JP2011206998A - Decorative sheet and decorative molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet which can suppress generation of a bubble from a porous decorative sheet and suppress generation of unevenness of a surface even when the decorative sheet is applied to a decorative molded article necessitating deep drawing, and which shows excellent designability and can meet various requirements for designability, and to provide a decorative molded article using the decorative sheet.SOLUTION: The decorative sheet 1 is used by making a curved part and integrating the same and a base resin material into one body by injection molding. The decorative sheet 1 is used for the decorative molded article. The decorative sheet 1 is made by laminating, orderly from the reverse surface side 19, an adhesive layer 11 on the base material side, the porous decorative sheet 13, an adhesive layer 15 on a protective layer side and a surface protective layer 16, and integrating them into one body. The adhesive layer 15 on the protective layer side and the surface protective layer 16 are each composed of a specific material. A print area 12 of ink is formed on the surface protective layer 16.

Description

  The present invention provides a decorative sheet integrated with a base resin by forming a curved portion by vacuum molding or hot press molding, and then injection-molding the base resin on the back side in the mold, and the decorative sheet and the above The present invention relates to a decorative molded product obtained by integrating a base resin.

For interiors of automobiles such as armrests, cosmetic molded products obtained by in-mold molding of a decorative sheet using a veneer of a wood (a porous decorative sheet) are used.
Conventionally, in producing a decorative molded product, as shown in FIG. 12A, first, a veneer 92 having a thickness of about 200 to 500 μm is prepared as a porous decorative sheet.

  Next, as shown in FIG. 12B, the veneer 92 is impregnated with a thermosetting resin 93 such as a polyester-based styrene crosslinked alkyd resin to obtain a decorative sheet 90. Next, as shown in FIG. 13A, an adhesive layer 94 suitable for a base resin to be molded later is joined to the back side of the decorative sheet 90. Next, as shown in FIG. 13 (b), a decorative sheet 90 is inserted into the molding die, and then a base resin is injection molded on the back side to obtain an intermediate molded product 97.

Next, as shown in FIGS. 13C to 13F, the surface of the decorative sheet 90 is added to the intermediate molded product 97 in order to add excellent appearance characteristics such as smoothness, transparency, and depth. After the first clear layer 95 made of polyester is formed by painting, the painted surface is polished. Furthermore, after coating the second clear layer 96 on the first clear layer 95, the coated surface is polished to obtain a cosmetic molded product 98.
However, in the conventional cosmetic molded product 98, it is necessary to repeatedly perform surface polishing and coating a plurality of times during manufacture. For this reason, the production efficiency is poor, which hinders cost reduction.

In order to improve production efficiency, a decorative sheet in which a decorative sheet having a wood veneer, a laminate of a transparent film and a hard coat film is bonded by an adhesive sheet is prepared, and a base resin is applied to the back side. A method for producing a cosmetic molded product by injection molding has been developed (see Patent Document 1).
Also, a polycarbonate / single plate obtained by laminating and sticking a single plate on a polycarbonate resin plate or sheet with either a moisture-curable hot melt adhesive, a thermoplastic polyester resin adhesive, or a thermoplastic silane-modified resin adhesive A laminated body has been proposed (Patent Document 2).

  Also, a step of placing a porous skin material in the mold and integrally molding the resin equipment on the back surface of the skin material, and opening a gap between the surface of the skin material and the mold surface to form a gap, After injecting a thermosetting paint into the gap, the mold is closed and heated while applying pressure to form a film that expands the function of the skin material on the surface of the skin material. A method has been proposed (see Patent Document 3).

Japanese Patent Laid-Open No. 9-226082 Japanese Patent Application Laid-Open No. 9-264759 JP 2003-159724 A

  In the method of laminating a sheet using an adhesive, it is necessary to form a curved portion on the decorative sheet by performing vacuum molding or hot press molding in order to improve the shape followability during injection molding of the base resin. In recent years, application of the above-described decorative molded product is also demanded for automobile interior materials that require a relatively large curved portion to be formed.

  However, when a deep drawing process for forming a curved portion having a large curvature is performed, when a polycarbonate sheet is used as a protruding sheet, that is, a clear sheet formed on a porous decorative sheet, the temperature is higher than 145 ° C. Need to be molded. As a result, bubbles are generated from the porous decorative sheet, and the bubbles generated in the adhesive layer may be enlarged during high-temperature molding, and the dimensional change of the decorative sheet may occur. Thereby, the unevenness | corrugation generate | occur | produced in the clear sheet and there existed a problem that the designability of a cosmetics molded product will be impaired.

  In addition, the requirements for the design properties of cosmetic molded products are diverse, and change according to the background of the times. Therefore, it is desired to develop cosmetic molded products that can meet various design requirements.

  The present invention has been made in view of such problems, and even when applied to a cosmetic molded product that requires deep drawing, it suppresses the generation of bubbles from the porous decorative sheet, and the surface unevenness is reduced. An object of the present invention is to provide a decorative sheet that can suppress the occurrence, has excellent design properties, and can meet various requirements for design properties, and a cosmetic molded article using the decorative sheet.

The first invention is a decorative sheet used by integrating with a base resin by forming a curved portion by vacuum molding or hot press molding, and then injection molding the base resin on the back side in a mold. There,
The decorative sheet is formed by laminating and integrating a base material side adhesive layer, a porous decorative sheet, a protective layer side adhesive layer, and a transparent surface protective layer in order from the back surface side.
The protective layer side adhesive layer is formed by curing a moisture-curing transparent polyurethane adhesive,
The surface protective layer is mainly composed of polymethyl methacrylate, or a composite resin of polycarbonate and polybutylene terephthalate, or a composite resin of polycarbonate and polyethylene terephthalate, and has a glass transition point of 90 to 130 ° C.
The surface protective layer has a thickness of 300 to 1000 μm,
The decorative sheet is characterized in that a printing region made of ink is formed on the surface protective layer.

According to a second aspect of the present invention, the decorative sheet is vacuum-formed or press-molded to form a curved portion in the decorative sheet, the decorative sheet is then placed in a mold, and a base material is provided on the back side of the decorative sheet. A decorative molded product made by injection molding of resin,
As the decorative sheet, the decorative sheet according to the first invention is employed (claim 6).

The decorative sheet of the first invention is used by integrating the base resin with the base resin by forming a curved portion by vacuum forming or hot press forming and then injection-molding the base resin on the back side in the mold. .
The decorative sheet is formed by laminating and integrating the base material side adhesive layer, the decorative sheet, the protective layer side adhesive layer, and the surface protective layer in this order from the back side to be integrated with the base resin. And the said protective layer side contact bonding layer is formed with the said moisture hardening type said polyurethane-type adhesive agent. The protective layer side adhesive layer made of such a polyurethane adhesive is excellent in flexibility.

  The surface protective layer is mainly composed of polymethyl methacrylate, a composite resin of polycarbonate and polybutylene terephthalate, or a composite resin of polycarbonate and polyethylene terephthalate, and has a glass transition point of 90 to 130 ° C. It has the thickness of. Therefore, the surface protective layer can exhibit excellent flexibility. Further, when the surface protective layer containing the composite resin as a main component is employed, the surface protective layer can exhibit further excellent scratch resistance.

