied to the side of the colored thermoplastic resin layer 2 opposite to the pattern layer 3, and then the grooves 7a can be formed by pressing with a mold having irregularities for forming the grooves 7a. Alternatively, a method can be adopted in which the grooves 7a can be formed by attaching a release paper layer 8 having irregularities for forming the grooves 7a.

[0038] [Release layer] The material constituting the release paper layer 8 is not particularly limited. Any material that can maintain the tackiness of the adhesive layer 7 by covering it can be used.

[0039] [Method for manufacturing decorative sheets] Next, an example of a method for manufacturing a decorative sheet according to this embodiment will be described. First, a colored thermoplastic resin layer 2 is formed using polyolefin as the base material. The thickness of the colored thermoplastic resin layer 2 may be in the range of 30 μm to 100 μm. Next, after surface treatment is applied to one side of the colored thermoplastic resin layer 2 as necessary, a pattern is printed on the surface-treated side of the colored thermoplastic resin layer 2 using a pattern ink that uses a urethane resin containing at least polycaprolactone polyol, polyalkylene glycol, and polyisocyanate as a binder resin, thereby forming the pattern layer 3.

[0040] Furthermore, an adhesive resin layer 4 containing polyester resin and bisphenol A type epoxy resin, and a surface protection layer 6 are laminated on the pattern layer 3 in that order. Then, infrared light (irradiation light) is applied to the laminate formed by these layers from the surface protection layer 6 side, and immediately after infrared irradiation, an embossing plate such as an embossing roll is pressed onto the surface of the surface protection layer 6 to form a raised and lowered pattern 6a. Next, an adhesive was applied to the side of the colored thermoplastic resin layer 2 opposite to the pattern layer 3, and a release paper was placed on top of it. This formed a decorative sheet 1 having an adhesive layer 7 and a release paper layer 8.

[0041] [Effects of this embodiment] (1) The decorative sheet 1 according to this embodiment is laminated in the following order: a colored thermoplastic resin layer, a pattern layer, a transparent thermoplastic resin layer, and a surface protection layer. The pattern layer contains a urethane resin as a binder resin, which includes polycaprolactone polyol, polyalkylene glycol, and polyisocyanate as constituent elements, and has a maximum point stress of 15 N / mm after a 192-hour pressure cooker test. 2Furthermore, the adhesive strength to the polypropylene board is 5N / 25mm or more. Therefore, a decorative sheet with excellent hydrolysis resistance and sufficient moisture and heat resistance can be obtained. In addition, the adhesion between the pattern layer and the transparent thermoplastic resin layer can be improved, making it suitable as a decorative sheet for exterior use. Moreover, by including neopentyl glycol as a component of the urethane resin, moisture and heat resistance can be further improved.

[0042] Furthermore, conventional decorative tack sheets with an adhesive layer tend to lack flexibility, making them difficult to handle, especially when wrapping and applying them to an object by hand, requiring additional processing such as applying heat to soften the sheet. The decorative sheet 1 according to this embodiment has a maximum point stress of 15 N / mm² after a 192-hour pressure cooker test. 2 As described above, and because it possesses a certain degree of flexibility, the decorative sheet can be handled more easily. For example, it can be easily applied to objects with complex shapes, such as corners. Furthermore, since an adhesive layer 7 is provided on the side opposite to the surface protective layer 6 of the decorative sheet 1, when attaching the decorative sheet 1 to an object, it can be attached simply by peeling off the release paper layer 8, eliminating the need to apply a separate adhesive, thus making the attachment process even easier.

[0043] (2) Since grooves 7a are provided on the side of the adhesive layer 7 of the decorative sheet 1 that faces the release paper layer 8, when the decorative sheet 1 is attached to an object, for example, air can easily escape through the grooves 7a. As a result, the decorative sheet can be easily handled, and the air removal process during application can also be easily performed, making the application of the decorative sheet even easier.

[0044] (3) The transparent thermoplastic resin layer 5 is composed of a resin made of petroleum-derived polypropylene or chemically recycled polypropylene and a hydroxyphenyltriazine-based ultraviolet absorber, thereby further improving the moisture and heat resistance of the decorative sheet. Furthermore, by including a hindered amine-based light stabilizer, the weather resistance of the decorative sheet can be improved.

