JP2018047698A - Decorative sheet and decorative molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a decorative sheet which is used for manufacturing a decorative molded body being decorated by a dyed artificial leather base material, and which is less likely to contaminate a target decorative molded body by transferring a dye thereto; and a decorative molded body using the same.SOLUTION: A decorative sheet is intended to decorate a target decorative molded body. The decorative sheet is an artificial leather base material containing a cationic dye dyeable polyester fiber and a polymer elastic body, and is dyed with a cationic dye. The decorative sheet is laminated and integrated into a decorative molded body.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a decorative sheet including a dyed artificial leather substrate and a decorative molded body.

  Artificial leather is used as a surface decoration sheet member for exterior devices such as mobile devices such as mobile phones, home appliances, and sanitary products, as well as interior members such as vehicles, ships, and aircraft, building materials, and furniture. The decorative molded body used is known. For example, Patent Document 1 below discloses a decorative sheet that is an artificial leather integrated into a resin molded body by in-mold molding, and a decorative molded body using the same.

  In general, an artificial leather base material includes a fiber material and a polymer elastic body such as polyurethane, and is used by being colored. Polyester fibers are preferably used as the fiber material contained in the artificial leather base material from the viewpoint of excellent heat resistance and moldability. As dyes for dyeing artificial leather base materials containing polyester fibers, disperse dyes having excellent color developability are widely used. However, artificial leather substrates dyed with disperse dyes have a problem that disperse dyes contaminate other members and decorated molded articles, and when the environmental temperature is high or the pressure applied to other members is high, or Contamination may be noticeable when the adhesive contains an organic solvent.

［式（III）中、Ｘは、金属イオン、４級ホスホニウムイオン又は４級アンモニウムイオンを表す。］で表される成分が含まれる合成皮革を開示する。 For example, Patent Document 2 listed below discloses an ultrafine fiber raised nonwoven fabric comprising a polyester ultrafine fiber and an elastomeric matrix that can be dyed with a cationic dye, and a UV stabilizer composition. Moreover, although the following patent document 3 is a technique regarding synthetic leather, it is synthetic leather in which a resin layer is formed on the surface of a double raschel fabric; the double raschel fabric is composed of a front knitted fabric, a back knitted fabric and those. Disclosed is a synthetic leather comprising a connecting pile layer, the fibers constituting the surface knitted fabric are polyester fibers dyed with a cationic dye, and the resin layer is formed on the surface knitted fabric side. And a polyester composed of a dicarboxylic acid component having terephthalic acid as a main component and a glycol component having ethylene glycol as a main component. The dicarboxylic acid component has the following formula (III):

[In Formula (III), X represents a metal ion, a quaternary phosphonium ion, or a quaternary ammonium ion. The synthetic leather containing the component represented by this is disclosed.

  Further, for example, Patent Document 4 below is a deodorizing fabric subjected to a deodorizing treatment, and as a copolymer component, a metal salt of sulfoisophthalic acid (A) and sulfoisophthalic acid in an acid component. Copolyester fiber containing quaternary phosphonium salt or quaternary ammonium salt (B) such that 3.0 ≦ A + B ≦ 5.0 (mol%), 0.2 ≦ B / (A + B) ≦ 0.7 A deodorant fabric dyed with a cationic dye containing a is disclosed.

International Publication No. 2015/029453 Pamphlet JP 2007-16378 A JP 2014-29050 A JP 2010-242240 A

  In the case where a decorative molded body is manufactured by integrating a decorative sheet with a decorated molded body that is a molded body to be decorated disclosed in Patent Document 1, there are the following problems. The decorative molded body, for example, injects a molten resin into the cavity and solidifies it in a state where a decorative sheet or a preform molded body formed in a three-dimensional shape is arranged in advance in the cavity of the mold. Thus, the decorative sheet is manufactured by primary decorative molding such as in-mold molding that molds a decorative molded body in which the surface of the resin molded body is integrated. Further, as another method, the decorative molded body may be formed by two methods such as an overlay method in which the decorative sheet is heated and shaped along the surface of the resin molded body, and bonded and integrated with an adhesive. Manufactured by next decorative molding. In the case of a decorative sheet dyed with a disperse dye, when the decorative sheet is integrated with the decorative molded body, the dye is sublimated by heat or pressure, or the dye is absorbed by the organic solvent contained in the adhesive. Or liberate. As a result, the disperse dye transferred from the decorative sheet contaminated the decorated molded body, which is a resin molded body. When the decorated molded body is white or light-colored, contamination with disperse dyes is more conspicuous, and the commercial value is greatly impaired.

  The present invention is a decorative sheet used for the production of a decorative molded body, and uses a dyed artificial leather base material that is difficult to transfer to a decorated molded body and other members as a base material. The object is to provide a decorative sheet and a decorative molded body using the same.

One aspect of the present invention is a decorative sheet for decorating a decorative molded body, which includes a cloth of a cationic dye-dyeable polyester fiber and a polymer elastic body imparted to the cloth. The decorative sheet includes a substrate and is dyed with at least one cationic dye. According to such a decorative sheet, for example, even if it is colored in a dark color such that the lightness L ^* value ≦ 50, it is difficult to transfer the dye to the decorative molded body or other members that come into contact. In particular, even if such a decorative sheet is integrated with a decorated molded body made of a white or light colored resin molded body, the decorated molded body is hardly contaminated. Examples of the fabric include a nonwoven fabric of a dye dyeable polyester fiber. The decorative sheet preferably has a raised surface.

  Moreover, since the determination of the water fastness test for cotton cloth according to JIS L 0846 is grade 4-5 or higher, the cationic dyes that are not ion-bonded and fall off by contact with water are sufficiently removed. From the point that migration of dye is sufficiently suppressed.

  Moreover, it is preferable that the decorating sheet is a preform molded body shaped into a three-dimensional shape. In such a preform molded body, migration of the dye to another member is suppressed even in the preform molding.

Another aspect of the present invention is a decorative molded body in which a decorative sheet as described above is laminated and integrated with a decorative molded body. Such a decorative molded body is not easily contaminated by the dye transferred from the decorative sheet, even if the decorated molded body is white, light color or transparent color having a lightness L ^* value> 50. This is particularly the case where the decorated molded body has white, light or transparent lightness L ^* value> 50, or the lightness difference ΔL ^* between the decorated molded body and the decorative sheet is 10 or more. However, it is preferable from the viewpoint that the migration of the dye becomes inconspicuous.