Thus, the decorative sheet is excellent in flexibility as a whole. Therefore, vacuum molding and hot press molding can be performed on the decorative sheet at a low temperature of 130 ° C. or lower, for example, and the curved portion having a large curvature (small curvature radius) can be formed even at a low temperature.
Therefore, it can prevent that a bubble generate | occur | produces from the said porous decoration sheet and an unevenness | corrugation generate | occur | produces in the said surface protective layer. Moreover, the dimensional change of the said decoration sheet at the time of shaping | molding can be suppressed, and it can prevent that an unevenness | corrugation generate | occur | produces in the said decoration sheet.
Therefore, if the said decorative sheet is used, even if it forms the said curved part and injection-molds with the said base resin, the said decorative sheet can exhibit the outstanding designability. That is, it is possible to produce a cosmetic molded article having excellent design properties.

Moreover, since the said surface protection layer is formed in the said decorative sheet, when a user visually recognizes the said decorative sheet, the said decorative sheet can be visually recognized through the said transparent surface protective layer. Therefore, a sense of depth can be given to the design of the decorative sheet.
The surface protective layer is formed with a printing region made of ink. Therefore, the said decorative sheet can exhibit the outstanding designability combining the designability by the said decoration sheet, and the designability by the said printing area | region. Furthermore, the printing area can be formed by printing with a desired color, pattern, and shape. Therefore, the decorative sheet can meet various design requirements.

  As described above, according to the first invention, even when applied to a decorative molded product that requires deep drawing, the generation of air bubbles from the porous decorative sheet is suppressed, and the occurrence of surface irregularities is prevented. It is possible to provide a decorative sheet that can be suppressed and has excellent design properties and can meet various demands for design properties.

The decorative molded product of the second invention employs the first invention as the decorative sheet.
As described above, the decorative sheet of the first invention can form a curved portion having a large curvature at a low temperature by vacuum forming or hot press forming. Therefore, generation | occurrence | production of the bubble from a porous decoration sheet | seat can be suppressed. Moreover, a dimensional change can be suppressed and generation | occurrence | production of the unevenness | corrugation on the surface of the said decorative sheet can be suppressed. Therefore, the decorative molded product can exhibit the excellent design properties of the decorative sheet of the first invention as it is, and can exhibit the excellent design properties.

Explanatory drawing which shows the cross-sectional structure of the cosmetic molded product which has a laminated body sheet | seat of a hard-coat sheet and a clear sheet as a surface protective layer concerning Example 1. FIG. Explanatory drawing which shows the process concerning an Example 1 which shape | molds a decorative sheet and forms a curved part. Explanatory drawing which shows the decorative sheet in which the curved part concerning Example 1 was formed. Explanatory drawing which shows the process of integrally forming base-material resin in the back surface of a decorative sheet by injection molding concerning Example 1. FIG. Explanatory drawing which shows the cross-sectional structure of the decorative sheet which has a laminated body sheet | seat of a hard-coat sheet and a clear sheet as a surface protection layer concerning Example 1. FIG. FIG. 3 is an explanatory diagram illustrating a configuration of a laminating apparatus according to the first embodiment. Explanatory drawing which shows the cross-sectional structure of the decorative sheet which has only a hard-coat sheet as a surface protective layer concerning Example 1. FIG. Explanatory drawing which shows the cross-sectional structure of the cosmetic molded product which has only a hard-coat sheet as a surface protective layer concerning Example 1. FIG. Explanatory drawing which shows the cross-sectional structure of the decorative sheet which has only a clear sheet as a surface protective layer concerning Example 1. FIG. Explanatory drawing which shows the cross-section of the cosmetic molded product which has only a clear sheet as a surface protective layer concerning Example 1. FIG. Explanatory drawing which shows the cross-section of the cosmetic molded product which formed the hard-coat layer on the surface protection layer which consists of clear sheets concerning Example 1. FIG. Explanatory drawing which shows the manufacturing procedure of the conventional decorative sheet. Explanatory drawing which shows the manufacturing procedure of the conventional cosmetics molded product. Explanatory drawing which shows the cross-sectional structure of the cosmetics molded product which has a laminated body sheet | seat of a hard-coat sheet and a clear sheet as a surface protective layer concerning Example 2. FIG. Explanatory drawing which shows the cross-sectional structure of the decorative sheet which has a laminated body sheet | seat of a hard-coat sheet and a clear sheet as a surface protective layer concerning Example 2. FIG. The photograph substitute figure (a) which shows the surface state of a veneer concerning Example 2, and explanatory drawing which shows the uneven | corrugated state of the veneer surface. Explanatory drawing which shows the cross-sectional structure of the laminated body concerning Example 2 which laminated and formed the surface protective layer with a large thickness on the veneer. Explanatory drawing which shows the cross-section of the laminated body which laminated | stacked the veneer and the clear sheet concerning Example 2 through the surface protective layer with a big thickness. Explanatory drawing which shows the cross-sectional structure of the laminated body concerning Example 2 which laminated and formed the surface protective layer with small thickness on the veneer. Explanatory drawing which shows the cross-section of the laminated body concerning Example 2 which laminated | stacked the veneer and the clear sheet through the surface protective layer with small thickness. Explanatory drawing which shows the cross-sectional structure of the cosmetic molded product which has a surface protection layer which forms a printing area | region between a hard-coat sheet and a clear sheet concerning Example 3. FIG. Explanatory drawing which shows the cross-section of the decorative sheet which has a surface protection layer which forms a printing area | region between a hard-coat sheet and a clear sheet concerning Example 3. FIG.

Next, a preferred embodiment of the present invention will be described.
The decorative sheet is formed by laminating and integrating the base material side adhesive layer, the decorative sheet, the protective layer side adhesive layer, and the surface protective layer in order from the back surface side, and the base resin on the back surface side. It is used to obtain a decorative molded product that is injection molded and integrated with a base resin.
The base material side adhesive layer in the decorative sheet is bonded to the base material resin on one surface (the back surface side) and further adhered to the decorative sheet on the other surface.

The base material side adhesive layer preferably has a base material joint layer that joins the base material resin and an adhesive layer that adheres between the base material joint layer and the decorative sheet.
In this case, the base material resin layer can be bonded to the base material resin on the base material bonding layer side and bonded to the decorative sheet on the adhesive layer side.

As the base material bonding layer, an impregnated paper impregnated with a resin excellent in adhesiveness to the base resin, a resin sheet, a nonwoven fabric, and the like can be employed. Specifically, as the impregnated paper, for example, an impregnated paper impregnated with an acrylic resin, a polyurethane resin, a phenol resin, a diallyl phthalate resin, an epoxy resin, or the like can be employed.
In addition, as the resin sheet, an ABS resin, a thermoplastic polyurethane resin, a polyester resin, an alloy material including a polycarbonate resin, a polypropylene resin, a polyethylene terephthalate resin, a polyvinyl chloride resin, a polymethyl methacrylate resin, and the like are adopted. The resin sheet can be bonded to the base resin by heat fusion.
The thickness of the base material bonding layer can be set to, for example, 50 μm to 1000 μm.