[0045] (4) The adhesive resin layer 4 is formed by comprising polyester resin and bisphenol A type epoxy resin, and the polyester resin further comprises phthalic acid, linear dicarboxylic acid, and alkylenediol as constituent elements, and the content of polyester resin and bisphenol A type epoxy resin is set to be in the range of "polyester resin / bisphenol A type epoxy resin" = 50 / 50 to 90 / 10 in terms of mass ratio, thereby improving the adhesion between the pattern layer 3 and the transparent thermoplastic resin layer 5, as well as improving the weather resistance of the decorative sheet, and making it possible to obtain a decorative sheet with excellent durability.

[0046] (5) As described above, a decorative sheet with excellent durability, moisture and heat resistance, and weather resistance can be obtained, making it less likely for the decorative sheet to peel off over a long period of time, and thus suitable for exterior decorative sheets as well as decorative sheets for repairs. When used as a decorative sheet for repairs, the adhesive layer 7 allows it to be easily applied over already attached decorative sheets, eliminating the need to apply additional adhesives, thus simplifying repair work.

[0047] (6) By forming the adhesive layer 7 with grooves on the side that comes into contact with the colored thermoplastic resin layer 2, it becomes easier to remove air, making the application of the decorative sheet easier and allowing the decorative sheet to adhere sufficiently to the object.

[0048] [Variation] As shown in Figure 2, the decorative sheet 1 according to the above embodiment may be used to attach the adhesive layer 7 to at least a portion of the surface of the exterior material 9 by peeling off the release paper layer 8, thereby forming a decorative member 10. In the decorative member 10, the decorative sheet 1 only needs to be provided on at least one side of the exterior material 9, or it may be provided on both sides. [Examples]

[0049] [Example 1] After applying corona discharge treatment to one side of a colored thermoplastic resin layer, which is made of a colored thermoplastic resin as a base material, a pattern layer made of urethane-based printing ink, a urethane-based adhesive layer, a transparent adhesive resin layer, a transparent thermoplastic resin layer mainly composed of polypropylene, and a surface protection layer mainly composed of an acrylic resin composition were laminated in this order. Details of each layer are as follows.

[0050] (Colored thermoplastic resin layer (base material)) Material: Polyethylene Thickness: 55 μm (Picture layer) (Adjustment of urethane-based printing inks) Polycaprolactone diol, polytetramethylene glycol, and neopentyl glycol were used as the polyol components, and isophorone diisocyanate was used as the polyisocyanate. A known addition polymerization method was used to obtain a number-average molecular weight of 2 × 10⁻¹⁶. 4 A urethane resin with hydroxyl group terminals was synthesized. A copper phthalocyanine pigment was dispersed in this urethane resin in a mass ratio of pigment / urethane resin = 20 / 80 to prepare a pattern ink. An isocyanate curing agent was added to this pattern ink, and the pattern layer was formed by gravure printing onto an opaque polyethylene base material (colored thermoplastic resin layer, 55 μm thick).

[0051] (Transparent adhesive resin layer) Polyester diol (polyester resin) P was synthesized using isophthalic acid (IP) and adipic acid (AD) as dicarboxylic acids, and ethylene glycol and hexanediol as diols. IP / AD = 90 / 10 (molar ratio) Number average molecular weight: 1×10 4 Solids content hydroxyl value: 10 mg KOH / g A polyester diol (polyester resin) P was mixed with bisphenol A type epoxy resin EP (jER1004AF, manufactured by Mitsubishi Chemical Corporation) in a solid content mass ratio of P / EP = 70 / 30, and an isocyanate curing agent and a diluent solvent were added to prepare the adhesive.

[0052] (Transparent thermoplastic resin layer) Material: Chemically recycled polypropylene Thickness: 70 μm Weather-resistant agent Light stabilizer: Chinuvin 123 (manufactured by BASF Japan Ltd.) ... 0.5 parts by mass UV absorber: Tinosorb S (manufactured by BASF Japan Ltd.) ... 0.5 parts by mass A transparent thermoplastic resin layer was obtained by laminating a resin composition prepared by adding 0.5 parts by mass of a light stabilizer and 0.5 parts by mass of an ultraviolet absorber to 100 parts by mass of transparent chemically recycled polypropylene resin to a thickness of 70 μm.

