JP2005104048A - Decorative sheet with temporarily bonded protective sheet and decorative sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative sheet with a temporarily bonded protective sheet enhanced in moldability, mirror surface properties and design properties when bonded to an adherend member having a curved surface part and excellent in scratch resistance and anti-staining properties. <P>SOLUTION: This decorative sheet with the temporarily bonded protective sheet is constituted by providing a temporarily bonded protective sheet 7, which is composed of a temporarily bonding base material sheet 71 and a pressure-sensitive adhesive layer 72 with the adhesive layer faced to the decorative sheet, on the surface of the protective film side of a decorative sheet 1 obtained by laminating a three-layered laminated sheet 5 containing a colorant at least in one layer thereof, an adhesive layer 4, a color ink layer 3, a transparent sheet 2 thinner than the three-layered laminated sheet 5 and a protective layer 6 in this order. The three-layered laminated sheet 5 is formed of a non-stretched resin layer 52 of polyethylene terephthalate forming a core layer and the copolyester resin layers 51 and 53 based on terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol formed on both upper and rear surfaces of the resin layer 52. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a decorative sheet with a temporary protective sheet, a decorative sheet, a decorative member with a temporary protective sheet, and a decorative member, and more specifically, formability when adhered to an adherent member having a curved surface portion, sheet surface The present invention relates to a decorative sheet excellent in specularity and design at a curved surface, and further excellent in scratch resistance and stain resistance, and a decorative member stuck on the decorative sheet.

  As a decorative sheet 11 used for surface materials such as furniture, doors, door frames, waistboards, window frames, etc., as shown in FIG. 6, for example, transparent sheet 12 / colored ink layer 13 / base resin layer that may be concealed and colored A laminated sheet consisting of 14 is generally used. Such a decorative sheet is generally manufactured by bonding a transparent sheet and a base resin layer by heat fusion.

Conventionally, a vinyl chloride resin has been widely used as a constituent material of such a decorative sheet (see, for example, Patent Document 1 and Patent Document 2). However, since a vinyl chloride resin generates hydrogen chloride during combustion, a polyolefin resin that is a non-vinyl chloride resin has been studied as an alternative material (see, for example, Patent Document 3).
Japanese Patent Publication No. 28-5036 (1st page) Japanese Patent Publication No.58-14312 (Fig. 4) JP 10-2111675 A

  A decorative sheet to be attached to an adherent member having a curved surface portion is required to have excellent follow-up properties so that no float or wrinkle is generated after the attachment. However, when a decorative sheet is formed using a polyolefin-based resin softened to the extent that the followability at the curved surface portion is satisfied, the surface of the sheet undulates when the decorative sheet is attached to the adherend, There has been a problem that the unevenness of the surface of the adherend member is raised after wearing, and the specularity (smoothness) of the surface of the decorative sheet is lowered.

  Further, since the polyolefin-based resin has a so-called necking property in which elongation is concentrated in a local portion when pulled, a decorative sheet having the conventional configuration (see FIG. 6) is made of this resin. When pasted on an adherent member having a curved surface portion, there has been a problem that remarkable elongation occurs in the decorative sheet at the curved surface portion.

  For example, FIG. 7 shows the elongation in the surface direction of each layer of the decorative sheet adhered to the adherend member 15 having a curved surface portion, but the curved surface portion is elongated at an arbitrary position in the thickness direction. It is considered that there is no neutral point N, the degree of compression increases from the neutral point N toward the adherend member 15 side, and the remarkable elongation x ′ occurs in each layer of the decorative sheet 11 toward the external space side. It was.

  In particular, when a remarkable elongation x ′ occurs in the colored ink layer 13, the thickness of the layer becomes thin, causing a thin pattern or color, and further, the color tone of the base resin layer 14 as a lower layer is caused by the thin color. There was a problem of seeing through. In FIG. 7, x ′ represents the elongation in the layer, the range surrounded by the one-dot broken line represents the range where the elongation x ′ occurs, and the range surrounded by the two-dot broken line represents the range where the shrinkage occurs. .

  In addition, a decorative member formed by attaching a decorative sheet to an adherent member has a surface of the decorative sheet during various processing, distribution, sales, delivery, construction, etc. before being delivered to the consumer as a product. There was a problem of being scratched and contaminated. Further, such a decorative member has a problem that the surface of the decorative sheet is damaged and contaminated when the consumer uses it after reaching the consumer's hand as a product.

  The present invention has been made in order to solve the above-mentioned problems, and its purpose is to formability when adhered to an adherend member having a curved surface portion, specularity of the sheet surface, and design in the curved surface portion. An object of the present invention is to provide a decorative sheet having improved properties and excellent scratch resistance and stain resistance. Moreover, it is providing the decorative member stuck with the decorative sheet.

  The decorative sheet with a temporary protective sheet according to the first embodiment of the present invention for solving the above problems is a three-layer laminated sheet containing a colorant in at least one layer, an adhesive layer, a colored ink layer, On the surface of the decorative sheet formed by laminating a transparent sheet thinner than the three-layer laminated sheet in this order, a temporary protective sheet comprising a temporary base material sheet and an adhesive layer is provided with the adhesive. A decorative sheet with a temporary protective sheet provided on the decorative sheet side, wherein the three-layer laminated sheet is formed on both sides of the unstretched resin layer of polyethylene terephthalate and the unstretched resin layer. Formed of a copolymerized polyester resin layer mainly composed of terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol, and the adhesive layer mainly comprises a polyol and an isocyanate. The transparent sheet and the temporary bonding base sheet are formed of a copolymerized polyester resin mainly composed of terephthalic acid, isophthalic acid, and ethylene glycol. And

  According to this invention, since a soft resin is used for the three-layer laminated sheet and a resin that is relatively hard but not too rigid is used for the transparent sheet, the followability to the adherend having a curved surface portion is improved. At the same time, the specularity of the decorative sheet surface can be improved.

  According to the present invention, the surface of the transparent sheet on the colored ink layer side and the three-layer laminated sheet made of a soft resin are bonded together with the above-described adhesive layer that is hard and hardly stretched. When the decorative sheet adheres to the curved surface portion, even if the decorative sheet follows the curved surface portion, the elongation of the three-layer laminated sheet is not transmitted to the colored ink layer, and the colored ink layer near the adhesive layer has a significant elongation. Does not occur. Furthermore, since the colored sheet is adjacent to the transparent sheet that is less likely to stretch than the three-layer laminated sheet, the elongation is suppressed. In addition, since the three-layer laminate sheet absorbs most of the elongation generated by the large elongation of the three-layer laminate sheet made of a soft resin, this also suppresses the elongation of the colored ink layer. . As a result, by suppressing the elongation of the colored ink layer, it is difficult for the pattern and color fading to occur due to the thickness of the colored ink layer being thin, and further, the color tone of the three-layer laminated sheet due to the color fading can be seen through. Can be prevented.

  According to this invention, since the temporary protection sheet is provided on the surface of the decorative sheet on the transparent sheet side, various processing, distribution, sale, delivery or construction before the decorative member is delivered to the consumer as a product. During the process, the surface of the decorative sheet can be prevented from being damaged or contaminated. Moreover, since the temporary attachment base sheet of the temporary protection sheet is formed of the same material as that of the transparent sheet, both sheets have the same mechanical properties at various temperatures. As a result, even when this decorative sheet with a temporary protective sheet is attached to an adherent member having a curved surface at various temperatures, it is difficult for the temporary protective sheet and the decorative sheet to float or peel off, Floating between the decorative sheet and the adherent member and deformation of the decorative sheet itself are less likely to occur. The temporary protective sheet is peeled off when the decorative member is used for consumer use.