The base material bonding layer is preferably made of a nonwoven fabric.
In this case, the adhesiveness to the base resin can be improved by the anchor effect by making use of the characteristics of the porous nonwoven fabric. As a nonwoven fabric, a polyester nonwoven fabric, a rayon nonwoven fabric, a polyolefin-type nonwoven fabric, etc. are employable, for example.

The adhesive layer is preferably formed by curing a moisture-curing transparent polyurethane adhesive.
In this case, the adhesive layer can be formed of the polyurethane adhesive having excellent flexibility. Therefore, the flexibility of the entire decorative sheet can be further improved.

Next, the protective layer side adhesive layer preferably has a thickness of 30 to 150 μm.
When thickness is less than 30 micrometers, there exists a possibility that the adhesive strength of the said protective layer side adhesive layer may become inadequate. On the other hand, when the thickness exceeds 150 μm, bubbles generated in the protective layer-side adhesive layer are difficult to escape, and there is a possibility that bubbles remain in the final product. From the same viewpoint, the thickness of the adhesive layer in the base material side adhesive layer is preferably 30 to 150 μm. More preferably, the thickness of the protective layer side adhesive layer and the adhesive layer is preferably 50 μm or more, and more preferably 80 μm or more.

The protective layer side adhesive layer is formed by curing a moisture curing type transparent polyurethane adhesive.
Here, the viscosity of the polyurethane adhesive is preferably 1000 to 15000 mPa · s.
When a polyurethane adhesive having a viscosity of less than 1000 mPa · s is used, the adhesiveness is lowered, and there is a possibility that peeling occurs at the adhesion interface. On the other hand, when it exceeds 15000 mPa · s, it becomes easy to bite bubbles from the decorative sheet, and the polyurethane adhesive itself tends to contain bubbles. Therefore, air bubbles are generated in the protective layer-side adhesive layer, and the appearance design may be deteriorated. From the same point of view, the adhesive layer in the base material side adhesive layer is preferably formed of a moisture-curable polyurethane adhesive having a viscosity of 1000 to 15000 mPa · s.

The Young's modulus of the polyurethane adhesive is preferably 10 MPa or less.
When the Young's modulus exceeds 10 MPa, there is a possibility that the curved portion may be peeled or peeled when a curved portion having a large curvature is formed during molding. From the same viewpoint, the adhesive layer in the base material side adhesive layer is also preferably formed of a moisture-curable polyurethane adhesive having a Young's modulus of 10 MPa or less.

It is preferable that the said protective layer side contact bonding layer is formed by the thickness of 2 times or more of the maximum value of the depth of the groove part in the surface of the said porous decoration sheet.
Since the decorative sheet is porous, when the decorative sheet and the protective layer are joined with the protective layer-side adhesive layer, and the protective layer-side adhesive layer has a small thickness, the protective layer is formed in the groove portion. There is a possibility that bubbles may remain between the side adhesive layer and the decorative sheet. Bubbles are generated because the protective layer-side adhesive layer cannot sufficiently enter the groove during pressure bonding in bonding.
As described above, when the protective layer-side adhesive layer is formed with a thickness that is twice or more the maximum depth of the groove, the protective layer-side adhesive layer sufficiently penetrates into the groove during bonding. Therefore, generation | occurrence | production of a bubble can be suppressed.
As described later, a veneer or the like can be adopted as the decorative sheet, and the groove is formed by a wood conduit or the like existing on the surface of the veneer (wood), for example.

It is preferable to have a sealing layer between the protective layer-side adhesive layer and the decorative sheet.
In this case, bubbles generated from the decorative sheet during molding can be prevented from entering the protective layer side adhesive layer and the like. Therefore, in this case, the design of the cosmetic molded product produced using the decorative sheet can be further improved.
The said sealing layer can exhibit the function which prevents the bubble which may generate | occur | produce from the said porous decoration sheet from invading the said protective layer side adhesion layer while improving the smoothness of the said decoration sheet.

It is preferable that the sealing layer is formed by applying and curing a sealing material mainly composed of polyurethane resin or acrylic resin on the decorative sheet.
In this case, a sealing layer having excellent flexibility can be formed, and the flexibility of the decorative sheet can be further improved. Further, when a veneer or the like of a main tree is used as the decorative sheet, the polyurethane resin exhibits excellent adhesiveness with veneer cellulose, so that the adhesiveness between the sealing layer and the decorative sheet is improved. be able to.
The thickness of the sealing layer is sufficiently smaller than that of the protective layer-side adhesive layer, and can be formed, for example, with a thickness of 10 μm or less.

In addition, pigments and / or dyes can be added to the sealing material. In this case, a desired colored sealing layer can be formed, and a color feeling can be further imparted to a design such as a wood grain of the decorative sheet. Therefore, the designability of the decorative sheet can be further improved.
Further, the same effect can be obtained by applying a dye on the decorative sheet instead of adding a pigment / dye to the sealing layer.

  As the decorative sheet, for example, a decorative sheet, cloth, carbon fiber, or a porous sheet such as a veneer of a wood cut out of a very thin wood can be used.

The decorative sheet is preferably formed by adhering a protruding plate and a non-woven fabric formed on the back side of the protruding plate with an adhesive.
Commercially available decorative sheets using a veneer are often provided as a laminate formed by adhering a veneer and a nonwoven fabric with an adhesive as described above. In this case, a commercially available decorative sheet may be used as it is. it can.

The above-mentioned protruding plate is a porous sheet obtained by cutting out wood very thinly, and can exhibit excellent design properties of the main wood.
As the above-mentioned veneer plate, it is preferable to employ a pressure-filled resin in the above-mentioned veneer plate with a resin having a hydroxyl group, forming a hydrogen bond with cellulose, and capable of forming a urethane bond with the above polyurethane adhesive. .
In this case, it is possible to further prevent air bubbles from being generated from the protruding plate during molding. Therefore, the design property can be further improved.
For example, polyethylene glycol, polypropylene glycol, or the like can be used as the resin to pressurize the conduit portion of the protruding plate. Moreover, polyester-type resin, such as polybutylene terephthalate or polyethylene terephthalate, can also be employ | adopted.

Next, the surface protective layer is transparent.
The term “transparency” as used herein includes not only complete transparency but also colored transparency and translucency. This is the same for the transparency in the hard coat sheet, the clear sheet, the protective layer side adhesive layer, the sealing layer, and the like, and these transparency can sufficiently exhibit the decorative effect by the decorative sheet. it can. What is necessary is just to have the transparency which can see through the design of the said decorative sheet through when the said decorative sheet is visually recognized from the said surface protective layer side.

In addition, as described above, the polyurethane adhesive similar to the protective layer side adhesive layer can be used for forming the adhesive layer, but the adhesive layer is not transparent even if it is transparent. May be.
In the adhesive layer, in order to avoid a phenomenon in which the back side of the decorative sheet can be seen through from the surface of the decorative sheet, it can be colored in the same color as the decorative sheet.

The surface protective layer preferably has a light transmittance of 90% or more.
In this case, when the user visually recognizes the decorative sheet or the decorative molded product obtained by integrating the decorative sheet with the base resin from the surface protective layer side, the decoration is provided via the surface protective layer. The decoration of the sheet can be sufficiently visually confirmed. That is, the design of the decorative sheet can be improved. The light transmittance is the total light transmittance.