  ADVANTAGE OF THE INVENTION According to this invention, the decorating molded object using the dyed | stained sheet | seat for decorating which does not easily contaminate a to-be-decorated molded object and another member with dye, and it is obtained.

Drawing 1 is an explanatory view explaining the process of shape | molding a preform molded object by vacuum forming using the sheet | seat for decorating of embodiment. Drawing 2 is an explanatory view explaining the process of manufacturing a decoration fabrication object by in-mold fabrication using a preform fabrication object. FIG. 3 is a schematic perspective view showing the shape and dimensions of the preform molded body of the example.

  First, one embodiment of the decorative sheet according to the present invention will be described in detail along an example of the production method.

  In the method for producing a decorative sheet according to this embodiment, first, an artificial leather base material including a fabric containing a cationic dye-dyeable polyester fiber and a polymer elastic body impregnated in the fabric is prepared. The cationic dye-dyeable polyester fiber is a polyester fiber having a dye dye seat in the molecule as described later.

  Examples of the fabric include non-woven fabrics, woven fabrics, knitted fabrics, and the like. Non-woven fabrics, in particular, are easily stretched during molding, and when in-mold molding is performed, it is difficult to allow the molten resin to penetrate into the artificial leather base material. From the standpoint that a high fiber feeling can be maintained, an entangled nonwoven fabric of ultrafine fibers (hereinafter also simply referred to as a nonwoven fabric) is particularly preferably used. In the present embodiment, as an example of a fabric of a cationic dye-dyeable polyester fiber, a tangled nonwoven fabric of ultrafine fibers of a cationic dye-dyeable polyester will be described in detail as a representative example.

  The fineness of the cationic dyeable polyester fiber is not particularly limited. For example, it may be a regular fiber of 1 dtex or more or an ultrafine fiber of less than 1 dtex, but it suppresses the migration of the cationic dye. From this point, it is preferably 0.05 to 5 dtex, more preferably 0.1 to 3 dtex. When the fineness is relatively high, the surface area of the fiber is smaller than when the fineness is low. On the other hand, when finished in suede, there is a tendency for the appearance and hardness to decrease, such as a decrease in lighting effect and a decrease in three-dimensional effect, and the extensibility during softening due to heating decreases, making it accurate during molding. It tends to be difficult to shape the shape.

  In the production of the entangled nonwoven fabric of the ultrafine fiber of the cationic dyeable polyester, first, the entangled nonwoven fabric of the ultrafine fiber generating fiber is produced. Examples of the method for producing the entangled nonwoven fabric of ultrafine fiber generation type fibers include, for example, melt spinning the ultrafine fiber generation type fibers and collecting them as long fibers without intentionally cutting them to form a fiber web Alternatively, there is a method in which a fiber web is formed by a card method or the like using staples obtained by cutting ultrafine fiber-generating fibers at a predetermined length, and then a known entanglement treatment is performed. The long fiber is not a staple but a continuous fiber in the length direction, and is also called a filament. The fiber length of the long fiber is preferably 100 mm or more, and more preferably 200 mm or more from the viewpoint that the fiber density can be sufficiently increased. The upper limit of the long fiber is not particularly limited, but may be a fiber length of several m, several hundreds m, several km or more continuously spun. In this embodiment, the case where a long fiber web is manufactured is demonstrated in detail as a representative example.

  The ultrafine fiber generating fiber is a fiber that generates ultrafine fibers with a small fineness, for example, by subjecting the spun fiber to chemical post-treatment or physical post-treatment. In the present embodiment, a manufacturing method using sea-island type composite fibers as ultrafine fiber-generating fibers will be described. Instead of sea-island type composite fibers, known ultrafine fiber-generating fibers such as exfoliated split-type composite fibers are used. Also good.

  The sea-island type composite fiber is a multi-component composite fiber composed of at least two kinds of polymers, and has a cross section in which the island component polymer is dispersed in a matrix composed of the sea component polymer. A long-fiber web of sea-island type composite fibers is formed by melt-spinning sea-island-type composite fibers and collecting them on a net without cutting them.

  In the present embodiment, as the island component polymer, the component represented by the following formula (I) is contained in an amount of 1.5 to 3 mol%, the dicarboxylic acid component containing terephthalic acid as the main component, and ethylene glycol as the main component. It is preferable to use a cationic dye-dyeable polyester obtained by copolymerizing a copolymerization monomer containing a glycol component and containing a cationic dye dyeing seat in the molecule.

［上記式(I)中、Ｒは水素、炭素数１〜１０個のアルキル基又は２−ヒドロキシエチル基を表し、Ｘは金属イオン、４級ホスホニウムイオン又は４級アンモニウムイオンを表す。］

[In the formula (I), R represents hydrogen, an alkyl group having 1 to 10 carbon atoms, or a 2-hydroxyethyl group, and X represents a metal ion, a quaternary phosphonium ion, or a quaternary ammonium ion. ]

  Examples of the compound represented by the formula (I) include alkali metal salts of 5-sulfoisophthalic acid (lithium salt, sodium salt, potassium salt, rubidium salt, cesium salt), 5-tetrabutylphosphonium sulfoisophthalic acid, 5- Examples include 5-tetraalkylphosphonium sulfoisophthalic acid such as ethyltributylphosphonium sulfoisophthalic acid, and 5-tetraalkylammonium sulfoisophthalic acid such as 5-tetrabutylammonium sulfoisophthalic acid and 5-ethyltributylammonium sulfoisophthalic acid. The compounds represented by formula (I) may be used alone or in combination of two or more. Among these, a cationic dye-dyeable polyester excellent in mechanical properties and high-speed spinnability can be obtained by including a compound represented by the formula (I) in which X is a quaternary phosphonium ion or a quaternary ammonium ion. To preferred. Preferably, it contains 1.5 to 3 mol% of a compound represented by the formula (I), particularly a compound represented by the formula (I) in which X is a quaternary phosphonium ion or a quaternary ammonium ion, and mainly contains terephthalic acid. Suppresses color transfer even when the dyeable polyester obtained by copolymerizing a copolymerization monomer containing a dicarboxylic acid component as a component and a glycol component containing ethylene glycol as the main component is dyed darkly. It is preferable from the point of being easy to do.