  In addition, a decorative sheet with a temporary protective sheet according to the second embodiment of the present invention for solving the above-mentioned problem is a three-layer laminated sheet containing a colorant in at least one layer, an adhesive layer, and a colored ink layer And a temporary attachment protection composed of a temporary attachment base sheet and an adhesive layer on the surface of the decorative sheet formed by laminating a transparent sheet thinner than the three-layer laminated sheet and a protective film in this order. The sheet is a decorative sheet with a temporary protective sheet provided with the pressure-sensitive adhesive layer side of the decorative sheet, and the three-layer laminated sheet comprises an unstretched resin layer of polyethylene terephthalate and the unstretched resin layer. Formed on both sides with a copolymerized polyester resin layer mainly composed of terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol, wherein the adhesive layer comprises a polyol and an isocyanate. The transparent sheet and the temporary bonding base sheet are formed of a copolymerized polyester resin mainly composed of terephthalic acid, isophthalic acid and ethylene glycol. It is characterized by.

  According to this invention, since the protective film is provided on the outer surface of the transparent sheet in addition to the configuration of the decorative sheet with the temporary protective sheet according to the first embodiment of the present invention, It is possible to prevent the sheet surface of the decorative member from which the temporary protective sheet is peeled off after being crossed from being damaged or contaminated during use by the consumer.

  The decorative sheet of the present invention for solving the above problems is a three-layer laminated sheet containing a colorant in at least one layer, an adhesive layer, a colored ink layer, and a transparent sheet thinner than the three-layer laminated sheet, , A protective sheet, and a three-layer laminated sheet formed of polyethylene terephthalate unstretched resin layer and both surfaces of the unstretched resin layer, terephthalic acid, ethylene glycol And a copolymerized polyester resin layer mainly composed of 1,4-cyclohexanedimethanol, and the adhesive layer is formed of a two-component curable urethane resin mainly composed of polyol and isocyanate, and the transparent layer. The sheet is formed of a copolyester resin mainly composed of terephthalic acid, isophthalic acid and ethylene glycol.

  In the decorative sheet or decorative sheet with the temporary protective sheet of the present invention, the two-component curable urethane resin preferably has a three-dimensionally crosslinked molecular structure.

  According to this invention, since the adhesive layer is formed of a two-component curable urethane resin having a three-dimensionally cross-linked molecular structure, the adhesive layer is hard and difficult to stretch, and the colored ink layer in the vicinity of the adhesive layer And the like, and adverse effects caused by significant elongation in these layers can be prevented.

  The decorative member with a temporary protective sheet according to the present invention for solving the above-mentioned problems is characterized in that the decorative sheet with a temporary protective sheet according to the present invention described above is adhered to an adherent member having a curved surface portion. And

  According to the present invention, since the decorative sheet with the temporary protective sheet having the above-described characteristics is attached to the adherend member, the decorative sheet is less likely to be floated or wrinkled, and at the same time has excellent formability at the curved surface portion. It is possible to obtain a decorative member in which unevenness on the surface of the member is hardly raised and the mirror surface of the decorative sheet surface is excellent. In addition, since the decorative sheet with the temporary protective sheet having the above-described characteristics is attached to the adherend member, it is difficult for the pattern and color fading and the pattern elongation on the curved surface portion to occur, and furthermore, the three layers are laminated by the fading of the color. A decorative member in which the color tone of the sheet is not seen through can be obtained. In addition, according to the present invention, it is possible to improve the scratch resistance and stain resistance of the decorative member before and after the product reaches the consumer.

  The decorative member according to the present invention for solving the above-described problems is characterized in that the decorative sheet of the present invention described above is adhered to an adherent member having a curved surface portion.

  According to the decorative sheet with a temporary protection sheet and the decorative sheet of the present invention, it is possible to improve the moldability of the decorative sheet attached to the adherend member having the curved surface portion and also improve the specularity of the sheet surface. it can. Further, it is possible to suppress the pattern and color fading of the decorative sheet formed on the adherend member having the curved surface portion, the elongation of the pattern, and the like, and further prevent the color tone of the three-layer laminated sheet from being seen through due to the fading of the color. The design of the decorative member can be improved. Furthermore, according to the decorative sheet with a temporary attachment protective sheet of the present invention, before the decorative member bonded to the adherend member reaches the consumer's hand as a product and / or after the consumer's hand, The sheet surface can be protected from scratches and contamination. Moreover, according to the decorative sheet provided with a protective film on the surface of the present invention, the sheet surface can be protected from scratches and contamination after the decorative member reaches the consumer as a product.

  According to the decorative member with a temporary protection sheet and the decorative member of the present invention, the decorative sheet can be improved in formability at the curved surface portion without being lifted or wrinkled, and at the same time, the unevenness of the adherent member is raised. The mirror surface property of the sheet surface can be improved without being seen. In addition, the decorative sheet has no pattern or color fading or pattern elongation on the curved surface, and the color tone of the three-layer laminated sheet cannot be seen through, and the design is excellent. In addition, according to the decorative member with a temporary attachment protective sheet of the present invention, the sheet surface is difficult to be scratched and dirty before it reaches the consumer's hand as a product and / or after the consumer's hand. It becomes difficult. According to the decorative member having a protective film on the surface of the present invention, after reaching the consumer's hand as a product, the sheet surface from which the temporary protective sheet is peeled is hardly scratched or difficult to be stained. .

  Hereinafter, the decorative sheet and the decorative member of the present invention will be described with reference to the drawings. Note that the present invention is not limited thereby. Further, in the present specification, “a decorative sheet and a decorative sheet with a temporary protective sheet” may be referred to as “decorative sheet or the like” and “a decorative member and a decorative member with a temporary protective sheet” may be referred to as “a decorative member or the like”. .

  FIG. 1 is a cross-sectional view showing an example of the decorative sheet of the present invention, FIG. 2 is a cross-sectional view of an example of the decorative member of the present invention, and FIG. 3 shows an adherent member having a curved surface portion. It is sectional drawing which shows the expansion | extension of the surface direction of each layer of the decorative sheet with a temporary protection sheet stuck.

  As shown in FIG. 1, the decorative sheet of the present invention is a decorative sheet having a multilayer structure comprising a transparent sheet 2, a colored ink layer 3, an adhesive layer 4, and a three-layer laminated sheet 5, and the transparent sheet 2 side. A decorative sheet 1 with a temporary protective sheet 7 (FIG. 1 (A)), a protective film 6, a transparent sheet 2, a colored ink layer 3, adhesive layers 4 and 3 provided with a temporary protective sheet 7 on the outermost surface of A multi-layer decorative sheet 1 (FIG. 1 (B)) composed of a layer laminated sheet 5 or a multilayer structure composed of a protective film 6, a transparent sheet 2, a colored ink layer 3, an adhesive layer 4 and a three-layer laminated sheet 5. There are three modes of the decorative sheet 1 with the temporary protective sheet 7 (FIG. 1C) provided with the temporary protective sheet 7 on the outermost surface on the transparent sheet side. The three-layer laminated sheet 5 is a multilayer structure sheet composed of a first resin layer 51, a second resin layer 52, and a third resin layer 53 from the adhesive layer 4 side. Further, the temporary protective sheet 7 is a sheet composed of a temporary base material sheet 71 and an adhesive layer 72. The protective film 6 is an arbitrary configuration of the decorative sheet 1, and the temporary protective sheet 7 is also optionally provided on the decorative sheet 1.

  The decorative sheet 1 or the like has a surface on the colored ink layer 3 side of the transparent sheet 2 in which the protective film 6 and the temporary protective sheet 7 are formed on one surface and the colored ink layer 3 is formed on the other surface, It is formed by bonding the first resin layer 51 of the three-layer laminated sheet 5 thicker than the transparent sheet 2 via the adhesive layer 4.

  Further, as shown in FIG. 2, the decorative member or the like of the present invention may or may not have a decorative sheet 1 with a temporary protective sheet 7 (with or without a protective film 6) on an adherent member 8 having a curved surface portion. ) Is attached to the decorative member 10 with the temporary protective sheet 7 (FIG. 2A) or the adherent member 8 having a curved surface portion, the decorative sheet 1 having the protective film 6 on the surface thereof. There are two modes of the decorative member 10 (FIG. 2B) formed by sticking.

(Transparent sheet)
The transparent sheet 2 is positioned on the outermost surface on the side that is not attached to the adherent member 8 among the essential constituent elements of the decorative sheet 1, and after the decorative sheet 1 is attached to the adherent member 8, its surface specularity. In addition, it plays a role of maintaining surface durability such as weather resistance and wear resistance.