The surface protective layer preferably has a haze of 2% or less.
Also in this case, the user can fully visually recognize the decoration of the decorative sheet through the surface protective layer.

Next, the thickness of the surface protective layer is preferably 300 to 1000 μm.
When the thickness is less than 300 μm, the sense of depth produced by the surface protective layer and the decorative sheet is impaired, and the designability may be impaired. Further, in this case, when the decorative sheet is held for a long time in a high temperature environment, there is a possibility that unevenness is likely to occur due to a dimensional change of the decorative sheet. Further, the thickness of the surface protective layer is preferably 1000 μm or less, more preferably 600 μm or less, for practical use.

The surface protective layer preferably has a glass transition point of 90 to 130 ° C.
When the glass transition point is less than 90 ° C., the heat resistance becomes insufficient, and the decorative sheet and the decorative molded product using the decorative sheet are used in a high-temperature environment such as an automobile interior product. May be difficult to apply to On the other hand, when the glass transition point exceeds 130 ° C., it is necessary to form at a high temperature when the decorative sheet is formed, and air bubbles are likely to be generated from the decorative sheet.

A printing region made of ink is formed on the surface protective layer.
The printing region can be formed by ink jet printing or gravure printing. More preferably, inkjet printing is good. In this case, it is possible to easily cope with the formation of a print area of a large variety of small lots.

The printing area can be formed on the protective layer side adhesive layer side surface of the surface protective layer.
That is, in this case, a printing region is formed between the protective layer side adhesive layer and the surface protective layer. In such a configuration, for example, the printing region is formed on the surface of the surface protective layer by inkjet printing or gravure printing, and the surface protective layer on which the printing region is formed is connected to the decorative sheet via the protective layer side adhesive layer. This can be realized by adhering to the substrate.

The surface protective layer includes, in order from the back side, a transparent clear sheet mainly composed of a composite resin composed of polycarbonate and polybutylene terephthalate or a composite resin composed of polycarbonate and polyethylene terephthalate, and a transparent composed mainly of polymethyl methacrylate. It is preferable to have a hard coat sheet (claim 3).
In this case, the surface protective layer can exhibit both hardness and flexibility at a high level. That is, the surface protective layer can exhibit excellent scratch resistance by the hard coat sheet mainly composed of polymethyl methacrylate having excellent hardness, and can be a clear material mainly composed of the composite material having excellent flexibility. Excellent flexibility can be exhibited by the sheet. In this case, since the surface protective layer itself has the hard coat sheet having high hardness on the outermost surface, the decorative sheet is prepared using the decorative sheet, and then the decorative sheet is used. The process of forming a hard coat layer on the surface of the film becomes unnecessary. This is because even if the hard coat layer is not formed, a sufficiently excellent hardness is exhibited and an excellent scratch resistance can be exhibited.

When the thickness of the hard coat sheet is T1 and the thickness of the clear sheet is T2, it is preferable that T1 / T2 = 1/7 to 1.
When T1 / T2 is less than 1/7, the property that the hardness of the hard coat sheet is high is impaired, and the scratch resistance of the surface protective layer may be reduced. On the other hand, when it exceeds 1, the heat resistance of the surface protective layer is lowered, and there is a risk that unevenness is likely to occur when the surface protective layer is kept in a high temperature environment for a long time.

Moreover, in the said clear sheet, the compounding ratio of polycarbonate (PC) and polybutylene terephthalate (PBT) or polyethylene terephthalate (PET) is PC: PBT (or PET) = 52-85: 48-15 by weight ratio. Preferably there is.
When the blending ratio of PC is less than 52, that is, when the blending ratio of PBT or PET exceeds 48, the glass transition point of the surface protective layer becomes too small and the heat resistance may be lowered. On the other hand, when the blending ratio of PC exceeds 85, that is, when the blending ratio of PBT or PET is less than 15, the glass transition point of the surface protective layer becomes too large, and molding at a high temperature is required during molding. There is a fear. Therefore, there is a possibility that bubbles are easily generated from the decorative sheet during molding.

The hard coat sheet preferably contains acrylic rubber as a subcomponent.
In this case, the flexibility of the hard coat sheet can be further improved.
In the hard coat sheet, the blending ratio of the main component and the subcomponent can be a main component: subcomponent = 75-100: 25-0 in weight ratio. If the amount of the auxiliary component is too large, the scratch resistance may be lowered. More preferably, the main component: subcomponent = 80-100: 20-0 in weight ratio.

Next, the surface protective layer is preferably formed by bonding a laminate sheet obtained by co-extrusion of the hard coat sheet and the clear sheet with the protective layer-side adhesive layer.
In this case, the surface protective layer made of the laminate sheet of the hard coat sheet and the clear sheet can be easily formed.

The printing area can be formed between the hard coat sheet and the clear sheet.
In this case, the print area is formed by forming a print area on the surface of the clear sheet and / or the hard coat, and joining the clear sheet and the hard coat sheet on the surface on which the print area is formed. It can be formed between the hard coat sheet and the clear sheet.

Next, the surface protective layer is preferably composed of a transparent hard coat sheet containing polymethyl methacrylate as a main component.
Specifically, the surface protective layer can be formed only from the hard coat sheet. In this case, the surface protective layer made of polymethyl methacrylate can exhibit both excellent flexibility and hardness.

Moreover, it is preferable that the said surface protective layer consists of a transparent clear sheet | seat which has as a main component the composite resin which consists of a polycarbonate and a polybutylene terephthalate or the composite resin which consists of a polycarbonate and a polyethylene terephthalate.
Specifically, the surface protective layer can be formed only from the clear sheet. In this case, the surface protective layer can exhibit excellent flexibility by taking advantage of the characteristics of the clear sheet mainly composed of the composite resin having excellent flexibility. In this case, since the surface protective layer does not have the hard coat sheet or the like having high hardness, the flexibility of the entire decorative sheet can be further improved. Therefore, molding at a lower temperature is possible at the time of molding, and the generation of the above-described bubbles can be further suppressed. In addition, the decorative sheet having a surface protective layer composed only of a clear sheet does not have a high hardness of the surface protective layer. In order to compensate for this, a hard coat layer made of a resin having high hardness such as an acrylic resin can be formed on the surface protective layer after injection molding and integration with the base resin.

The decorative sheet can be produced, for example, by performing the following base material side adhesive layer joining step, printing step, and surface protective layer joining step.
In the base material side adhesive layer joining step, the base material side adhesive layer is formed on the back surface side of the decorative sheet. When the adhesive layer and the base material bonding layer are formed as the base material-side adhesive layer, an adhesive such as polyurethane is applied to the back surface side of the decorative sheet, and the adhesive is coated on the adhesive surface. A base material joining layer is affixed.

In the printing step, a printing area is formed by printing ink on the surface protective layer.
The printing area can be formed on the back side of the surface protective layer. Further, when the laminate sheet of the hard coat sheet and the clear sheet is employed as the surface protective layer, ink is printed on the surface of the hard coat and / or the clear sheet so that the print region is formed. By forming and joining the hard coat sheet and the clear sheet on the surface on which the print area is formed, the print area can be formed between the hard coat sheet and the clear sheet. In this case, the hard coat sheet and the clear sheet can be joined using, for example, an adhesive.