  The following formula (II) derived from formula (I) in the cationic dyeable polyester:

［上記式(II)中、Ｘは金属イオン、４級ホスホニウムイオン又は４級アンモニウムイオンを表す。］
で表される単位の割合は１．５〜３モル％、さらには１．６〜２．５モル％であることが好ましい。式（II）で表される単位の割合が、１．５モル％未満の場合には、カチオン染料で染色したときの染色堅牢性が低下する傾向がある。一方、式(II)で表される単位の割合が、３モル％を超える場合には、高速紡糸性が低下することにより極細繊維が得られにくくなるとともに、得られる加飾用シートの引裂強力等の機械的特性が著しく低下する傾向がある。

[In the above formula (II), X represents a metal ion, a quaternary phosphonium ion or a quaternary ammonium ion. ]
It is preferable that the ratio of the unit represented by is 1.5 to 3 mol%, more preferably 1.6 to 2.5 mol%. When the proportion of the unit represented by the formula (II) is less than 1.5 mol%, the dyeing fastness when dyed with a cationic dye tends to be lowered. On the other hand, when the proportion of the unit represented by the formula (II) exceeds 3 mol%, it becomes difficult to obtain ultrafine fibers due to a decrease in high-speed spinnability, and the tear strength of the resulting decorative sheet The mechanical properties such as

  Here, terephthalic acid as a main component means that 50 mol% or more of the dicarboxylic acid component in the copolymerization monomer is terephthalic acid. The content of terephthalic acid in the dicarboxylic acid component is preferably 75 mol% or more. The purpose is to lower the glass transition temperature in order to improve dyeing fastness with cationic dyes, improve high-speed spinnability, and improve shapeability when using artificial leather substrates for molding applications. As the dicarboxylic acid component, other dicarboxylic acids other than the compound represented by the formula (I) may be included. Specific examples of other dicarboxylic acid components include, for example, aromatic dicarboxylic acids such as isophthalic acid, cyclohexanedicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and other aliphatic dicarboxylic acids such as adipic acid. Dicarboxylic acids or derivatives thereof may be included. Among these, it is particularly preferable to use isophthalic acid, a combination of 1,4-cyclohexanedicarboxylic acid and adipic acid, or a derivative thereof from the viewpoint of excellent mechanical properties and high-speed spinnability.

  As the dicarboxylic acid component, the copolymerization ratio of other dicarboxylic acids is preferably 2 to 12 mol%, more preferably 3 to 10 mol%. When the copolymerization ratio of other dicarboxylic acids is less than 2 mol%, the glass transition temperature does not sufficiently decrease, and the degree of orientation of the amorphous part inside the fiber tends to increase, so that the dyeability tends to decrease. . On the other hand, when the copolymerization ratio of other dicarboxylic acids exceeds 12 mol%, the glass transition temperature is too low, and the degree of orientation of the amorphous part inside the fiber tends to be low, so that the fiber strength tends to decrease. is there. In addition, when an isophthalic acid unit is contained as another dicarboxylic acid unit, it is preferable that the dicarboxylic acid unit contains an isophthalic acid unit in an amount of 1 to 6 mol%, further 2 to 5 mol%. It is preferable from the point which is excellent in property. Further, when it contains a 1,4-cyclohexanedicarboxylic acid unit and an adipic acid unit, it contains 1 to 6 mol%, further 2 to 5 mol% of 1,4-cyclohexanedicarboxylic acid unit and adipic acid unit, respectively. It is preferable to obtain a dye-dyeable polyester having excellent mechanical properties and high-speed spinnability.

  Moreover, having ethylene glycol as a main component means that 50 mol% or more of the glycol component in the copolymerization monomer is ethylene glycol. The ethylene glycol content in the glycol component is preferably 75 mol% or more, more preferably 90 mol% or more. Examples of other components include diethylene glycol and polyethylene glycol.

  Although the glass transition temperature (Tg) of cationic dyeable polyester is not specifically limited, It is preferable that it is 60-70 degreeC, Furthermore, it is 60-65 degreeC. When Tg is too high, the high-speed stretchability is lowered, and when the resulting decorative sheet is used after being thermoformed, the formability tends to be lowered.

  Moreover, in the cationic dyeable polyester, a colorant such as carbon black, a weathering agent, an antifungal agent, and the like may be blended as necessary within a range not impairing the effects of the present invention.

  As the sea component polymer, a polymer having higher solubility in a solvent or decomposability by a decomposing agent than a cationic dye dyeable polyester is selected. Specific examples of the sea component polymer include, for example, a water-soluble polyvinyl alcohol resin (water-soluble PVA), polyethylene, polypropylene, polystyrene, an ethylene-propylene copolymer, an ethylene-vinyl acetate copolymer, and a styrene-ethylene system. Examples thereof include a copolymer and a styrene-acrylic copolymer.

  The sea-island type composite fiber can be produced by melt spinning in which a sea component polymer and a dye dyeable polyester that is an island component polymer are melt-extruded from a die for composite spinning. The fineness of the sea-island composite fiber is not particularly limited, but is preferably 0.5 to 10 dtex, more preferably 0.7 to 5 dtex.

  The molten sea-island type composite fiber discharged from the die is cooled by a cooling device, and further pulled and thinned to a desired fineness by a suction device such as an air jet nozzle. Then, the long fiber web is obtained by depositing the stretched long fibers on a collecting surface such as a movable net. In addition, as needed, in order to stabilize a form, you may crimp | bond partly by further pressing a long fiber web.

  And the entangled nonwoven fabric of a sea-island type composite fiber is manufactured by performing an entanglement process to the obtained long fiber web. As a specific example of the entanglement treatment of the long fiber web, for example, after laminating a plurality of layers in the thickness direction using a cross wrapper or the like, at least one barb is formed simultaneously or alternately from both sides. An example of such a process is needle punching under conditions of penetration.

In addition, an oil agent or an antistatic agent may be added to the sea-island type composite fiber at any stage from the spinning process to the entanglement treatment of the sea-island type composite fiber. Furthermore, if necessary, the entangled state of the entangled nonwoven fabric of the sea-island type composite fibers may be made dense in advance by performing a shrinkage treatment in which the sea-island type composite fibers are immersed in warm water of about 70 to 150 ° C. . Further, after the needle punch, the fiber density may be further refined by hot press treatment to give form stability. It is preferably in the range of about 100 to 2000 g / m ² as a weight per unit area of the entangled nonwoven fabric of sea-island type composite fibers thus obtained.