  The constituent material of the transparent sheet 2 is selected from thermoplastic polyester resins that can play the above-described role and have excellent solvent resistance. Solvent resistance refers to the property of not dissolving or sticking to an organic solvent. In the present invention, such a property is required for producing the decorative sheet 1 by forming the colored ink layer 3 on the transparent sheet 2. The

  Among the thermoplastic polyester resins, copolymer polyethylene terephthalate having an ethylene terephthalate unit as a main constituent component is preferably used as the material for the transparent sheet 2 from the viewpoint of followability to the adherend.

  Examples of the "container having an ethylene terephthalate unit as a main constituent" include, for example, a terephthalic acid component containing at least about 75 mol% of the total dicarboxylic acid component and an ethylene glycol component containing at least about 75 mol% of the total diol component. It can be illustrated. As such copolymerized polyethylene terephthalate, for example, copolymerized polyester terephthalate having terephthalic acid, isophthalic acid and ethylene glycol as main components exemplified in paragraph numbers 0011 and 0012 of JP-A-2001-257129 can be preferably exemplified. The copolymerized polyester terephthalate mentioned in the publication has a melting point in the range of 210 to 245 ° C., a plane orientation coefficient in the range of 0.10 to 0.16, and 100 at 100 ° C. in the MD direction and the TD direction. Each of the resins has a stress at the time of% elongation in the range of 10 to 150 MPa. Here, the “MD direction” refers to a direction parallel to the film surface and along the film forming direction, and the “TD direction” refers to a direction parallel to the film surface and perpendicular to the film forming direction. Further, the plane orientation coefficient represents the orientation state of molecular chains in the film, and is calculated from the refractive index of each direction component of the film measured by the Abbe method, according to the general formula (1). means.

(Wherein P is the plane orientation coefficient, n _MD is the refractive index in the MD direction of the film, n _TD is the refractive index in the TD direction of the film, and n _Z is the refractive index in the thickness direction perpendicular to the film surface. Rate.)

  Since the copolymerized polyester terephthalate having the above-described characteristics is excellent in heat resistance, the transparent sheet 2 made of this copolymerized polyester terephthalate is not distorted by the heat applied to the adherend member. The sticking of the decorative sheet to the adherent member is facilitated. In addition, since such a copolymerized polyester terephthalate is relatively hard, the transparent sheet 2 formed from this resin has surface irregularities, surface roughness, uneven application of the adhesive layer, etc. on the surface thereof. I will not let you. Moreover, since such copolymer polyester terephthalate is not too rigid, the transparent sheet 2 formed from this resin has an advantage of improving the followability of the decorative sheet to the curved surface portion.

  The ratio of the copolymerization component of the copolymerized polyester terephthalate is adjusted so that the melting point of the copolymerized polyester terephthalate is in the range of 210 to 245 ° C. For example, when isophthalic acid is copolymerized with polyethylene terephthalate, the total dicarboxylic acid component It is preferable that the ratio of isophthalic acid occupying therein is in the range of approximately 5.5 to 18 mol%.

  The transparent sheet 2 is formed by a known method for producing a thermoplastic polyester film, such as a melt extrusion method.

  The thickness of the transparent sheet 2 is adjusted so that the colored ink layer 3 as a lower layer can be visually recognized and the unevenness of the adherend can be prevented from being raised, and is usually in the range of 20 to 100 μm. In addition, this thickness is thinner than the thickness of the 3 layer lamination sheet 5 mentioned later.

  The transparent sheet 2 thus formed is preferable as a weather resistance imparting layer because it is excellent in gloss retention, color retention, scratch resistance, stain resistance, water resistance, boiling water resistance and chemical resistance.

(Colored ink layer)
The colored ink layer 3 is a layer having one or more colors and patterns. The colored ink layer 3 may be in any form of a solid layer, a partial solid layer, a pattern layer, or a multi-color layer of two or more colors, and a pattern such as a painting, a logo, a character, a symbol, or a figure may be used. It may be formed. The colored ink layer 3 preferably has a solid layer containing a white pigment and / or a black pigment so as to conceal the color tone of the three-layer laminated sheet 5 and the background of the adherend, and the solid layer is transparent. Various patterns may be formed on the sheet side. In the decorative sheet 1 of the present invention, the three-layer laminated sheet 5 described later is concealed, so that the solid layer can be omitted for the purpose of concealing the color tone of the adherend. Of course, both may be used together, and in that case, the concealing effect of the adherend can be further improved.

  As a constituent material of the colored ink layer 3, a material obtained by kneading a pigment or dye colorant, a plasticizer, a stabilizer, other additives, a solvent or a diluent in a vehicle is used. As the vehicle, a two-component curable urethane resin is used. The two-component curable urethane resin is a urethane resin having a polyol as a main component and an isocyanate as a crosslinking agent (curing agent). As the polyol, those having two or more hydroxyl groups in the molecule are used, and for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol and the like are used. In addition, as the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in the molecule is used, for example, an aromatic isocyanate such as 2,4-tolylene diisocyanate, xylene diisocyanate or 4,4'-diphenylmethane diisocyanate, Alternatively, aliphatic (or alicyclic) isocyanate such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, or hydrogenated diphenylmethane diisocyanate can be used. As the isocyanate, adducts or multimers of the above-mentioned various isocyanates may be used. For example, an adduct of tolylene diisocyanate, a tolylene diisocyanate trimer, or the like can be used.

  As the coloring pigment, a commonly used organic or inorganic pigment can be used. Among these colored pigments, the yellow pigment includes an azo pigment such as monoazo, disazo or polyazo, an organic pigment such as isoindolinone, or an inorganic material such as yellow lead, yellow iron oxide, cadmium yellow, titanium yellow or antimony yellow. Pigments can be used. As the red pigment, azo pigments such as monoazo, disazo or polyazo, organic pigments such as quinacridone, or inorganic pigments such as petal, vermilion, cadmium red chrome or vermilion can be used. As the blue pigment, organic pigments such as phthalocyanine blue or indanthrene blue, or inorganic pigments such as bitumen, ultramarine blue, or cobalt blue can be used. Moreover, as a black pigment, organic pigments, such as aniline black, or inorganic pigments, such as carbon black, can be used. Moreover, as a white pigment, inorganic pigments, such as titanium dioxide, zinc white, or antimony trioxide, can be used.

  The coating liquid for the colored ink layer for forming the colored ink layer 3 includes an ultraviolet absorber, an ultraviolet shielding agent, a light stabilizer, a colorant, a heat stabilizer, an antistatic agent, a plasticizer, a curing agent, a lubricant, and the like. It is also possible to contain additives having various functions. In addition, it is preferable that the constituent material of the coloring ink layer 3 is resin which has moderate stretchability of the grade which can follow when a decorative sheet is affixed on the to-be-adhered member which has a curved-surface part.

  The colored ink layer 3 is formed by providing a colored ink layer coating liquid on the surface of the transparent sheet 2 by coating or printing, and then drying the coating liquid. The colored ink layer 3 constituting the decorative sheet of the present invention is not formed on the three-layer laminated sheet 5 that is a flexible elastic resin layer but on the transparent sheet 2 that is harder than the three-layer laminated sheet 5. Therefore, the problem of misregistration due to the elongation of the sheet due to the tension during printing, and blocking caused by the organic solvent contained in the coating liquid for the colored ink layer (when the printed sheets are wound or stacked) There is an advantage that the problem of adhesion between the printed ink and the non-printing surface of the sheet does not occur.

  As the coating method, various known methods such as roll coating, curtain flow coating, wire bar coating, reverse roll coating, gravure coating, gravure reverse coating, and micro gravure coating can be used. In addition, as printing methods, various known methods such as relief printing such as gravure, letterpress and flexo, lithographic printing such as lithographic offset and dilitho printing, stencil printing such as silk screen, electrostatic printing and ink jet printing are used. Can do. Although the thickness of the colored ink layer 3 is not particularly limited, it is usually formed with a thickness of about 1 to 10 μm, for example.