[0053] (Surface protective layer) Main ingredient: Methyl methacrylate / 2-hydroxyethyl methacrylate =95 / 5 copolymer) 90 parts by mass UV absorber: Chinuvin 479; manufactured by BASF Japan Ltd. ... 9 parts by mass Light stabilizer: Chinuvin 123 (manufactured by BASF Japan Ltd.) ... 1 part by mass Hardener: Takenate D170 (manufactured by Mitsui Chemicals, Inc.) ... 10 parts by mass Solvent: Ethyl acetate ··· 240 parts by mass Application amount: 10g / m² 2

[0054] (Laminated structure) The total thickness of the laminate consisting of a colored thermoplastic resin layer, a pattern layer, a urethane adhesive layer, a transparent adhesive resin layer, a transparent thermoplastic resin layer, and a surface protection layer, prepared using the above method. Total thickness: 135μm (Decorative sheet) A decorative sheet (with tack processing) was obtained by applying a 20 μm layer of "Olivine BPS5762K" adhesive manufactured by Toyo Chem Co., Ltd. to the side of the colored thermoplastic resin layer of the above laminate, and then laminating an embossed release paper layer onto it.

[0055] [Example 2] The decorative sheet of Example 2 (with tack processing) was obtained in the same manner as in Example 1, except that the composition of the colored thermoplastic resin layer was different in the decorative sheet of Example 1. (Colored thermoplastic resin layer (base material)) Material: Polypropylene Thickness: 70 μm

[0056] [Example 3] The decorative sheet of Example 3 (with tack processing) was obtained in the same manner as in Example 1, except that neopentyl glycol was not used as the polyol component in the urethane-based printing ink for the pattern layer of the decorative sheet of Example 1. [Example 4] In the decorative sheet of Example 1, the decorative sheet of Example 4 (with tack processing) was obtained by laminating a release paper layer that was not embossed, except that the adhesive layer did not have grooves for air release.

[0057] [Comparative Example 1] A decorative sheet (with tack processing) for Comparative Example 1 was obtained in the same manner as in Example 1, except that polytetramethylene glycol was not used as the polyol component in the urethane-based printing ink for the pattern layer of the decorative sheet of Example 1. [Comparative Example 2] A decorative sheet (with tack processing) was obtained in the same manner as in Example 1, except that polycaprolactone diol was not used as the polyol component in the urethane-based printing ink for the pattern layer of the decorative sheet of Example 1.

[0058] [Comparative Example 3] A decorative sheet (with tack processing) was obtained in the same manner as in Example 1, except that Olivine BPS5330 manufactured by Toyo Chem Co., Ltd. was used as the adhesive in the adhesive layer of the decorative sheet of Example 1. [Comparative Example 4] A decorative sheet (with tack processing) was obtained in the same manner as in Example 1, except that polytetramethylene glycol was not used as the polyol component in the urethane-based printing ink for the pattern layer of the decorative sheet of Example 1, and that no air-venting grooves were provided in the adhesive layer by laminating an unembossed release paper layer.

[0059] [Comparative Example 5] A decorative sheet (with tack processing) was obtained in the same manner as in Example 1, except that the thickness of the colored thermoplastic resin layer in the adhesive layer of the decorative sheet of Example 1 was set to 25 μm. [Comparative Example 6] A decorative sheet (with tack processing) was obtained in the same manner as in Example 1, except that the thickness of the colored thermoplastic resin layer in the adhesive layer of the decorative sheet of Example 1 was set to 110 μm. 〔evaluation〕 For each decorative sheet in the examples and comparative examples, the maximum point stress was measured, and the adhesion to the substrate, resistance to humidity and heat, adhesion (adhesion), long-term environmental testing, printability, and workability were evaluated.

[0060] (Maximum point stress) The maximum point stress was measured after a 192-hour pressure cooker test. The pressure cooker test was conducted under the following conditions. The samples were placed in a chamber heated to 105°C and 100% RH, ensuring they did not overlap, and left undisturbed in the chamber for the set test time. The sample width was 25 mm. The maximum point stress was measured under the following conditions. The T-shaped peel strength between the transparent thermoplastic resin layer and the colored thermoplastic resin layer (substrate) was measured (sample width: 25 mm, tensile speed: 50 mm / min).

[0061] (Adhesion to substrate) The T-shaped peel strength between the transparent thermoplastic resin layer and the colored thermoplastic resin layer (substrate) was measured (sample width: 25 mm, tensile speed: 50 mm / min). The evaluation criteria are as follows. ◎: The substrate breaks without forming a delamination interface. ○: Delamination surface is formed while substrate deformation occurs. △: A peeling surface is generated without deformation of the substrate. ×: Peeling occurred during sample handling, making measurement impossible.

[0062] (Heat and moisture resistance) After conducting a pressure cooker test (105°C, 100%RH, 192 hours) using a HAST chamber, the T-peel strength between the transparent thermoplastic resin layer and the colored thermoplastic resin layer (substrate) was measured (sample width: 25 mm, tensile speed: 50 mm / min). The evaluation criteria are as follows. ◎: The substrate breaks without forming a delamination interface. ○: Delamination surface is formed while substrate deformation occurs. △: A peeling surface is generated without deformation of the substrate. ×: Peeling occurred during sample handling, making measurement impossible.