  Moreover, you may give the process which a fiber density and an entanglement degree are raised by heat-shrinking the entangled nonwoven fabric of a sea-island type composite fiber as needed. The purpose is to further densify the entangled nonwoven fabric of sea-island composite fibers densified by heat shrink treatment, to fix the shape of the entangled nonwoven fabric of sea-island composite fibers, and to smooth the surface, etc. As necessary, the fiber density may be further increased by performing a hot press treatment.

  Then, by removing the sea component polymer from the sea-island composite fiber in the densified sea-island composite fiber, a entangled non-woven fabric of cationic dye-dyeable polyester can be obtained. As a method for removing the sea component polymer from the sea-island type composite fiber, there is a conventionally known method for forming an ultrafine fiber such that the entangled web is treated with a solvent or a decomposing agent that can selectively remove only the sea component polymer. It can be used without particular limitation. Specifically, for example, when water-soluble PVA is used as the sea component polymer, hot water is used as the solvent.

  When water-soluble PVA is used as the sea component polymer, it can be extracted and removed until the removal rate of water-soluble PVA reaches about 95 to 100% by treatment in hot water at 85 to 100 ° C. for 100 to 600 seconds. preferable. In addition, water-soluble PVA can be efficiently extracted and removed by repeating the dip nip process.

The basis weight of the entangled nonwoven fabric of the ultrafine fibers of the cationic dyeable polyester thus obtained is preferably 140 to 3000 g / m ² , more preferably 200 to 2000 g / m ² .

  In the production of the artificial leather base material of the present embodiment, the entanglement of the ultrafine fiber of the cationic dyeable polyester in one or both of before and after the ultrafine fiber generation type fiber such as the sea-island type composite fiber is made into the ultrafine fiber. In order to impart shape stability and a sense of fulfillment to the synthetic nonwoven fabric, a polymer elastic body such as polyurethane is impregnated into the internal voids of the entangled nonwoven fabric.

  Specific examples of the polymer elastic body include polyurethane, acrylonitrile elastomer, olefin elastomer, polyester elastomer, polyamide elastomer, acrylic elastomer, and the like. Of these, polyurethane is preferred.

  The polymer elastic body is a colorant such as a pigment or dye such as carbon black, a coagulation regulator, an antioxidant, an ultraviolet absorber, a fluorescent agent, an antifungal agent, and a permeation as long as the effects of the present invention are not impaired. Agents, antifoaming agents, lubricants, water repellents, oil repellents, thickeners, extenders, curing accelerators, foaming agents, water-soluble polymer compounds such as polyvinyl alcohol and carboxymethyl cellulose, inorganic fine particles, conductive agents, etc. You may contain.

  The content of the polymer elastic body is 0.1 to 50% by mass, more preferably 3 to 40% by mass, and particularly 5 to 25% by mass, based on the total amount with the cationic dyeable polyester fiber. 10 to 15% by mass makes it difficult to transfer the cationic dye from the decorative sheet dyed with the cationic dye to the decorative molded body and other members, and also provides a sense of fulfillment and flexibility. This is preferable because an artificial leather base material excellent in balance can be obtained.

  In this way, the nonwoven fabric of the cationic dye-dyeable polyester is impregnated with the polymer elastic body to obtain the raw material of the artificial leather base material. Even if the raw material of the artificial leather base material is used as it is as an artificial leather base material, the thickness of the artificial leather can be adjusted by slicing or grinding in multiple pieces in the direction perpendicular to the thickness direction as needed. It may be used as a substrate. In addition, if necessary, at least one side is preferably 120-600 counts, more preferably 320-600 count grade sandpaper or emery paper is used for buffing to raise the suede or nubuck tone An artificial leather base material may be used.

で表される単位中に含まれるスルホニウムイオンにカチオン染料がイオン結合により固定されて優れた染色堅牢性を発揮する。 The artificial leather substrate is dyed with a cationic dye. By dyeing an artificial leather base material with a cationic dye, the following formula (I _a ) is obtained, which becomes a cationic dye dyeable dye dyeable polyester:

A cationic dye is fixed to the sulfonium ion contained in the unit represented by the formula (I) by an ionic bond, and exhibits excellent dyeing fastness.

  Any cationic dye may be used as long as it is a conventionally known cationic dye. The cationic dye is dissolved in the dyeing liquid and becomes a dye ion having cationic properties such as a quaternary ammonium group, and is ionically bonded to the cationic dyeable polyester fiber. Such cationic dyes generally form salts with anions such as chloride ions. Such anions such as chloride ions are contained in the cationic dye, but are washed away by washing after dyeing. Specific examples of the cationic dye include azo blue cationic dyes such as CI Basic Blue 54 and CI Basic Blue 159, CI Basic Blue 3, CI Basic Blue 6, CI Basic Blue 10, CI Basic Blue 12, CIBasic Blue 75, Oxazine blue cationic dyes such as CI Basic Blue 96, C.I. I. Coumarin dyes such as Basic Yellow 40, C.I. I. Methine dyes such as Basic Yellow 21, C.I. I. C. is an azomethine dye such as Basic Yellow 28 or an azo red dye. I. Basic Red 29 or C.I. I. Basic Red 46, C.I., a xanthene dye. I. Basic Violet 11 etc. are mentioned. These may be used alone or in combination of two or more.

  The dyeing method is not particularly limited, and examples thereof include a method of dyeing using a dyeing machine such as a liquid dyeing machine, a beam dyeing machine, and a jigger. As conditions for the dyeing process, dyeing may be performed at high pressure, but dyeing at normal pressure is preferable from the viewpoint of reducing environmental burden and reducing dyeing costs. When dyeing at normal pressure, the dyeing temperature is preferably 60 to 100 ° C., more preferably 80 to 100 ° C. Further, a dyeing aid such as acetic acid or mirabilite may be used for dyeing.

When dyeing using a cationic dye, the concentration of the cationic dye in the dye solution is 0.05 to 20% owf, more preferably 0.1 to 15% owf, with respect to the artificial leather substrate to be dyed. Such a range is preferable from the viewpoint that the cationic dye-dyeable polyester fiber sufficiently develops a dark color and that the cationic dye is less likely to migrate to a decorative molded body and other members. When the concentration of the cation dye in the dye solution is too high, the cation dye tends to move to the decorated molded article due to the presence of a large amount of cation dye that is not fixed to the dyeing seat of the dye dyeable polyester fiber. There is. Further, when the concentration of the cationic dye is too low, it tends to be difficult to develop a dark color such that the lightness L ^* value ≦ 50.