(Adhesive layer)
The adhesive layer 4 is formed by bonding the transparent sheet 2 on which the colored ink layer 3 is formed and the three-layer laminated sheet 5 with good adhesion, and when the adhesive layer 4 is adhered to an adherent member having a curved surface portion. It has a role of suppressing the elongation of the sheet 2 and preventing harmful effects caused by the elongation.

  As the adhesive used for the adhesive layer 4, a two-component curable urethane resin is preferably used.

  The two-component curable urethane resin is a urethane resin having a polyol as a main component and an isocyanate as a crosslinking agent (curing agent). The polyol is a compound having two or more hydroxyl groups in the molecule, and for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol or the like is used. In addition, as the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in the molecule is used, for example, an aromatic isocyanate such as 2,4-tolylene diisocyanate, xylene diisocyanate or 4,4'-diphenylmethane diisocyanate, Alternatively, aliphatic (or alicyclic) isocyanates such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, or hydrogenated diphenylmethane diisocyanate are used. As the isocyanate, adducts or multimers of the above-mentioned various isocyanates may be used. For example, an adduct of tolylene diisocyanate, a tolylene diisocyanate trimer, or the like may be used.

  In the present invention, the adhesive layer 4 has a hardness that can suppress the elongation of a nearby layer when the decorative sheet 1 is attached to an adherent member having a curved surface portion. That is, the adhesive layer 4 needs to have a higher elastic modulus than the transparent sheet 2 made of a thermoplastic resin under a temperature of room temperature (about 20 to 25 ° C.) or higher. For that purpose, it is preferable to give the two-component curable urethane resin, which is the material of the adhesive layer 4, to a three-dimensionally crosslinked molecular structure. As such a two-component curable urethane resin, it is preferable to select a combination in which the average number of functional groups of the polyol and isocyanate is larger than 2 (exceeding 2). As the adhesive, other curable resins other than the two-component curable urethane resin, for example, an electron beam curable resin composed of a polyfunctional acrylate prepolymer or a polyfunctional monomer, an epoxy resin, and a moisture-humidity curable type 1 A liquid urethane resin or the like can also be used.

  Since the adhesive layer 4 made of such a two-component curable urethane resin becomes higher in elasticity than the transparent sheet 2 at a temperature of room temperature (about 20 to 25 ° C.) or higher, it becomes a hard and hardly stretchable layer. When the decorative sheet 1 is attached to an adherent member having a curved surface portion, the elongation of the layer located in the vicinity of the adhesive layer can be suppressed. In particular, when the elongation of the colored ink layer 3 is suppressed, it is possible to prevent the pattern and color fading and the elongation of the pattern due to the thickness of the colored ink layer 3 being reduced. Furthermore, it is possible to prevent the color tone of the three-layer laminated sheet 5 from being seen through due to the color fading of the colored ink layer 3. In addition, since the adhesive made of the two-component curable urethane resin is cured without applying high heat, the decorative sheet 1 can be prevented from being distorted by heat.

  In the following, the mechanism by which such an effect occurs will be considered. In the decorative sheet 1 of the present invention, the adhesive layer 4 which is hard and hardly stretched is formed adjacent to the colored ink layer 3, so that the decorative sheet 1 is attached to the adherend member 8 having a curved surface portion. The colored ink layer 3 is pulled in the shrinking direction by the adhesive layer 4, and the elongation x in the surface direction is small as shown in FIG. In FIG. 3, x indicates the elongation in the layer, and the range indicated by the one-dot broken line indicates the range in which the elongation in the layer occurs. As a result, the layer thickness of the colored ink layer 3 is not reduced, and it is difficult for the pattern and color to fade and the pattern to elongate, resulting in a result different from the conventional decorative sheet 11 shown in FIG.

  The adhesive layer 4 is usually formed by applying an adhesive to the surface of the colored ink layer 3 formed on the transparent sheet 2, then laminating the three-layer laminated sheet 5, and then curing, A decorative sheet is formed. Also, an adhesive is applied to the surface of the three-layer laminated sheet 5, and then the transparent sheet 2 on which the colored ink layer 3 is formed is bonded so that the colored ink layer 3 side faces the three-layer laminated sheet 5, and then cured. You may form by making.

  As an adhesive coating method, a known coating method such as roll coating, gravure coating, comma coating or the like can be used, and the thickness is preferably about 5 to 20 μm.

(Three-layer laminated sheet)
The three-layer laminated sheet 5 is a multilayer sheet composed of a first resin layer 51, a second resin layer 52, and a third resin layer 53. The three-layer laminated sheet 5 is softer than other layers constituting the decorative sheet (lower elastic modulus) and has a role of improving the followability to the adherend member. Each layer is made of a flexible resin.

  Among the three layers, the constituent material of the second resin layer 52 that forms the core layer is flexible enough to ensure followability to the curved surface portion of the adherend, particularly a three-dimensional curved surface portion such as a rectangular parallelepiped corner portion. An amorphous or low-crystalline thermoplastic polyester elastomer having For example, a polyethylene terephthalate resin for an unstretched resin layer that is inexpensive and widely used can be mentioned, and it is more preferable to add polybutylene terephthalate to this.

  Among the three layers, the constituent material of the first resin layer 51 and the third resin layer 53 constituting the front and back layers ensures the followability to the curved surface portion of the adherend, particularly the three-dimensional curved surface portion such as a rectangular parallelepiped corner portion. Of the polyester elastomers having a degree of flexibility, an amorphous polyester elastomer that does not crystallize even when heated is preferably used. Preferred examples of the amorphous polyester elastomer include a copolymer polyester elastomer obtained by polymerization from terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol described in paragraph No. 0005 of JP-A-2002-103544. Can do. In this copolymerized polyester elastomer, the glycol components are preferably 50 to 90 mol% ethylene glycol and 10 to 50 mol% 1,4-cyclohexanedimethanol, and 60 to 80 mol% ethylene glycol and 1,4-cyclohexane. It is more preferable that it is 20-40 mol% of dimethanol. Examples of such an amorphous polyester elastomer include those commercially available as KODAR PETG (trade name) from Eastman Chemical Company.

  The decorative sheet 1 of the present invention is a decorative sheet that has excellent followability to a curved surface portion because the three-layer laminated sheet 5 has a three-layer structure made of the above materials.

  That is, in the present invention, the unstretched resin layer of polyethylene terephthalate, which is a layer constituting the second resin layer 52 in the present invention, is easily crystallized when subjected to heat treatment. Therefore, the base resin layer (3 When the layered sheet 5 is formed, the adhesive force at the interface with the adhesive layer 4 is reduced by the heat at the time of manufacturing the decorative sheet and the heat at the time of sticking to the adherend member, and the decorative sheet There arises a problem that the followability with respect to the curved surface portion becomes worse. However, the three-layer laminated sheet 5 having a three-layer structure like the decorative sheet of the present invention is composed of a resin that does not crystallize even when heated, the first resin layer 51 and the third resin layer 53 on the front and rear surfaces. For this reason, the adhesive force at the interface with the adhesive layer 4 does not decrease, the followability to the curved surface portion is improved, and no float or wrinkle occurs even when it is attached to the adherend.

  By the way, the base resin layer was formed only by the resin (amorphous polyester elastomer that does not crystallize even when heated) that forms the first resin layer 51 or the third resin layer 53 without using the three-layer structure. In this case, since the elongation due to heating at the time of molding becomes too large, when the decorative sheet is attached to the curved surface portion, the base resin layer is excessively stretched and the concealment effect described later is reduced, and The background will be seen through. However, in the three-layer laminated sheet 5 having a three-layer structure like the decorative sheet 1 of the present invention, the second resin layer 52 serving as the core layer does not extend too much even by heating during molding for attaching the decorative sheet. Therefore, excessive elongation of the three-layer laminated sheet 5 itself can be suppressed, and the background of the adherend can be prevented from being seen through. Note that the decorative sheet 1 of the present invention has an advantage that the cost can be reduced as compared with the decorative sheet in which the base resin layer is formed only by the resin forming the first resin layer 51.