  In the surface protective layer joining step, an adhesive that forms the protective layer side adhesive layer after curing is applied to the surface side opposite to the back side of the decorative sheet, and the adhesive is applied on the application surface. The surface protective layer is bonded.

Next, the decorative molded product performs vacuum forming or press molding on the decorative sheet to form a curved portion in the decorative sheet, and then arranges the decorative sheet in a mold, and the back surface of the decorative sheet. A base resin is injection-molded on the side.
The molding temperature of the decorative sheet can be 90 ° C to 130 ° C (sheet temperature). In this case, a curved part having a large curvature can be formed even at a low temperature, and a cosmetic molded product having an excellent surface appearance can be obtained. More preferably, the molding temperature can be 120 ° C. or lower, more preferably 110 ° C. or lower.
The first invention can be employed as the decorative sheet.

Main component of thermosetting or UV curable acrylic resin, or thermosetting or UV curable urethane resin on the surface protective layer made of the clear sheet in the cosmetic molded article obtained after the injection molding The coating material is preferably applied and cured.
In the molding die, a base resin is injection-molded from the back side of the decorative sheet, and a thermosetting or UV curable acrylic resin, or a thermosetting type or UV curing from the front side of the decorative sheet. It is preferable that a coating material mainly composed of a urethane type resin is injection-molded on the surface protective layer made of the clear sheet.
In these cases, it is possible to obtain the cosmetic molded article having the hard coat layer having high hardness on the outermost surface of the decorative sheet. Therefore, the scratch resistance of the cosmetic molded product can be improved.
In particular, the formation of the hard coat layer is effective when a decorative sheet having the surface protective layer consisting only of the clear sheet is used.

Example 1
Next, examples of the present invention will be described.
In this example, a decorative sheet is produced and a cosmetic molded product is produced using the decorative sheet.
As shown in FIGS. 1 to 4, the decorative sheet 1 of this example is formed by forming the curved portion 199 by vacuum forming or hot press forming, and then injection-molding the base resin 2 on the back surface 19 in the forming die 5. The base resin 2 is used in an integrated manner.

  As shown in FIG. 5, the decorative sheet 1 is composed of a base material side adhesive layer 11, a porous decorative sheet 13, a sealing layer 14, and a protective layer side in order from the back surface side 19 where the base resin is injected and integrated. The adhesive layer 15 and the transparent surface protective layer 16 are laminated and integrated. The base material side adhesive layer 11 includes a base material bonding layer 111 and an adhesive layer 112.

The adhesive layer 112 is formed by curing a moisture-curable polyurethane adhesive between the decorative sheet 13 and the base material bonding layer 111.
The protective layer side adhesive layer 15 is formed by curing a transparent moisture-curable polyurethane adhesive having a viscosity of 5000 mPa · s between the sealing layer 14 formed on the decorative sheet 13 and the surface protective layer 16. Become.
In this example, the adhesive layer 112 and the protective layer side adhesive layer 15 were produced using the same polyurethane adhesive (moisture curable polyurethane hot melt adhesive).

  The surface protective layer 16 is a laminate sheet of a transparent hard coat sheet 161 mainly composed of polymethyl methacrylate and a transparent clear sheet 162 made of a composite resin material of polycarbonate (PC) and polybutylene terephthalate (PBT). Is adhered on the sealing layer 14 by the protective layer side adhesive layer 15 on the clear sheet 162 side (see FIG. 5). The surface protective layer 16 has a glass transition point of 120 ° C. and a thickness of 400 μm. The thickness ratio between the hard coat sheet 161 and the clear sheet 162 is T1 / T2 = 1/7 where the thickness of the hard coat sheet 161 is T1 and the thickness of the clear sheet 162 is T2.

  The surface protective layer 16 is formed with a printing region 12 made of ink. In this example, the printing region 12 is formed on the protective layer side adhesive layer 15 side of the surface protective layer 16, more specifically, on the protective layer side adhesive layer 15 side of the clear sheet 162. That is, the printing region 12 is formed between the surface protective layer 16 (clear sheet 162) and the protective layer side adhesive layer 15.

Hereinafter, the decorative sheet of this example will be described in detail.
As shown in FIG. 5, the decorative sheet 1 has a base material bonding layer 111 on the back surface side 19 from which the base material resin is injected. In this example, the base material bonding layer 111 is made of a polyester nonwoven fabric. The thickness of the base material bonding layer 111 is about 100 μm. The thickness of the base material bonding layer 111 can be set to, for example, 30 μm to 150 μm.

As the decorative sheet 13, a laminated sheet in which a veneer 131 of a main tree and a nonwoven fabric 133 were joined with a vinyl acetate adhesive 132 was used. The thickness configuration of the decorative sheet used in this example is that the thickness of the protruding plate 131 is 300 μm, the thickness of the nonwoven fabric 133 is 200 μm, and the thickness of the adhesive layer 132 made of a vinyl acetate adhesive is about 100 μm.
As the decorative sheet 13, for example, a sheet having a thickness of about 0.3 mm to 1 m can be employed.
The decorative sheet 13 and the base material bonding layer 111 are bonded to each other by an adhesive layer 112 having a thickness of about 100 μm made of a moisture-curable polyurethane adhesive. The adhesive layer 112 can be about 30-150 μm thick.

  In the decorative sheet 13, a sealing layer 14 made of a polyurethane resin is formed on the surface side 18 opposite to the back surface side 19 on which the base material bonding layer 111 is formed. By forming this sealing layer 14, the surface smoothness of the decorative sheet 13 can be enhanced. The sealing layer 14 can be formed by applying a sealing material of polyurethane resin on the protruding plate 131 of the decorative sheet 13. A part of the sealing material is likely to soak into the porous protruding plate 131. In this example, a sealing layer 14 having a thickness of about 20 μm is formed. The sealing layer 14 can have a thickness of about 10 μm to 30 μm.

A surface protective layer 16 is formed on the sealing layer 14 via a protective layer side adhesive layer 15.
The surface protective layer 16 is composed of a laminate sheet of a hard coat sheet 161 having a thickness of 50 μm and a clear sheet 162 having a thickness of 350 μm, and is adhered onto the sealing layer 14 via the protective layer side adhesive layer 15 on the clear sheet 162 side. ing.
Moreover, the printing area | region 12 is formed in the clear sheet by inkjet printing. The print region 12 is formed on the bonding side surface of the protective layer side adhesive layer 15 in the clear sheet 162.

  The hard coat sheet 161 is made of polymethyl methacrylate (PMMA), and the clear sheet 162 is made of a composite resin material of polycarbonate (PC) and polybutylene terephthalate (PBT). The compounding ratio of PC and PBT of the composite resin material in the clear sheet 162 is PC: PBT = 70: 30 in weight ratio.

Moreover, the glass transition point of the surface protective layer 16 which consists of a laminated body sheet is 120 degreeC.
The glass transition point can be measured with a viscoelasticity measuring apparatus (FT Rheospector DVE-V4 manufactured by Rheology Co., Ltd.).