  In the present embodiment, it is preferable to remove the cationic dye having a low binding force by washing the artificial leather substrate dyed with the cationic dye in a hot water bath containing an anionic surfactant. By such a washing treatment, the cationic dye having a low binding force is sufficiently removed, so that the cationic dye does not easily move to the decorated molded body or other members. Specific examples of the anionic surfactant include, for example, Soljin R manufactured by Nissei Kasei Co., Ltd., Senkanol A-900 manufactured by Senka Co., Ltd., Meisanol KHM manufactured by Meisei Chemical Industry Co., Ltd., and the like.

  The washing treatment in a hot water bath containing an anionic surfactant is preferably performed in a hot water bath of 50 to 100 ° C, more preferably 60 to 80 ° C. Moreover, it is preferable to use the dyeing machine which performed the dyeing | staining process as a hot water bath tank from the point which can simplify a manufacturing process. Moreover, it is preferable to perform washing | cleaning for about 10 to 30 minutes, Furthermore, about 15 to 20 minutes. The washing is preferably repeated once or more, preferably twice or more. The artificial leather substrate dyed with the cationic dye is washed and then dried. By such a washing method, the color transfer of the cationic dye is sufficiently suppressed by sufficiently washing to about 90 ppm or less with respect to the weight of the artificial leather base material dyed with washable chlorine in the cationic dye. This is preferable.

  Various finishing treatments may be applied to the artificial leather base as necessary. Finishing treatment includes stagnation softening treatment, reverse seal brushing treatment, antifouling treatment, hydrophilic treatment, lubricant treatment, softener treatment, antioxidant treatment, UV absorber treatment, fluorescent agent treatment, flame retardant treatment, etc. Can be mentioned.

  In this way, a decorative sheet which is an artificial leather substrate dyed with a cationic dye is obtained. The decorative sheet preferably has a water fastness of cotton contamination determined by the JIS method (JIS L 0846) of grade 4-5 or higher. When the water fastness of the decorative sheet is 4-5 or higher, the decorative sheet has few cationic dyes that are not ion-bonded so as to fall off by contact with water, resulting in color transfer. It is suppressed.

In addition, the decorative sheet contains 0.05 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and particularly 0.1 to 10 parts by mass of a cationic dye with respect to 100 parts by mass of the artificial leather substrate. It is preferable to contain. When there is too much content of the cationic dye with respect to 100 mass parts of artificial leather base materials, there exists a tendency for transfer of a cationic dye to become difficult to be suppressed sufficiently. On the other hand, when the content of the cationic dye is too small, it tends to be difficult to dye a deep color such as lightness L ^* value ≦ 50, and further L ^* value ≦ 35.

Since the decorative sheet of this embodiment is dyed with a cationic dye, for example, even if the lightness L ^* value ≦ 50 is a dark color, the dye is transferred to the decorative molded body and other members. Hard to do. In addition, when the dyed decorative sheet has a dark color such that the L ^* value ≦ 35, the effect of the present invention becomes more remarkable. In the case of L ^* value ≦ 35, not only dyeing but also color transfer property may be suppressed by adding a pigment such as carbon black to a cationic dye dyeable polyester fiber or a polymer elastic body. . Even if such a decorative sheet is a dark color, the above-described cationic dye-dyeable polyester fiber is used and washed in a hot water bath containing an anionic surfactant as described above. When the content of the cationic dye is within the range, color transfer is sufficiently suppressed.

The apparent density of the decorative sheet is preferably 0.3 to 0.6 g / cm ³ , particularly 0.45 to 0.55 g / cm ³ from the viewpoint of obtaining a supple texture.

  Even if the artificial leather base material is used as it is as a decorative sheet, or if the surface fibers are brushed and used as a decorative sheet for suede-like artificial leather, a silver-tone resin layer is provided on the surface. It may be used after being finished on a decorative sheet of silver-tone artificial leather.

  The decorative sheet is formed into a decorative molded body having a three-dimensional shape that is integrated with the surface of the decorated molded body, for example, by the following method.

  First, as an example of a method for manufacturing a decorative molded body, a preform molded body in which a decorative sheet is molded into a three-dimensional shape is placed in a cavity of a mold, and a molten resin is injected into the cavity and solidified. A method for molding a resin molded body in which a decorative sheet is integrated with the surface layer will be described.

  First, a method for manufacturing a preform molded body by vacuum forming a decorative sheet, which is a napped artificial leather including an artificial leather base material dyed with a cationic dye, to form a three-dimensional shape will be described. In addition, as a molding method for obtaining the preform molded body, a molding method such as vacuum / pressure forming, pressure forming, or hot press forming may be used instead of vacuum forming.

  As shown in FIG. 1A, a stack 3 is formed by placing a non-breathable thermoplastic resin sheet 2 on a decorative sheet 1. The thermoplastic resin sheet 2 is used for imparting airtightness to the decorative sheet 1 in vacuum forming.

  The thermoplastic resin sheet is not particularly limited as long as it is softened so that it can be shaped by heating during vacuum forming, and can be kept airtight without pinholes, and can be selectively peeled off in later steps. Used. Examples of the thermoplastic resin that forms such a thermoplastic resin sheet include amorphous thermoplastic resins such as (meth) acrylic resins, and crystalline heat having a low melting point such as polyolefin resins such as polyethylene and polypropylene. A plastic resin is mentioned. The thickness of the thermoplastic resin sheet is preferably 10 to 300 μm, more preferably 15 to 200 μm, and particularly preferably about 30 to 100 μm. If the thermoplastic resin sheet is too thick, the formability tends to decrease. Moreover, when the thermoplastic resin sheet is too thin, it tends to be difficult to peel the thermoplastic resin sheet 2 from the decorative sheet 1 after preform molding.

  Then, the stack 3 is heated and softened by the heater H as shown in FIG. The heating temperature by the heater H is a temperature at which the stacked body 3 can be deformed into a shape along the mold M1 of the vacuum forming machine M, and is selected from a range of, for example, 100 to 180 ° C. so as not to be completely melted. Is done.