  At least one of the layers constituting the three-layer laminated sheet 5 contains a colorant for providing a concealing effect. When the three-layer laminated sheet 5 contains a colorant, when the decorative sheet 1 is attached to the curved surface portion, the colored ink layer 3 (solid layer) located near the outer surface extends in the plane direction. The covering power of the colored ink layer 3 (solid layer) that is lowered can be compensated for and the background of the adherend can be prevented from being seen through. Further, when the concealing effect is not given to the three-layer laminated sheet 5 and the concealing effect is provided only by the solid layer, color separation may occur and the concealing effect may be insufficient. If the layer laminated sheet 5 is provided with a concealing effect, the above-described colored ink layer 3 can be made more prominent without causing the problem of color separation. As such a colorant, a known colorant can be used. For example, inorganic pigments such as titanium white and carbon black and metal pigments such as aluminum powder can be used.

  If sufficient concealment can be obtained without adding a colorant to all three layers, it is preferable to add a colorant to the second resin layer 52 that is the core layer. By not adding a colorant to both the front and back surfaces (the first resin layer 51 and the second resin layer 52), it is possible to reduce film formation defects caused by the colorant when the three layers are formed by coextrusion. In addition, when a higher concealing effect is required, a colorant may be contained in all three layers constituting the three-layer laminated sheet 5.

  The composition material of each layer of the three-layer laminated sheet contains additives having various functions such as ultraviolet absorbers, light stabilizers, heat stabilizers, antistatic agents, plasticizers, curing agents, and lubricants as necessary. It can also be made.

  The three-layer laminated sheet 5 is formed by co-extrusion of the constituent materials of the respective layers so that the first resin layer 51 and the third resin layer 53 are formed on both surfaces of the second resin layer 52. The layer thickness of the three-layer laminated sheet 5 is preferably in the range of 50 to 300 μm and thicker than the transparent sheet 2. The second resin layer 52 needs to be distributed with the largest thickness among the three layers in order to ensure the concealment of the entire decorative sheet mainly by adding a colorant. Specifically, it is preferable to secure a thickness of 30 to 95% of the total thickness of the three-layer laminated sheet. In addition, the thickness of the 1st resin layer 51 and the 2nd resin layer 52 is not specifically limited, These both layers may be the same thickness.

  The three-layer laminated sheet 5 formed by coextrusion is formed as a constituent layer of the decorative sheet 1 by previously forming the colored ink layer 3 on the transparent sheet 2 and further applying an adhesive thereon. Is done. Further, an adhesive is applied on the three-layer laminated sheet 5 formed by coextrusion, and the transparent sheet 2 on which the colored ink layer 3 is formed is adhered thereon to form a constituent layer of the decorative sheet 1 May be. At this time, in order to obtain stronger adhesiveness, corona discharge treatment, primer coating, etc., etc. are applied to the surface or both surfaces of the three-layer laminated sheet 5 on the side where the adhesive layer 4 is formed. You may give a well-known easy-adhesion process. Since the three-layer laminated sheet 5 is made of a highly flexible resin, if a colored ink layer is formed on this layer, blocking is caused by the organic solvent contained in the colored ink layer coating liquid. Although there is a problem, in the present invention, since the colored ink layer 3 is formed on the surface on the transparent sheet 2 side, such a problem is avoided.

  In the present invention, since the three-layer laminated sheet 5 formed of a highly flexible resin is formed adjacent to the adhesive layer 4, when a decorative sheet is attached to an adherent substrate having a curved surface portion, Problems due to the resulting elongation can be reduced. Hereinafter, the mechanism will be considered and described in detail. As shown in FIG. 3, the decorative sheet 1 of the present invention is formed adjacent to the adhesive layer 4 in which the three-layer laminated sheet 5 is hard and hardly stretched, so that the decorative sheet 1 has a curved surface portion. 8 is pulled in the direction of contraction by the adhesive layer 4 on the outer surface of the three-layer laminated sheet 5 when adhered to the substrate 8, and is also contracted by the adhesive force with the adherend substrate on the inner surface. Pulled on. Therefore, it is considered that in the vicinity of the middle in the layer thickness direction of the three-layer laminated sheet 5, the elongation suppressed in the vicinity of the adhesive layer 4 is shared and a large elongation in the surface direction occurs. Accordingly, the elongation required for following the curved surface portion in the entire decorative sheet 1 is secured at this portion, so that significant elongation in other constituent layers (colored ink layer 3 and transparent sheet 2) is suppressed, and this layer The problem caused by the elongation of can be reduced. In the present invention, since the three-layer laminated sheet 5 is formed adjacent to the adhesive layer 4, the three-layer laminated sheet 5 is attached when the decorative sheet 1 is attached to the adherend having a curved surface portion. Excessive elongation in the vicinity of the outer surface (range a in FIG. 2) is suppressed, and whitening (crystallization) is also prevented.

(Protective film)
The protective film 6 is an arbitrary configuration of the decorative sheet 1, is adjacent to the transparent sheet 2, and is provided on the outermost surface of the decorative sheet 1. When the decorative member 10 formed by adhering the decorative sheet 1 to the adherent member 8 is used by the consumer after reaching the consumer's hand as a product, the protective film 6 is damaged on the surface of the decorative sheet. It has a role of preventing contamination and / or contamination. That is, the protective film 6 imparts at least one characteristic of scratch resistance and contamination resistance to the decorative sheet surface (transparent sheet 2).

  The material of the protective film 6 can be selected from known materials used in the technical field of decorative sheets according to the properties (scratch resistance and / or stain resistance) given to the decorative sheet surface. For example, ionizing radiation curable type comprising a thermosetting silicon resin such as silicon (meth) acrylate, polysiloxane or the like, a two-component curable urethane resin, or a monomer or prepolymer of an unsaturated (meth) acrylic acid ester Resin or the like can be used. Here, (meth) acrylate means acrylate or methacrylate, and (meth) acrylic acid ester means acrylic acid ester or methacrylic acid ester. The ionizing radiation means electromagnetic waves or charged particles capable of crosslinking and polymerizing molecules such as electron beams and ultraviolet rays.

  The protective film 6 is formed by applying a protective film resin composition to the surface of the transparent sheet 2. The thickness of the protective film 6 is preferably 1 μm or more and 10 μm or less. When the thickness is 10 μm or more, the followability to the curved surface portion of the decorative sheet is deteriorated. Moreover, when it is 1 micrometer or less, when a decorative sheet is affixed on a to-be-adhered member, the protective film 6 becomes thin too much in a curved surface part, and a protective function is not fully exhibited. The thickness of the protective film 6 is more preferably 6 μm or less from the viewpoint of followability to the curved surface portion.

(Temporary protection sheet)
The temporary protection sheet 7 is provided on the surface of the decorative sheet 1 on the transparent sheet 2 side, and includes a temporary attachment base sheet 71 and an adhesive layer 72. This temporary protection sheet 7 is used for various processing, distribution, sales, delivery, construction, etc. before the decorative member 10 formed by sticking the decorative sheet 1 to the adherent member 8 is delivered to the consumer as a product. In addition, it has a role of preventing the surface of the decorative sheet 1 from being damaged and contaminated. The temporary protective sheet 7 is peeled off after reaching the consumer's hand, and the peeled decorative member 10 is used for the consumer.

  The temporary attachment base sheet 71 has a role of protecting the transparent sheet 2 serving as the surface of the decorative member having the decorative sheet 1 attached to the adherend member 8 from scratches and contamination.

  As the material of the temporary attachment base sheet 71, it is preferable to use the same material as the transparent sheet 2, and like the transparent sheet 2, it is preferable to use a copolymerized polyester terephthalate mainly composed of terephthalic acid, isophthalic acid and ethylene glycol. preferable.

  The temporary attachment base sheet 71 formed of this material has sufficient heat resistance against heat applied at the time of forming the decorative sheet on the adherend member 8 and sufficient strength to prevent scratches and contamination of the transparent sheet 2. Have.