The surface protective layer 16 has a total light transmittance of 91.2% and a haze of 1%.
The total light transmittance L _t is the light transmittance of a transparent plastic, and there are tests for visible light and ultraviolet light. When the haze value is small, the test is performed using an integrating sphere light transmittance measuring device, and the ratio of the incident light amount L ₁ to the total light amount L ₂ passing through the test piece for visible light and ultraviolet light is expressed as a percentage (L _t (%)). = L ₂ / L ₁ × 100).

The haze (haze; L _h ) is a degree of an unclear cloudy appearance inside or on the surface of the transparent plastic, and the numerical value is called a cloudiness value (haze, haze). The cloudiness value test method measures the light transmittance of the test piece by the same operation as the total light transmittance test, and L _h (%) = L _d / L _t × 100 (L _d is the scattered light transmittance, L _t can be calculated by the equation (total light transmittance).
In this example, a digital haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd. was used as an integrating sphere light transmittance measuring device.

  The surface protective layer 16 is bonded onto the sealing layer 14 by a protective layer side adhesive layer 15 made of a moisture-curing polyurethane adhesive and having a thickness of about 100 μm. The protective layer side adhesive layer 15 can have a thickness of about 30 to 150 μm.

Next, a method for producing the decorative sheet of this example will be described.
First, the decorative sheet 13 is prepared. In this example, as the decorative sheet 13, a commercially available sheet in which a nonwoven fabric 133 was formed on the back surface of a veneer 131 of a main tree via a vinyl acetate adhesive 132 was prepared. The protruding plate 131 is preliminarily filled with polyethylene glycol to improve flexibility.

Next, a polyester nonwoven fabric having a thickness of about 100 μm is prepared for forming the base material bonding layer 111, and a moisture-curing polyurethane hot melt adhesive having a viscosity of 5000 mPa · s and a Young's modulus of 1 MPa is used as a moisture-curing polyurethane adhesive. Got ready.
The viscosity of the polyurethane adhesive can be measured using a cone plate viscometer DV1 manufactured by Yamato Scientific Co., Ltd. Further, the Young's modulus can be measured using a strograph VG manufactured by Toyo Seiki Co., Ltd.
Next, the base material bonding layer 111 is formed on the back side of the decorative sheet 13 through the adhesive layer 112 made of a polyurethane-based adhesive as follows.

The base material bonding layer is formed using a laminator 6 as shown in FIG.
The laminating apparatus 6 includes a melter 61 that stores a moisture-curing polyurethane adhesive in a molten state (moisture-curing polyurethane hot melt adhesive), a T-die 62 that discharges the adhesive, and an adhesive that is discharged from the T-die 62. An application roller 63 for applying the agent 120 onto the decorative sheet 13, a pressure roller 64 for pressing the decorative sheet 13 and the polyester nonwoven fabric 11, and a pressure table 65 are provided.

The laminating apparatus 6 was provided with a decorative roll 130 made of a decorative sheet 13 and a base material roll 110 made of a polyester nonwoven fabric 111.
From the decoration roll 130, the decoration sheet 13 is sent out to the application roller 63 via the feed roll 66. In the application roller 63, the moisture-curing polyurethane hot melt adhesive 120 in the melter 61 is extruded from the T die 62, applied to the back surface (nonwoven fabric side) of the decorative sheet 13 with a predetermined thickness, and further sent to the pressure roller 64. . On the other hand, the polyester nonwoven fabric 111 is sent out from the base roll 110 to the pressure roller 64 along the pressure table 65. The decorative sheet 13 and the polyester nonwoven fabric 111 fed to the pressure roller 64 are pressure-bonded between the pressure roller 64 and the pressure table 65. At this time, the decorative sheet 13 and the polyester nonwoven fabric 111 are bonded together by the adhesive 120 applied to the decorative sheet 13. The decorative sheet 13 and the polyester nonwoven fabric 111 bonded and integrated are wound up by the finished sheet roll 100.
Thus, the base material joining layer 111 which consists of a polyester nonwoven fabric was formed in the back surface of the decoration sheet 13 through the adhesive bond layer 112 (refer FIG. 5).

  Next, a sealing material made of polyurethane resin was applied on the surface of the decorative sheet 13 opposite to the side on which the base material bonding layer 111 was formed, that is, on the protruding plate 131, and dried. Thereby, the sealing layer 14 made of polyurethane resin was formed on the surface of the decorative sheet 13.

Next, the surface protective layer 16 is bonded onto the decorative sheet 13 on which the sealing layer 14 and the base material bonding layer 111 are formed through the protective layer side adhesive layer 15 made of a polyurethane-based adhesive as follows. To do.
First, as the polyurethane adhesive for forming the protective layer side adhesive layer, an adhesive similar to the above adhesive layer, that is, a moisture-curing polyurethane hot melt adhesive having a viscosity of 5000 mPa · s and a Young's modulus of 1 MPa was prepared.

  Moreover, as the surface protective layer 16, a laminated sheet was prepared by laminating a hard coat sheet 161 (thickness 50 μm) made of PMMA and a clear sheet 162 (thickness 350 μm) by coextrusion. Next, ink was printed by inkjet printing on the surface of the laminated sheet on the clear sheet 162 side to form the print region 12.

In joining the surface protective layer to the decorative sheet, a laminating apparatus 6 having the same configuration as that for forming the base material joining layer was used (see FIG. 6).
The laminating apparatus 6 includes a decorative roll 138 made of a decorative sheet 139 on which a base material bonding layer, a sealing layer, and the like are formed, and a laminating roll 160 made of a laminated sheet 16 in which a printing region 12 is formed on the surface of the clear sheet. Arranged.
From the decoration roll 138, the decoration sheet 139 is sent to the application roller 63 via the feed roll 66. In the application roller 63, the moisture-curing polyurethane hot melt adhesive 150 in the melter 61 is extruded from the T die 62 and applied to the surface (sealing layer side) of the decorative sheet 139 with a predetermined thickness, and further to the pressure roller 64. Sent. On the other hand, the laminated sheet 16 is sent out from the lamination roll 160 to the pressure roller 64 along the pressure table 65. The decorative sheet 139 and the laminated sheet 16 delivered to the pressure roller 64 are pressure-bonded between the pressure roller 64 and the pressure table 65. At this time, the decorative sheet 139 and the laminated sheet 16 are bonded by the adhesive 150 applied to the decorative sheet 139. The decorative sheet 139 and the laminated sheet 16 bonded together are wound up by the completed sheet roll 101.
In this way, the surface protective layer 16 composed of a laminated sheet of the hard coat sheet 161 and the clear sheet 162 was formed on the surface of the decorative sheet 13 via the protective layer side adhesive layer 15 (see FIG. 5). In addition, since the printing region 12 is formed on the surface of the laminated sheet on the clear sheet 162 side, with the formation of the surface protective layer 16 described above, the surface protective layer 16 and the protective layer side adhesive layer 15 are disposed between. A print area 12 is formed.

As described above, a decorative sheet 1 was produced as shown in FIG. Moreover, the release sheet 10 can be stuck on the back surface side (base material bonding layer side) of the decorative sheet.
The structure of the decorative sheet produced in this example is shown in Table 1 described later.