[0063] (Adhesion / Stickyness) After leaving the decorative sheet (including the adhesive layer) for 30 minutes, it is bonded to a polypropylene board, pressed back and forth with a 2kg load roll, and the adhesive strength is measured after 24 hours. The measurement involved peeling the material in a 180° direction at a speed of 300 mm / min, and recording its strength. A value of 5N / 25mm or higher was considered acceptable (○).

[0064] (Long-term environmental test (adhesion)) The decorative sheet (including the adhesive layer) was bonded to an aluminum plate, pressed back and forth with a 2 kg load roll, and after the following repeated temperature and water resistance tests were performed, the adhesive strength was measured. Adhesion strength was measured by peeling the material in a 180° direction at a speed of 50 mm / min, and the strength was recorded. A value of 20 N / mm or higher was considered acceptable (〇). · Repeated heat and cold test: Repeat the cycle of exposing the test piece to an environment of 80°C for 2 hours and then to an environment of -20°C for 2 hours, 100 times. · Water resistance test: Expose the test piece in warm water at 40°C for 500 hours.

[0065] (Printing suitability) 〇: It can be printed normally without flare and there is no peeling of the printed pattern. ×: Flare occurs and it cannot be printed normally. (Workability) The workability when laminating the decorative sheet (including the adhesive layer) to the aluminum plate was evaluated. 〇: It is easy to remove air and the decorative sheet does not wrinkle. Also, the reworkability when re-laminating is good and it is easy to handle. △: It is easy to remove air and the decorative sheet does not wrinkle, but the reworkability is poor and it is a bit difficult to handle. ×: It is difficult to remove air and air enters the working surface. Also, the reworkability is poor and it is difficult to handle. It is stiff and the sheet bounces back. The evaluation results are shown in Table 1.

[0066]

Table 1

[0067] 〔Results〕 The decorative sheets of Examples 1 to 4, which contain a urethane resin containing polycaprolactone polyol, polyalkylene glycol, and polyisocyanate as components in the pattern layer and have a maximum principal stress of 15 N / mm or more after a 192-hour pressure cooker test and an adhesive force to the polypropylene plate of 5 N / 25 mm or more, were confirmed to obtain good results in terms of substrate adhesion (between the colored thermoplastic resin layer and the transparent thermoplastic resin layer), heat and humidity resistance, adhesion (between the polypropylene plate and the decorative sheet), and long-term environmental tests. Furthermore, it was confirmed that the heat and humidity resistance was further improved by adding neopentyl glycol to the pattern layer. Also, it was confirmed that the workability was improved by providing the groove 7a in the adhesive layer. 2

[0068] Furthermore, the present invention can take the following configuration, for example. (1) A colored thermoplastic resin layer, a pattern layer, and a transparent thermoplastic resin layer are laminated in order, The colored thermoplastic resin layer has an adhesive layer and a release paper layer laminated on the side opposite to the pattern layer, The aforementioned pattern layer contains a urethane resin as a binder resin, which includes polycaprolactone polyol, polyalkylene glycol, and polyisocyanate as constituent elements. The maximum point stress after a 192-hour pressure cooker test was 15 N / mm². 2 A decorative sheet characterized by having the above characteristics and an adhesive strength of 5N / 25mm or more to a polypropylene board.

[0069] (2) The decorative sheet according to (1) above, further comprising neopentyl glycol as a component of the urethane resin. (3) The decorative sheet according to (1) or (2) above, characterized in that the colored thermoplastic resin layer contains a polyolefin resin, and the thickness of the colored thermoplastic resin layer is 30 μm or more and 100 μm or less.

[0070] (4) The transparent thermoplastic resin layer comprises a resin made of petroleum-derived polypropylene or chemically recycled polypropylene, a hydroxyphenyltriazine-based ultraviolet absorber, and a hindered amine-based light stabilizer. The decorative sheet according to any one of (1) to (3) above, characterized in that the content of the ultraviolet absorber in the resin is in the range of 0.2% by mass or more and 10% by mass or less, and the content of the light stabilizer in the resin is in the range of 0.2% by mass or more and 10% by mass or less. (5) The transparent thermoplastic resin layer has a thickness of 10 μm to 150 μm and a density of 0.91 g / m³. 2 More than 0.96g / m 2The decorative sheet described in (4) above, characterized in that it is as follows.