  Moreover, since the temporary attachment base material sheet 71 is formed of the same material as that of the transparent sheet 2, peeling and floating are unlikely to occur between the temporary attachment protection sheet 7 and the transparent sheet 2 for the following reason. That is, since the temporary attachment protective sheet 7 is disposed at a position close to the transparent sheet 2 (an adjacent position or an adjacent position through a protective film), when attached to the adherent member, FIG. As shown in FIG. 4, the elongation x on the curved surfaces of the temporary attachment base sheet 71 and the transparent sheet 2 is approximately the same. In addition, the temporary protection sheet 7 and the decorative sheet 1 are simultaneously formed on the adherend member 8 by vacuum forming. The temperature at the time of forming depends on the shape of the adherend member 8, the forming apparatus, the type of adhesive used, and the like. It varies and is set to various temperatures depending on molding conditions. At this time, if both sheets are formed of the same material, both sheets have the same material mechanical properties (elastic modulus, elongation, elastic limit, yield point, etc.) at various temperatures. Peeling and lifting are less likely to occur. In addition, for the reasons described above, the decorative sheet 1 is hardly deformed, and the decorative sheet 1 is less likely to float from the adherend member 8.

  Further, since the temporary base material sheet 71 is formed of the same material as the transparent sheet 2, the transparent sheet 2 substantially increases the thickness of the temporary base material sheet 71 to the original thickness of the transparent sheet 2. Since the thickness becomes thicker, the transparent sheet 2 is not excessively stretched by the heat during molding, and the surface of the transparent sheet 2 is less likely to raise the unevenness of the adherend member 8.

  From the viewpoint of more exerting the above effects, the copolymer that is the material of the temporary bonding base sheet 71 is preferably such that the copolymerization ratio, the molecular weight, or the plane orientation coefficient is the same as the material of the transparent sheet 2. . However, strictly speaking, the temporary protective sheet 7 has a slightly larger elongation. Therefore, the copolymer forming the temporary base material sheet 71 by adjusting these numerical values is slightly different from the copolymer of the transparent sheet 2. If it is soft (low elastic modulus), the moldability is improved.

  The thickness of the temporary bonding base sheet 71 is preferably thinner than the thickness of the transparent sheet 2, and specifically, it is preferably 12 μm or more and 50 μm or less. If the thickness is less than 12 μm, the strength of the temporary protective sheet 7 is lowered, so that a sufficient protective function cannot be achieved, and sufficient heat resistance against heat during molding cannot be maintained. Moreover, when thicker than 50 micrometers, the followable | trackability with respect to the curved surface part of the decorative sheet 1 will fall. However, since the thickness of the transparent sheet 2 is substantially increased as described above when the thickness of the temporary bonding base sheet 71 is large within the range satisfying this followability, the surface of the transparent sheet 2 is There is an effect that it is difficult to raise the unevenness of the adherend member 8.

  The pressure-sensitive adhesive layer 72 has a role of adhering the temporary attachment base sheet 71 to the surface (the transparent sheet 2 or the protective film 6) of the decorative sheet 1 and temporarily holding this adhesion state.

  As a material used for the pressure-sensitive adhesive layer 72, among known pressure-sensitive adhesives, the adhesive layer 72 has a degree of adhesiveness that allows the surface of the temporary bonding base sheet 71 and the decorative sheet 1 to adhere, and is temporarily attached from the decorative sheet 1. When the protective sheet 7 is peeled off, a material that does not remain on the surface of the decorative sheet is appropriately selected. As such an adhesive, for example, an acrylic resin-based or rubber-based adhesive can be used. The thickness of the pressure-sensitive adhesive layer 72 is about 5 to 20 μm.

  The temporary protective sheet 7 is formed by applying a pressure-sensitive adhesive as a material for the pressure-sensitive adhesive layer 72 to the surface of the temporary bonding base sheet 71. The temporary protective sheet 7 is attached to the decorative sheet by attaching the surface of the temporary protective sheet 7 on the pressure-sensitive adhesive layer 72 side and the surface of the transparent sheet 2 (when the protective film 6 is formed on the transparent sheet, the protective film 6 is formed). 6 surface) and dry lamination. After that, the colored ink layer 3 and the adhesive layer 4 are formed on the surface of the transparent sheet 2 on which the temporary protective sheet 7 and the protective film 6 are not formed, and the three-layer laminated sheet 5 is bonded. A decorative sheet 1 with a temporary protective sheet 7 can be obtained.

(Decorative material)
As shown in FIG. 2, the decorative member 10 of the present invention is obtained by adhering the decorative sheet 1 having the above-described configuration to an adherent member 8 having a curved surface portion. A temporary protective sheet 7 is optionally provided.

  As the adherend member 8, various materials such as a wood material, a metal, a resin, and a ceramic material are used. As a typical material, a wood fiber board having a flat plate shape or a curved surface portion is used. A wood fiberboard is a powder or small piece of wood such as lauan, rubber tree, pine, cedar, etc., bonded and bonded with an adhesive such as urea resin, melamine resin, urethane resin, etc., and stuck in a plate shape by heat press Is. Typical examples include a medium density fiberboard (abbreviated as MDF), a particle board, and the like.

  FIG. 4 is a schematic view showing the production process of the decorative member 10 with a temporary protective sheet of the present invention. Here, the decorative member 10 with the temporary protective sheet 7 is taken as an example, but the decorative member 10 without the temporary protective sheet 7 is also manufactured by the same method. The decorative member 10 with the temporary protective sheet 7 has the surface of the adherend member 8 and the surface of the decorative sheet 1 with the temporary protective sheet 7 facing the three-layer laminated sheet 5 with an adhesive 9 therebetween (FIG. 4). (A)), is formed by a vacuum forming and laminating method in which the decorative sheet 1 with the temporary attachment protective sheet 7 is adhered to the adherent member 8 by a pressure difference due to vacuum suction from the adherent member 8 side (FIG. 4B). ). In order to obtain stronger adhesiveness, a known easy adhesion treatment such as corona discharge treatment or primer coating is applied to the three-layer laminated sheet 5 side surface of the decorative sheet 1 with the temporary protective sheet 7 as necessary. May be applied. Thereafter, the temporary protective sheet 7 is peeled from the obtained decorative member 10 with the temporary protective sheet 7 (FIG. 4C), and the decorative member 10 after peeling is used for consumers.

The adhesive is preferably a urethane resin, and a two-component curable urethane resin, a one-component (moisture) curable urethane resin, or a water-dispersed emulsion can be used, and a dry solid of a water-dispersed emulsion is preferably used. In this case, usually, an adhesive is applied to the adherend member 8 side by spraying (spraying), brushing, or the like, and the decorative sheet 1 or the like is stacked thereon and molded by a vacuum forming lamination method described later. The adhesive may be applied to the decorative sheet 1 side or both the decorative sheet 1 side and the adherend member 8 side. The coating amount of the adhesive is about 50 to 100 g / ^{m 2.} An adhesive other than urethane resin can also be used.

  For the formation of the decorative member 10 and the like of the present invention, the vacuum pressing method is preferably used among the lamination methods using the vacuum forming lamination method. The vacuum pressing method is similar to the vacuum laminating method. However, when forming a decorative sheet or other adherent member, the compression pressure of the rubber elastic film is used in addition to the air pressure, and the decorative sheet is heated by a heater. However, it is characterized by uniform heating of the decorative sheet or the like and a stronger pressing force.

  As an example, a method for forming the decorative member 10 with the temporary protective sheet 7 will be described below. FIG. 5 is a schematic configuration diagram illustrating an example of a vacuum press apparatus. The vacuum press device 40 has an upper chamber 42 that can be moved up and down by a vertical movement means 41 such as a fluid pressure cylinder, and a lower chamber 43 that faces the upper chamber 42 and that is below. An infrared radiation type heater 44 is disposed inside the upper chamber 42. The lower opening of the upper chamber 42 is entirely covered with a rubber-like elastic film 45. Silicon rubber or the like is usually used for the rubber-like elastic film 45. The upper surface of the lower chamber 43 serves as a table 46. The upper chamber 42 and the lower chamber 43 have supply / exhaust ports 47 and 48, respectively, and the internal pressures can be adjusted independently.