  The stack 3 heated and softened is vacuum-formed using a vacuum forming machine M as shown in FIG. Specifically, as shown in FIG. 1C, the mold M1 of the vacuum forming machine M is brought into close contact with the softened stack 3, and the air between the stack 3 and the mold M1 is formed into the mold M1. The stack 3 is adsorbed by the molding die M1 by being evacuated from the vacuum hole v formed in the above by a vacuum pump, and is brought into close contact with the atmospheric pressure, and then the formed stack 3 is cooled and solidified. In this way, the preform molded body 4 'is molded.

  Then, as shown in FIG. 1 (d), the preform molded body 4 'is released from the molding die M1. As shown in FIG. 1E, the preform molded body 4 'is trimmed with an unnecessary portion N as necessary.

  Then, as shown in FIG. 1 (f), the preform molded body 4 is obtained by peeling the thermoplastic resin sheet 2 from the preform molded body 4 ′.

  The preform molded body thus obtained is integrated with the decorated molded body to form a decorated molded body. As a method for integrating the preform molded body into the decorated molded body, in-mold molding, in which the preform molded body is integrated with the decorated molded body, which is a resin molded body molded by injection molding, or preform The method of adhering to the decorating molded object previously shape | molded through the adhesive agent on one surface of the molded object is mentioned. In the present embodiment, as a representative example, FIG. 2 shows a method of manufacturing a decorative molded body 10 obtained by integrating the preform molded body 4 with a decorated molded body 5 to be injection-molded by in-mold molding. The description will be given with reference. In the present embodiment, a method for performing in-mold molding using the preform molded body 4 obtained by peeling the thermoplastic resin sheet 2 from the preform molded body 4 ′ will be described, but instead of the preform molded body 4. The preform molded body 4 ′ from which the thermoplastic resin sheet 2 has not been peeled may be subjected to in-mold molding as it is, and the thermoplastic resin sheet 2 may be peeled after in-mold molding.

  As shown in FIG. 2A, the mold 17 includes a movable mold 17a including a cavity C and a fixed mold 17b. A stripper plate 17c is disposed between the movable mold 17a and the fixed mold 17b. First, the preform molded body 4 is disposed in the cavity portion C.

  The method for disposing the preform molded body 4 in the cavity portion C is not particularly limited, but the preform molded body 4 is preferably fixed to the cavity portion C for positioning. When the preform molded body 4 is not fixed to the cavity portion C, the preform molded body 4 may be displaced in the cavity portion C due to the flow of the injection resin at the time of injection molding in the next process. . Specific examples of the method of fixing the preform molded body 4 to the cavity portion C include, for example, a method of fixing the preform molded body 4 to the surface of the movable mold with an adhesive, a hole or a recess included in the shape of the preform molded body 4 Can be fixed by fitting it in the core of the movable mold that matches the shape.

  Then, as shown in FIG. 2B, an in-mold molded body which is a decorative molded body in which the preform molded body 4 is integrated on the surface by injecting a molten resin 5a into the cavity C by injection molding. Is molded. Specifically, the movable mold 17a and the fixed mold 17b are clamped, and the cylinder 18 of the injection molding machine 16 is advanced until the nozzle 15 contacts the sprue bush 17f of the fixed mold 17b. The molten resin 5a melted in the cylinder 18 is injected with a screw 19 to inject the molten resin 5a into the mold 17 for injection molding. The injected molten resin 5a flows through the resin flow path R in the mold 17 and flows into the cavity portion C and is filled. At this time, in order for the molten resin 5a to appropriately permeate into the artificial leather base material of the preform molded body 4, the injection molded body which is the decorated molded body 5 molded by injection molding has high adhesiveness due to the anchoring effect. It is integrated with the preform molded body 4 so as to be maintained.

  Examples of the resin for forming an injection-molded body molded by in-mold molding include ABS resins, polycarbonate resins, polyolefin resins such as polypropylene, and polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT). Various thermoplastic resins such as resins and various polyamide-based resins are used without particular limitation, and are appropriately selected depending on the application. For example, as a resin used for a casing of a mobile phone, a mobile device, a home appliance, etc., a resin having excellent impact resistance such as an ABS resin, a polycarbonate resin, and a polyolefin resin such as polypropylene is preferably used.

  The injection molding conditions are such that the resin can flow to the flow end depending on the melting point and melt viscosity of the resin to be injected, the shape of the molded body, and the resin thickness (resin temperature, mold temperature, injection pressure, injection speed, injection) The subsequent holding pressure and cooling time) are appropriately selected.

  And after completion | finish of injection, as shown in FIG.2 (c), the molten resin 5a is cooled and the decorating molded object 5 which is an injection molded object is formed. In this way, the decorative molded body 10 in which the preform molded body 4 is integrated with the decorated molded body 5 is molded. Then, by opening the mold 17, the movable side mold 17a and the fixed side mold 17b are isolated, and the decorative molded body 10 is taken out as shown in FIG. In this way, a decorative molded body 10 in which the decorated molded body 5 that is an injection molded body is integrated on one surface of the preform molded body 4 is obtained.

In the decorative molded body thus obtained, a decorative sheet including an artificial leather base material dyed with a cationic dye is laminated and integrated on the surface layer. In such a decorative molded body, even if a light-colored, white, or transparent decorated molded body having a lightness L ^* value> 50, and further a lightness L ^* value> 70 is used, Color transfer is also suppressed by heating during production and use. In addition, the decorative molded body is excellent in contrast when ΔL ^*, which is a difference in L ^* value between the decorative sheet and the decorated molded body, is 10 or more, further 20 or more, and particularly 30 or more. Since it has color, it is preferable from the point which is excellent in design property. Such a decorative molded body is preferably used as a casing for mobile phones, smartphones, various mobile devices, home appliances, etc., an interior member for vehicles, aircraft, etc., an exterior member for building materials, furniture, and the like.

  Hereinafter, the present invention will be described more specifically with reference to examples. The scope of the present invention is not limited by the examples.

[Example 1]
Ethylene-modified polyvinyl alcohol (PVA; ethylene unit content of 8.5 mol%, polymerization degree 380, saponification degree 98.7 mol%) as a sea component thermoplastic resin, and sulfoisophthalic acid as an island component thermoplastic resin Polyethylene terephthalate (PET) modified with tetrabutylphosphonium salt: (containing 1.7 mol% of tetrabutylphosphonium salt unit of sulfoisophthalic acid, 5 mol% of 1,4-cyclohexanedicarboxylic acid unit, 5 mol% of adipic acid unit; A non-woven fabric in which sea-island type composite continuous fibers were three-dimensionally entangled was prepared, which contained a glass transition temperature of 62 ° C. and the mass ratio of sea component to island component was sea component / island component = 25/75.