Next, a decorative molded article was produced using this decorative sheet.
Specifically, as shown in FIG. 2, first, the decorative sheet 1 was placed in the mold 4 having the upper mold 41 and the lower mold 42, and vacuum forming was performed. The heating temperature during vacuum forming was 100 ° C. (sheet surface temperature).
By this vacuum forming, a curved portion 199 was formed on the decorative sheet 1 as shown in FIG.

Next, the decorative sheet 1 in which the curved portion 199 was formed was placed in the cavity 55 of the injection mold 5 including the upper mold 51 and the lower mold 52. And base material resin was inject | poured in the cavity 55 from the nozzle 201 of the injection molding machine 200, and base material resin 2 was injection-molded on the back surface side 19 of the decorative sheet 1. As the base resin 2, a composite resin of PC resin and ABS resin (PC / ABS resin) was used.
In this way, as shown in FIG. 1, a cosmetic molded product 3 was produced by injection molding the base resin 2 on the back surface 19 of the decorative sheet 1. This is designated as Sample E1.

Next, with sample E1, 10 types of decorative molded products (sample E2 to sample E11) were prepared by changing the configuration of the decorative sheet, molding conditions, and the like.
Sample E2 was prepared in the same manner as Sample E1 except that the glass transition point of the surface protective layer was changed by changing the blending ratio of PC and PBT in the clear sheet.
Sample E3 and Sample E4 were prepared in the same manner as Sample E1, except that the viscosity of the moisture-curing polyurethane hot melt adhesive and the thickness of the adhesive layer made of this adhesive and the protective layer-side adhesive layer were changed. did.
Sample E5 was produced in the same manner as Sample E1 except that hot press molding (heating temperature 100 ° C.) was performed instead of vacuum molding.

Sample E6 was prepared in the same manner as Sample E1 except that a hard coat sheet containing PMMA and acrylic rubber in a weight ratio of PMMA: acrylic rubber = 95: 5 was used.
In Sample E7, a hard coat sheet containing PMMA and acrylic rubber in a weight ratio of PMMA: acrylic rubber = 80: 20 was used, and the thickness of the hard coat sheet was changed. Furthermore, the compounding ratio of PC and PBT in the clear sheet and the thickness of the clear sheet were changed to change the glass transition point of the surface protective layer, and the molding temperature during vacuum forming was changed. Except these, it was fabricated in the same manner as Sample E1.

Next, sample E8 is a cosmetic molded product produced using a decorative sheet having only the hard coat sheet as the surface protective layer, instead of the laminate sheet of the hard coat sheet and the clear sheet in sample E1.
As shown in FIG. 7, the decorative sheet 105 used for the sample E8 has a base material bonding layer 111 and an adhesive layer 112 in order from the back side 19 where the base resin is injected and integrated, as in the case of the sample E1. The porous decorative sheet 13, the sealing layer 14, the protective layer side adhesive layer 15, and the surface protective layer 16 are laminated and integrated.
In the decorative sheet 105 used for the sample E8, the surface protective layer 16 is composed of a transparent hard coat sheet 163 mainly composed of polymethyl methacrylate, having a glass transition point of 90 ° C. and a thickness of 400 μm. On the hard coat sheet 163, the printing region 12 is formed by inkjet printing in the same manner as the sample E1. And the surface protective layer 16 is formed by adhere | attaching the hard coat sheet | seat 163 in which this printing area | region 12 was formed on the sealing layer 14 with the protective layer side contact bonding layer 15. FIG. The decorative sheet 105 can be produced in the same manner as in the case of the sample E1 except that the hard coat sheet 163 described above is used instead of the laminate sheet.

As shown in FIG. 8, the decorative molded article 31 of the sample E8 is press-molded on the decorative sheet 105 having the hard coat sheet 163 on the surface to form a curved portion 199 on the decorative sheet 105, and then the decorative sheet 105 The base resin 2 is injection-molded on the back side.
This decorative molded article 31 can be produced in the same manner as the sample E1 except that hot press molding (temperature 100 ° C.) is performed instead of vacuum molding.

Sample E9 and sample E10 are decorative molded products 33 having the hard coat layer 17 formed on the outermost surface (see FIG. 11).
As shown in FIG. 9, the decorative sheet 106 used for the sample E9 and the sample E10 is similar to the sample E1 in that the base material bonding layer 111 and the adhesive are bonded in order from the back side 19 where the base resin is injected and integrated. The agent layer 112, the porous decorative sheet 13, the sealing layer 14, the protective layer side adhesive layer 15, and the surface protective layer 16 are laminated and integrated.
In the decorative sheet 106 used for the samples E9 and E10, the surface protective layer 16 is made of a composite resin of PC and PBT, and is made of a transparent clear sheet 162 having a glass transition point of 120 ° C. and a thickness of 400 μm. On the clear sheet 162, the printing region 12 is formed by ink jet printing in the same manner as the sample E1. And the surface protection layer 16 is formed by adhere | attaching the clear sheet 162 in which this printing area | region 12 was formed on the sealing layer 14 with the protective layer side contact bonding layer 15. FIG. That is, the decorative sheet 106 has substantially the same configuration as that of the sample E1 except that a surface protective layer that does not have a hard coat sheet is employed, and only the clear sheet is used instead of the laminate sheet. It can be manufactured by the same method as the sample E1 except that it is used.

The decorative molded article of sample E9 was produced as follows.
That is, first, as in the case of the sample E1, the decorative sheet 106 is press-molded to form the curved portion 199 on the decorative sheet 106 (see FIGS. 2 and 3), and then the decorative sheet 106 is formed into the mold 5 The base resin 2 is injection molded on the back side of the decorative sheet 106 (see FIG. 4). In this way, a decorative molded product 32 is obtained in which the base resin 2 is integrally formed on the back side of the decorative sheet 106 (see FIG. 10). Here, as for the cosmetic molded product 32 obtained, the outermost surface of the surface protective layer 16 consists of the clear sheet 162, and scratch resistance is inadequate.

Therefore, a UV curable acrylic resin was applied on the clear sheet 162 and cured by UV irradiation to form a transparent hard coat layer 17 made of PMMA (see FIG. 11). In this way, a decorative molded product 33 having the hard coat layer 17 on the surface was obtained. This is designated as Sample E9.
Sample E10 was prepared in the same manner as Sample E9 except that a thermosetting urethane resin was used instead of the UV curable resin.

  Sample E11 was prepared in the same manner as Sample E1, except that the thickness ratio T1 / T2 between the hard coat sheet and the clear sheet was reduced.

With respect to the decorative molded articles of Sample E1 to Sample E11 produced as described above, the presence or absence of irregularities on the design surface, the presence or absence of lifting or peeling, and the presence or absence of bubbles were visually determined. Further, the hardness of the outermost surface of the decorative molded product and the adhesive strength of the protective layer side adhesive layer were measured. Furthermore, the samples E1 to E11 were placed in an environment at a temperature of 100 ° C. for 400 hours to evaluate heat resistance. In the evaluation of heat resistance, the presence or absence of occurrence of lifting or peeling at the curved portion after 400 hours and the presence or absence of irregularities in the surface protective layer were visually determined. The results are shown in Tables 1 and 2 below.
Tables 1 and 2 show the configuration of the decorative sheet used for producing each sample and the molding conditions. In addition, in the table | surface, although the description regarding the adhesive bond layer etc. of a design sheet is abbreviate | omitted, these abbreviate | omitted structures show that it is the same as the said sample E1, and there is no change.