  In the vacuum press method, first, the upper chamber 42 is moved upward and separated from the lower chamber 43, the covering member 8 is placed on the table 46, and the decorative sheet on which the temporary protection sheet 7 is further adhered. 1 is arranged from the top of the adherend member 8 so that the three-layer laminated sheet side faces. When the adhesive is applied to the surface of the decorative sheet 1 with the temporary protective sheet 7 or the adherend member 8, it is applied at this stage by spray coating or the like. If the adhesive contains a solvent, it is dried at this stage.

  Next, the upper chamber 42 is moved downward and pressed against the lower chamber 43, and the upper chamber 42 and the lower chamber 43 are sealed. FIG. 5 shows this state. Next, the inside of the lower chamber 43 is depressurized and the inside of the upper chamber 42 is pressurized. Further, the decorative sheet 1 with the temporary attachment protective sheet 7 is heated and softened through the rubber-like elastic film 45 using the heater 44 so that it can be attached. As a result, the decorative sheet 1 with the temporary protective sheet 7 is deformed and pressed by the pressure difference between the upper chamber 42 and the lower chamber 43 and the contraction pressure of the rubber-like elastic film 45 in a state along the surface of the adherend member 8. The decorative sheet 1 with the temporary protection sheet 7 comes into close contact with the adherend member 8. Finally, after releasing the decompression of the lower chamber 43 and releasing the pressurization of the upper chamber 42 to bring both chambers to atmospheric pressure, the upper chamber 42 is moved upward to separate the upper chamber 42 and the lower chamber 43. The decorative member 10 with the temporary protective sheet 7 is obtained by taking out the adherent member 8 to which the decorative sheet 1 with the temporary protective sheet 7 is attached.

  Since the decorative sheet 10 and the like of the present invention are formed by adhering the above-described decorative sheet 1 and the like to the adherend member 8 having a curved surface portion, the decorative sheet 1 does not float or wrinkle even at the curved surface portion and is excellent in moldability. At the same time, the specularity of the surface of the decorative sheet 1 is also excellent. Further, the decorative member 10 of the present invention does not cause the pattern or color of the decorative sheet 1 to fade or the pattern to elongate on the curved surface portion, and prevents the three-layer laminated sheet 5 from being seen through due to the color fading. Therefore, it exhibits excellent design properties at the curved surface portion. Furthermore, the decorative member 10 of the present invention is less likely to be scratched or contaminated by the temporary protective sheet 7 during various processing, distribution, sales, delivery, construction, etc. before reaching the consumer's hands. The protective film 6 is unlikely to cause scratches or contamination when the temporary protective sheet is peeled over the consumer's hand and then used for the consumer.

  Hereinafter, the present invention will be described in more detail based on examples and comparative examples. Note that the present invention is not limited thereby.

(Example 1)
A 25 μm-thick transparent sheet comprising the following components wound in a roll shape is supplied, and a two-part curable acrylic silicon resin composition is layered on one surface as a protective film resin composition It was applied by a gravure roll coating method so as to have a thickness of 2 μm.

On the other hand, a 19 μm-thick temporary base material sheet made of the same component as the long strip-shaped transparent sheet wound up in a roll shape is supplied, and an acrylic resin is used as a pressure-sensitive adhesive for the pressure-sensitive adhesive layer on one surface thereof. 5 g / m ² (coating amount at the time of drying) was applied by a roll coating method.

  Transparent sheet and temporary protective sheet; copolymerized polyester terephthalate resin sheet of terephthalic acid isophthalic acid and ethylene glycol (manufactured by Teijin DuPont Co., Ltd., product name; teflex, polymerization ratio; terephthalic acid 88 mol%, isophthalic acid 12 mol%)

  Next, the transparent sheet and the temporary attachment base sheet are supplied so that the surface of the transparent sheet on which the protective film is formed and the surface of the temporary attachment base sheet on which the adhesive is applied face each other, Dry laminated and bonded together.

Then, after supplying the sheet on which the transparent sheet and the temporary protective sheet are bonded together, and performing corona discharge treatment on the surface on the transparent sheet side, the colored ink layer coating liquid comprising the following components is subjected to gravure rotary printing. Then, the entire surface was solid-printed with a coating amount of 6 g / m ² and dried, and this was wound up. Thereafter, it was cured in an atmosphere of 40 ° C. for 3 days to form a colored ink layer. At this point, the printability of the transparent sheet on which the colored ink layer was formed was evaluated.

  Coating liquid for colored ink layer; mixed system of polyester polyol and hexamethylene diisocyanate as binder (weight ratio 100: 10), 30wt% titanium white as pigment

  Next, as a constituent material of the first resin layer and the third resin layer, a copolymerized polyester elastomer of terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol (manufactured by Eastman Chemical Co., product name; KODER PETG, polymerization ratio; (Ethylene glycol 67 mol%, 1,4-cyclohexanedimethanol 33 mol%) As a constituent material of the unstretched resin layer, which is the second resin layer, polyethylene terephthalate is the main component and polybutylene terephthalate is added as a subcomponent The resin used was used. At this time, 5 wt% titanium white was contained as a colorant in the constituent material of each layer. Each of these constituent materials is coextruded in three layers so that the first resin layer as the front surface layer and the third resin layer as the back surface layer are formed on both surfaces of the second resin layer to be the core layer, and the layer thickness A 200 μm three-layer laminated sheet was formed. At this time, the layer thickness of the second resin layer was 170 μm, and the layer thicknesses of the first resin layer and the third resin layer were each 15 μm. Thereafter, corona treatment was performed on both the front and back surfaces of the three-layer laminated sheet.

Next, an adhesive composed of a mixed system of polyester polyol and hexamethylene diisocyanate (weight ratio 100: 10) is applied to the colored ink layer formed on the transparent sheet by a gravure roll coating method at 15 g / m ² (when dried). Application amount) Thereafter, before the adhesive is cured, the above-mentioned three-layer laminated sheet is dry-laminated on the adhesive and bonded together, followed by curing in a 40 ° atmosphere for 3 days. Formed.

Next, a 15 mm thick rectangular MDF substrate (manufactured by Sumitomo Forestry Co., Ltd., “Nelson Pine”) formed by chamfering the peripheral edge of the surface with a radius of curvature of 3 mm is used as the adherent member, and the surface is water-dispersed. A urethane emulsion adhesive was spray applied at 70 g / m ² . A decorative sheet with a temporary protective sheet of Example 1 is superimposed on the MDF substrate so that the three-layer laminated sheet side faces and laminated by a vacuum press as shown in FIG. A decorative member was produced. The vacuum forming was performed under the conditions of preheating of the decorative sheet: 120 ° C./120 seconds, vacuum pressure heating time: 120 ° C./120 seconds.

  The temporary protective sheet of the decorative member with the temporary protective sheet was peeled off to obtain the decorative member of Example 1 in which no adhesive remained on the surface. The following evaluation was performed on the decorative member of Example 1 thus obtained.

(Comparative Example 1)
In the method for forming a decorative sheet of Example 1, a 25 μm thick biaxially stretched film of polyethylene terephthalate (product name: Lumirror) was used as a transparent sheet, and a base resin sheet (3-layer laminated sheet of Example 1) was used. The biaxially stretched film of the same polyethylene terephthalate having a thickness of 200 μm and containing 5 wt% titanium white as a colorant was used. Moreover, the protective film and the temporary attachment protective sheet were not provided in the transparent sheet. Otherwise, the decorative sheet of Comparative Example 1 was formed in the same procedure as in Example 1. In addition, when the colored ink layer was formed on the transparent sheet and subjected to curing treatment, the printability evaluation of the transparent sheet on which the colored ink layer was formed was performed.

  Next, the decorative member of Comparative Example 1 was obtained by the same method as the decorative member forming method of Example 1. Thus, the following evaluation was performed about the decorative member of the comparative example 1 obtained.

(Comparative Example 2)
In the method for forming the decorative sheet of Example 1, an unstretched film having a thickness of 25 μm made of the same polyethylene terephthalate resin as the constituent material of the second resin layer used in Example 1 was used as the transparent sheet, and 5 wt. An unstretched film of the same polyethylene terephthalate having a thickness of 200 μm and containing% titanium white as a colorant was used. Moreover, the protective film and the temporary attachment protective sheet were not provided on the transparent sheet, and the transparent sheet and the base resin sheet were bonded together by thermal fusion without using an adhesive layer. Otherwise, the decorative sheet of Comparative Example 2 was formed in the same procedure as in Example 1. In addition, when the colored ink layer was formed on the transparent sheet and subjected to curing treatment, the printability evaluation of the transparent sheet on which the colored ink layer was formed was performed.