Then, a polyurethane emulsion (polyurethane / ether polyurethane-based polyurethane solid content concentration 30% emulsion) is impregnated into a nonwoven fabric in which sea-island composite long fibers are three-dimensionally entangled, and then dried in a 150 ° C. drying oven. By drying, polyurethane was applied. Then, a sea component contained in the sea-island composite long fiber is extracted and removed by immersing a nonwoven fabric in which the sea-island composite fiber provided with polyurethane is three-dimensionally entangled in hot water at 95 ° C. for 20 minutes. Dried in a drying oven. Thus, the raw material of the artificial leather base material which is the entangled nonwoven fabric of the ultrafine fiber of the cationic dye dyeable polyester fiber impregnated with the polyurethane was obtained. The raw material of the artificial leather base material was sliced and divided into two parts, and the surface was buffed with a 600th sandpaper to finish a suede-like surface. The artificial leather base material having a suede-like surface thus obtained includes an entangled nonwoven fabric of a cationic dye-dyeable polyester fiber having a fineness of 0.08 dtex, a polyurethane content of 10% by mass, and a thickness of 0. It was 5 mm and the apparent density was 0.55 g / cm ³ .

  The artificial leather base material is bathed in a dye solution at 90 ° C. containing 18% owf as a cationic dye, Nichilon Red-GL (manufactured by Nissei Kasei Co., Ltd.), and 90% acetic acid 1 g / L as a dyeing assistant. It was immersed for 40 minutes at a ratio of 1:30 and dyed red. And the process of soaping at 70 degreeC using the hot water bath containing Solgin R2g / L as an anionic surfactant in the same dyeing bath was repeated twice. And the dyeing | staining sheet | seat for dyeing | staining was obtained by drying after soaping.

In this way, a decorative sheet was obtained which was a suede-like artificial leather in which an artificial leather base material containing a non-woven fabric of cationic dye-dyeable polyester fibers of 0.08 dtex and polyurethane was dyed in a deep red color with a cationic dye. The obtained decorative sheet had a thickness of 0.55 mm and an apparent density of 0.50 g / cm ³ . Further, the L ^* value measured by the following method was 36, and the water fastness was 4-5 grade.

[L ^* value]
Using a spectrophotometer (manufactured by Minolta: CM-3700), the brightness from the coordinate value of the L ^* a ^* b * color system of the surface of the dyed decorative sheet cut out according to JISZ 8729 L ^* was determined. The value is an average value of three points measured by uniformly selecting an average position from the test piece.

[Water fastness]
This was carried out as a water fastness test for cotton cloth according to the JIS method (JIS L 0846). Specifically, a 6 × 6 cm test piece was cut out from the decorative sheet. Then, the test piece was immersed in water at room temperature, then attached to a sweat tester and applied with a load of about 45 N, and placed in a dryer at 37 ± 2 ° C. and held for 4 hours. And the firmness was judged compared with the gray scale for contamination. And the series at that time was determined.

  And the obtained sheet for decorating was shape | molded using the metal mold | die which has a cavity for obtaining a preform molded object. The specific shape of the preform molded body was a dish-shaped molded body assuming a smartphone cover having a height of 7 mm from the bottom surface to the outer surface as shown in FIG.

  Specifically, a stack was formed by placing a transparent acrylic sheet having a thickness of 75 μm on one surface of the decorative sheet. Then, the stack was heated with an infrared heater to a temperature of 150 ° C., and vacuum-pressure forming was performed with a predetermined pressure pressure using a mold having each shape. A preform molded body with a thermoplastic resin sheet in which the surface of the transparent acrylic sheet forming the stack and the decorative sheet was thermocompression bonded was obtained by vacuum / pressure forming. And the transparent acrylic sheet was peeled from the preform molding with a thermoplastic resin sheet, and the preform molding was obtained.

And in-mold shaping | molding was performed using the obtained preform molded object. Specifically, an in-mold mold corresponding to the shape of the preform molded body was prepared. Then, the mold was mounted on an injection molding machine, and the preform molded body was placed in the cavity of the mold. And milky white ABS resin (Toyolac ABS700 manufactured by Toray Industries, Inc.) was injection molded under the conditions of a resin temperature of 240 ° C and a mold temperature of 50 ° C. Thus, a decorative molded body was obtained by in-mold molding. The L ^* value of the injection-molded decorated molded body was 92.

In addition, a different color was added in the same manner except that clear polycarbonate (Iupilon S2000 manufactured by Mitsubishi Engineering Plastics Co., Ltd.) was used instead of ABS resin and the resin temperature was changed to 280 ° C and the mold temperature was set to 80 ° C. A decorative molded body was also molded. The L ^* value of the injection-molded decorated molded body was 93.

  And the color transferability of the decorative molded body was evaluated according to the following evaluation method.

[Color transfer of decorative molded body]
The obtained decorative molded body was visually observed, and the migration of the dye to the decorated molded body was determined to be 1 (large transition) to 5 (no transition) using a contamination gray scale.

[Evaluation of color migration by accelerated test of decorative molded body]
A decorative sheet was placed on the surface of a 30 × 50 mm square plate of the ABS resin or polycarbonate having a thickness of 1.5 mm, and pressure was applied uniformly so that the load was 7.5 g / cm ² . Then, it was left for 24 hours in an atmosphere of 70 ° C. and 95% RH. Then, the color difference ΔE ^* between the square plate before being left and the square plate after being left was measured using a spectrophotometer, and judged according to the following criteria.
Grade 5: 0.0 ≦ ΔE ^* ≦ 0.2
Grade 4-5: 0.2 <ΔE ^* ≦ 1.4
4th class: 1.4 <ΔE ^* ≦ 2.0
Grade 3-4: 2.0 <ΔE ^* ≦ 3.0
Third grade: 3.0 <ΔE ^* ≦ 3.8
Grade 2-3: 3.8 <ΔE ^* ≦ 5.8
Second grade: 5.8 <ΔE ^* ≦ 7.8
Class 1-2: 7.8 <ΔE ^* ≦ 11.4
First grade: 11.4 <ΔE ^*

  The results are shown in Table 1 below.