[0071] (6) The pattern layer and the transparent thermoplastic resin layer are bonded together by an adhesive resin layer. The adhesive resin layer comprises a polyester resin and a bisphenol A type epoxy resin. The polyester resin contains phthalic acid, linear dicarboxylic acid, and alkylenediol as constituent elements. The decorative sheet according to any one of the above (1) to (5), characterized in that the content of the polyester resin and the bisphenol A type epoxy resin is in the range of "polyester resin / bisphenol A type epoxy resin" = 50 / 50 to 90 / 10 in terms of mass ratio.

[0072] (7) The transparent thermoplastic resin layer has a surface protective layer on the side opposite to the pattern layer, The decorative sheet according to any one of (1) to (6) above, characterized in that the surface protective layer contains at least one of the following: an ultraviolet absorber, a heat stabilizer, a light stabilizer, an anti-blocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a gloss modifier. (8) The decorative sheet according to any one of (1) to (7) above, characterized in that the adhesive layer has grooves on the surface that is in contact with the colored thermoplastic resin layer. (9) A decorative sheet according to any one of the above items (1) to (8), characterized in that it is attached to exterior materials. (10) Exterior materials and A decorative member characterized by comprising a decorative sheet according to any one of the above items (1) to (8) provided on at least a portion of the surface of the exterior material. [Explanation of symbols]

[0073] 1 Decorative sheet 2 Colored thermoplastic resin layer 3 Pattern Layers 4 Adhesive resin layer 5 Transparent thermoplastic resin layer 6 Surface protective layer 6a Embossed pattern 7. Adhesive layer 7a Groove 8. Release liner layer 9. Exterior materials 10 Decorative components

Claims

1. A colored thermoplastic resin layer, a pattern layer, and a transparent thermoplastic resin layer are laminated in order, The colored thermoplastic resin layer has an adhesive layer and a release paper layer laminated on the side opposite to the pattern layer, The aforementioned pattern layer contains a urethane resin as a binder resin, which includes polycaprolactone polyol, polyalkylene glycol, and polyisocyanate as constituent elements. The maximum point stress after a 192-hour pressure cooker test was 15 N / mm². ２ A decorative sheet characterized by having the above characteristics and an adhesive strength of 5 N / 25 mm or more to a polypropylene board.

2. The decorative sheet according to claim 1, further comprising neopentyl glycol as a component of the urethane resin.

3. The decorative sheet according to claim 1 or 2, characterized in that the colored thermoplastic resin layer contains a polyolefin resin, and the thickness of the colored thermoplastic resin layer is 30 μm or more and 100 μm or less.

4. The transparent thermoplastic resin layer comprises a resin made of petroleum-derived polypropylene or chemically recycled polypropylene, a hydroxyphenyltriazine-based ultraviolet absorber, and a hindered amine-based light stabilizer. The decorative sheet according to claim 1 or 2, characterized in that the content of the ultraviolet absorber in the resin is in the range of 0.2% by mass or more and 10% by mass or less, and the content of the light stabilizer in the resin is in the range of 0.2% by mass or more and 10% by mass or less.

5. The transparent thermoplastic resin layer has a thickness of 10 μm to 150 μm and a density of 0.91 g / m³. ２ 0.96g / m or more ２ The decorative sheet according to feature 4 below.

6. The pattern layer and the transparent thermoplastic resin layer are bonded together by an adhesive resin layer. The adhesive resin layer comprises a polyester resin and a bisphenol A type epoxy resin. The polyester resin contains phthalic acid, linear dicarboxylic acid, and alkylenediol as constituent elements. The decorative sheet according to claim 1 or 2, characterized in that the content of the polyester resin and the bisphenol A type epoxy resin is in the range of "polyester resin / bisphenol A type epoxy resin" = 50 / 50 to 90 / 10 in terms of mass ratio.

7. The transparent thermoplastic resin layer has a surface protective layer on the side opposite to the pattern layer, The decorative sheet according to claim 1 or 2, characterized in that the surface protective layer contains at least one of the following: an ultraviolet absorber, a heat stabilizer, a light stabilizer, an anti-blocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a gloss modifier.

8. The decorative sheet according to claim 1 or 2, characterized in that the adhesive layer has grooves on the surface that is in contact with the colored thermoplastic resin layer.

9. The decorative sheet according to claim 1 or 2, characterized in that it is attached to exterior materials.

10. Exterior materials and A decorative member comprising a decorative sheet according to claim 1 or claim 2, provided on at least a portion of the surface of the exterior material.

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