  Next, the decorative member of Comparative Example 2 was obtained by the same method as the decorative member forming method of Example 1. Thus, the following evaluation was performed about the decorative member of the comparative example 2 obtained.

(Comparative Example 3)
In the method for forming a decorative sheet of Example 1, as a transparent sheet, a thickness made of the same polyethylene terephthalate resin as the constituent materials of the first resin layer and the third resin layer used in Example 1 (with no colorant added). A 25 μm thick film was used. Further, as the base resin sheet, a film having a thickness of 200 μm containing 5 wt% titanium white as a colorant in the constituent materials of the first resin layer and the third resin layer used in Example 1 was used. Moreover, the protective film and the temporary attachment protective sheet were not provided on the transparent sheet, and further, the transparent sheet and the base resin sheet were bonded together by thermal fusion without using an adhesive layer. Otherwise, the decorative sheet of Comparative Example 3 was formed in the same procedure as in Example 1. In addition, when the colored ink layer was formed on the transparent sheet and subjected to curing treatment, the printability evaluation of the transparent sheet on which the colored ink layer was formed was performed.

  Next, the decorative member of Comparative Example 3 was obtained in the same manner as the decorative member forming method of Example 1. Thus, the following evaluation was performed about the decorative member of the comparative example 3 obtained.

(Corner stickiness evaluation)
The state of sticking of the decorative sheet on the curved surface portion of the decorative member was visually observed. In the case where no float or wrinkle was observed, it was indicated by ○, and in the case where float or wrinkle was observed, it was indicated by ×. The results are shown in Table 1.

(Evaluation of concealment of corners)
The state of concealment of the decorative sheet in the curved surface portion of the decorative member was confirmed visually. When the color of the colored ink layer did not fade and the color tone of the three-layer laminated sheet was not observed, it was indicated as “◯”, and when the color of the colored ink layer was faint and the color tone of the three-layer laminated sheet was observed, it was indicated as “x”. The results are shown in Table 1.

(Solvent resistance evaluation)
After applying lacquer thinner to the decorative sheet attached to the decorative member by rubbing, the state of the decorative sheet attached was visually observed. When the change did not occur on the surface of the decorative sheet, it was indicated by ○, and when the change such as the surface of the decorative sheet melted or turned white was indicated by ×. The results are shown in Table 1.

(Interfacial adhesion evaluation)
The decorative member was subjected to a two-cycle cryogenic test with a period of 12 hours at + 60 ° C and 12 hours at -20 ° C, and then the presence or absence of spontaneous peeling (floating) of the decorative sheet from the MDF substrate was observed. Thus, the interfacial adhesion between the decorative sheet and the MDF substrate was evaluated. In the case where the decorative sheet was not peeled off from the adherent member, it was indicated by ◯. The results are shown in Table 1.

(Contamination resistance evaluation)
On the surface of the decorative member, draw a line with a red and black oil marker (Mitsubishi Pencil Co., Ltd., trade name: Mitsubishi oil marker, varieties: peace middle letter, round core, product number: A-50E) (written), 24 hours After leaving at room temperature of 25 ° C., the written part was wiped off with a cloth. When the residual ink of the marker was not visually recognized, it was indicated by ◯, and when the residual ink of the marker was visually observed, it was indicated by ×. The results are shown in Table 1.

(Printability evaluation)
The transparent sheet wound up into a roll after the colored ink layer was formed and cured was unwound, and the state of the printed surface and the non-printed surface was visually observed. When the transfer (blocking) of the ink was not recognized on the non-printing surface of the transparent sheet, it was indicated as “◯”, and when the transfer of the ink was recognized on the non-printing surface of the transparent sheet, it was indicated as “X”. The results are shown in Table 1.

It is sectional drawing which shows an example of the decorative sheet etc. of this invention. It is sectional drawing which shows an example of the decorative member etc. of this invention. It is sectional drawing which shows the expansion | extension of the surface direction of each layer which comprises the decorative sheet of this invention formed in the to-be-adhered member which has a curved surface part. It is the schematic which shows an example of manufacturing processes, such as a decorative member of this invention. It is a schematic block diagram which shows an example of a vacuum press apparatus. It is sectional drawing which shows an example of the conventional decorative sheet. It is sectional drawing which shows the expansion | extension of the surface direction of each layer which comprises the conventional decorative sheet formed in the to-be-adhered member which has a curved surface part.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 Transparent sheet 3 Colored ink layer 4 Adhesive layer 5 Three-layer laminated sheet 6 Protective film 7 Temporary attachment protective sheet 51 First resin layer 52 Second resin layer 53 Third resin layer 71 Temporary attachment base sheet 72 Adhesive Agent layer

Claims (7)

The transparent sheet side of the decorative sheet in which a three-layer laminated sheet containing a colorant in at least one layer, an adhesive layer, a colored ink layer, and a transparent sheet thinner than the three-layer laminated sheet are laminated in this order. A temporary protective sheet comprising a temporary base material sheet and a pressure-sensitive adhesive layer on the surface of the protective sheet with a temporary protective sheet provided with the pressure-sensitive adhesive layer facing the decorative sheet side,
The three-layer laminated sheet is a polyethylene terephthalate unstretched resin layer and a copolymer polyester resin mainly composed of terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol, formed on both surfaces of the unstretched resin layer. Formed with layers,
The adhesive layer is formed of a two-component curable urethane resin mainly composed of polyol and isocyanate,
The decorative sheet with a temporary protective sheet, wherein the transparent sheet and the temporary base material sheet are formed of a copolyester resin mainly composed of terephthalic acid, isophthalic acid and ethylene glycol. A decorative sheet formed by laminating a three-layer laminated sheet containing a colorant in at least one layer, an adhesive layer, a colored ink layer, a transparent sheet thinner than the three-layer laminated sheet, and a protective film in this order. A temporary protective sheet comprising a temporary base material sheet and an adhesive layer on the surface of the protective film is a decorative sheet with a temporary protective sheet provided with the adhesive layer facing the decorative sheet. ,
The three-layer laminated sheet is a polyethylene terephthalate unstretched resin layer and a copolymer polyester resin mainly composed of terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol, formed on both surfaces of the unstretched resin layer. Formed with layers,
The adhesive layer is formed of a two-component curable urethane resin mainly composed of polyol and isocyanate,
The decorative sheet with a temporary protective sheet, wherein the transparent sheet and the temporary base material sheet are formed of a copolyester resin mainly composed of terephthalic acid, isophthalic acid and ethylene glycol. The decorative sheet with a temporary protective sheet according to claim 1 or 2, wherein the two-component curable urethane resin has a three-dimensionally crosslinked molecular structure. A decorative member with a temporary protective sheet, wherein the decorative sheet with a temporary protective sheet according to any one of claims 1 to 3 is adhered to an adherent member having a curved surface portion. A decorative sheet in which a three-layer laminated sheet containing a colorant in at least one layer, an adhesive layer, a colored ink layer, a transparent sheet thinner than the three-layer laminated sheet, and a protective film are laminated in this order. There,
The three-layer laminated sheet is a polyethylene terephthalate unstretched resin layer and a copolymer polyester resin mainly composed of terephthalic acid, ethylene glycol and 1,4-cyclohexanedimethanol, formed on both surfaces of the unstretched resin layer. Formed with layers,
The adhesive layer is formed of a two-component curable urethane resin mainly composed of polyol and isocyanate,
A decorative sheet, wherein the transparent sheet is formed of a copolyester resin mainly composed of terephthalic acid, isophthalic acid and ethylene glycol. The decorative sheet according to claim 5, wherein the two-component curable urethane resin has a three-dimensionally crosslinked molecular structure. A decorative member, wherein the decorative sheet according to claim 5 or 6 is adhered to an adherent member having a curved surface portion.

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