[Example 2]
In Example 1, an artificial leather base material was dyed in the same manner as in Example 1 except that the sheet was decorated under the following dyeing conditions to obtain a decorative sheet.

  Bath ratio in a 90 ° C dye solution containing 5% owf of Nichilon Blue-AZN (manufactured by Nissei Kasei Co., Ltd.) as a cationic dye, and 90% acetic acid as a dyeing assistant. It was immersed for 40 minutes at a ratio of 1:30 and dyed blue. And the process of soaping at 70 degreeC using the hot water bath containing Solgin R2g / L as an anionic surfactant in the same dyeing bath was repeated twice. And the dyeing | staining sheet | seat for dyeing | staining was obtained by drying after soaping.

In this way, a decorative sheet was obtained in which an artificial leather base material containing a 0.08 dtex cationic dye-dyeable polyester fiber nonwoven fabric and polyurethane was dyed dark blue with a cationic dye. The obtained decorative sheet had a thickness of 0.83 mm and an apparent density of 0.47 g / cm ³ . The L ^* value was 47.
Then, the preform molded body and the decorative molded body were molded in the same manner as in Example 1, except that the obtained decorative sheet was used instead of the decorative sheet obtained in Example 1, and the molding was carried out. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[Example 3]
In place of the artificial leather substrate produced in Example 1, a non-woven fabric of cationic dye-dyeable polyester fibers having a fineness of 0.2 dtex, a polyurethane ratio of 10% by mass, a thickness of 0.82 mm, and an apparent density of 0.46 g / A cm ³ artificial leather substrate was produced. The artificial leather base material is bathed in a dye solution at 90 ° C. containing 6% owf of cationic dye Nichilon Red-GL (manufactured by Nissei Kasei Co., Ltd.) and 90% acetic acid 1 g / L as a dyeing assistant. It was immersed for 40 minutes at a ratio of 1:30 and dyed red. And the process of soaping at 70 degreeC using the hot water bath containing Solgin R2g / L as an anionic surfactant in the same dyeing bath was repeated twice. And the sheet | seat for decorating which is the artificial leather base material dye | stained with the cationic dye was obtained by drying after soaping. The obtained decorative sheet contained a non-woven fabric of cationic dye-dyeable polyester fibers having a fineness of 0.2 dtex, a thickness of 1.19 mm, and an apparent density of 0.40 g / cm ³ . The L ^* value was 42.
Then, the preform molded body and the decorative molded body were molded in the same manner as in Example 1, except that the obtained decorative sheet was used instead of the decorative sheet obtained in Example 1, and the molding was carried out. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[Example 4]
In Example 1, an artificial leather base material was dyed in the same manner as in Example 1 except that the sheet was decorated under the following dyeing conditions to obtain a decorative sheet.

  Bath ratio in a 90 ° C dye solution containing 18% owf of Nichilon Blue-AZN (manufactured by Nissei Kasei Co., Ltd.) as a cationic dye and 90% acetic acid as a dyeing assistant. It was immersed for 40 minutes at a ratio of 1:30 and dyed blue. And it washed with water once at 70 degreeC with the same dyeing bath. And the sheet | seat for decorating which is the dyed artificial leather base material was obtained by drying.

The obtained decorative sheet had a thickness of 0.83 mm and an apparent density of 0.47 g / cm ³ . The L ^* value was 33.
Then, the preform molded body and the decorative molded body were molded in the same manner as in Example 1, except that the obtained decorative sheet was used instead of the decorative sheet obtained in Example 1, and the molding was carried out. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

[Comparative Example 1]
Artificial leather base material in the same manner as in Example 1 except that PET modified with isophthalic acid (containing 6 mol% isophthalic acid unit) was used as the island component thermoplastic resin instead of the cationic dyeable polyester fiber. Got. Artificial leather base material is dyed in dark red by liquid dyeing at 130 ° C for 1 hour using D.Red-W, KiwalonRubin2GW and KiwalonYellow6GF, which are disperse dyes. A decorative sheet as a leather base material was obtained. And it evaluated similarly to Example 1 using the obtained sheet | seat for decorating. The results are shown in Table 1.

[Comparative Example 2]
Artificial leather base material in the same manner as in Example 1 except that PET modified with isophthalic acid (containing 6 mol% isophthalic acid unit) was used as the island component thermoplastic resin instead of the cationic dyeable polyester fiber. Got. Then, the artificial leather base material is dyed with a disperse dye such as D Blue HLA, D Red HLA, and D Yellow HLA for 1 hour at 130 ° C, reduced and washed in the same dye bath, and dyed dark blue. A decorative sheet as an artificial leather base was obtained. And it evaluated similarly to Example 1 using the obtained sheet | seat for decorating. The results are shown in Table 1.

  According to the decorative sheet of the present invention, the surface of a resin molded body such as a mobile terminal body (smartphone, tablet PC) and accessories such as a case and a cover, a casing of an electronic device, a vehicle interior material, and cosmetics is textile-like. Can be decorated.

DESCRIPTION OF SYMBOLS 1 Sheet for decoration 2 Thermoplastic resin sheet 3 Stack body 4 Preform molded body 5 Decorated molded body 10 Decorated molded body

Claims (9)

A decorative sheet for decorating a decorated molded body,
An artificial leather base material including a fabric of a cationic dye-dyeable polyester fiber and a polymer elastic body imparted to the fabric and dyed with at least one cationic dye Sheet.   The decorative sheet according to claim 1, wherein the fabric includes a nonwoven fabric of the cationic dye-dyeable polyester fiber.   The decorative sheet according to claim 1 or 2, which has a raised surface.   The decorative sheet according to any one of claims 1 to 3, wherein the water fastness test for cotton fabric according to JIS L 0846 is 4-5 or higher. Lightness L ^* value <= 50, The decorative sheet according to any one of claims 1 to 4.   The decorative sheet according to any one of claims 1 to 5, which is a preform molded body shaped into a three-dimensional shape.   A decorative molded body obtained by laminating and integrating the decorative sheet according to any one of claims 1 to 6 on the decorated molded body. The decorative molded body according to claim 7, wherein the decorated molded body has a lightness L ^* value> 50. The decorative molded body according to claim 8, wherein a brightness difference ΔL ^* between the decorative sheet and the decorated molded body is 10 or more.

Images