In this example, six types of comparative decorative molded articles (sample C1 to sample C6) were prepared for comparison of samples E1 to E11.
Sample C1 to Sample C6 can be basically manufactured by the same manufacturing method as Sample E1, and the changes from Sample E1 are shown in Tables 3 and 4 described later.
For samples C1 to C6, as in samples E1 to E10, the presence or absence of irregularities on the design surface, the presence or absence of lifting or peeling, the presence or absence of bubbles are visually determined, and the hardness and protective layer of the outermost surface of the cosmetic molded product The adhesive strength of the side adhesive layer was measured. Furthermore, heat resistance was evaluated. The results are shown in Tables 3 and 4.

  As can be seen from Tables 3 and 4, Sample C1, Sample C2, Sample C5, and Sample C6 on which the surface protective layer whose glass transition point is outside the range of 90 to 130 ° C are formed have irregularities on the design surface. Floating and peeling were observed. In addition, the generation of bubbles was observed. These have poor design properties and low commercial value.

  Further, the sample C3 in which the protective layer-side adhesive layer was formed using a polyurethane adhesive having a very low viscosity may have insufficient adhesive strength. On the other hand, in Sample C4 in which the protective layer-side adhesive layer was formed using a polyurethane adhesive having a very high viscosity, floating and peeling were observed in the heat resistance test. In addition, the generation of bubbles was observed.

On the other hand, Sample E1 to Sample E11 according to the examples of the present invention were excellent in appearance characteristics and exhibited excellent design properties. Moreover, it was excellent also in adhesiveness and heat resistance.
However, in the sample E11 in which the thickness ratio T1 / T2 between the hard coat sheet and the clear sheet is very small, the generation of bubbles is suppressed and the appearance characteristics are excellent, but the surface hardness is insufficient, and the scratch resistance Attaching becomes worse.

Further, as shown in FIGS. 5, 7, and 9, since the surface protective layer 16 is formed on the decorative sheets 1, 105, and 106 of this example, the user visually recognizes the decorative sheets 1, 105, and 106. At this time, the decorative sheet 13 can be visually recognized through the transparent surface protective layer 16. Therefore, a sense of depth can be given to the design of the decorative sheet 13.
The surface protective layer 16 is formed with a printing region 12 made of ink. Therefore, the decorative sheets 1, 105, and 106 can exhibit excellent design properties that combine the design properties of the decorative sheet 13 and the design properties of the printing region 12. Furthermore, the printing region 12 can be formed with a desired color, pattern, and shape by printing. Therefore, the decorative sheets 1, 105, and 106 can meet various design requirements.

  Thus, according to this example, even when applied to a cosmetic molded product that requires deep drawing, it is possible to suppress the generation of bubbles from the porous decorative sheet and to suppress the occurrence of surface irregularities. It is possible to provide decorative sheets and decorative molded articles (sample E1 to sample E11) that are excellent in design properties and can meet various design requirements.

(Example 2)
In this example, as shown in FIG. 14, similarly to Example 1, the curved portion 199 is formed on the decorative sheet 1, and the base resin 2 is injection-molded on the back side 19 of the decorative sheet 1, thereby forming the decorative molding. Product 3 is produced.
As shown in FIG. 15, the decorative sheet of this example is similar to Example 1 in that the base material side adhesive layer 11 and the porous decorative sheet 13 are sequentially formed from the back surface side 19 where the base resin is injected and integrated. The sealing layer 14, the protective layer side adhesive layer 15, and the transparent surface protective layer 16 are laminated and integrated. The substrate-side adhesive layer 11 can be composed of a substrate bonding layer 111 and an adhesive layer 112. The surface protective layer 16 can be composed of a hard coat sheet 161 and a clear sheet 162. A printing region 12 made of ink is formed on the surface protective layer 16. Specifically, the printing region 12 is formed on the protective layer side adhesive layer 15 side of the clear sheet 162. In addition, the decorative sheet 13 can be composed of a protruding plate 131, an adhesive layer 132, and a nonwoven fabric 133.

  In this example, 17 types of decorative molded products (sample E12 to sample E22 and sample C7 to sample C12) were manufactured in the same manner as in Example 1 by changing the configuration and molding conditions of the decorative sheet. Tables 5 to 8 show the configuration of the decorative sheet used for the preparation of each sample and the molding conditions. Table 5 shows the material of the decorative sheet (the veneer), the groove (conduit) depth, the ratio of the protective layer side adhesive layer thickness to the groove (conduit) depth (protective layer side adhesive layer thickness / conduit depth). To Table 8.

The groove depth of the decorative sheet was defined as the groove depth with the maximum value of the conduit depth in the cross section of the veneer. In the measurement, it measured using the digital microscope VHX-900 made from Keyence Corporation.
FIG. 16A shows a micrograph (magnification 100 times) of a groove (conduit) on the surface of Bubinga as an example of a decorative sheet (a veneer). FIG. 16B shows the depth of the groove on line X shown in FIG. The depth of the groove portion is measured on the entire surface of the decorative sheet, and the maximum depth value, that is, the maximum height between A and B in FIG. The pipe depth).

  For each sample (sample E12 to sample E22, sample C7, and sample C12), as in Example 1, the presence or absence of irregularities on the design surface, the presence or absence of lifting or peeling, and the presence or absence of bubbles were determined visually. Further, the hardness of the outermost surface of the decorative molded product and the adhesive strength of the protective layer side adhesive layer were measured. Furthermore, each sample was placed in an environment at a temperature of 100 ° C. for 400 hours to evaluate heat resistance. In the evaluation of heat resistance, the presence or absence of occurrence of lifting or peeling at the curved portion after 400 hours and the presence or absence of irregularities in the surface protective layer were visually determined. The results are shown in Tables 9 to 12 below. Tables 9 to 12 show the curvature radii of the curved portions. For the radius of curvature, the curvature of the outermost surface of each sample (or the clear sheet surface when a clear sheet or the like is provided) was measured using an R gauge.

As is known from Tables 5 to 12, Sample E12 to Sample E22 according to the examples of the present invention have excellent appearance characteristics and excellent design properties even when a curved portion having a small curvature radius of 2.0 mm is formed. showed that. Moreover, it was excellent also in adhesiveness and heat resistance.
However, in the sample E22 in which the thickness ratio T1 / T2 between the hard coat sheet and the clear sheet is very small, the generation of bubbles is suppressed and the appearance characteristics are excellent, but the surface hardness is insufficient, and the scratch resistance Attaching becomes worse.
On the other hand, Sample C7 to Sample C12 have at least a problem in appearance characteristics.

In Samples E12 to E22, the protective layer-side adhesive layer is formed with a thickness that is twice or more the maximum depth of the groove on the surface of the porous decorative sheet (see Tables 5 and 6). ). For this reason, the generation of bubbles is sufficiently suppressed (see Tables 9 and 10).
On the other hand, in sample C9 and sample C10, the thickness of the protective layer-side adhesive layer is not sufficient with respect to the depth of the groove (see Table 7). Therefore, it is considered that bubbles were more easily generated in the sample C9 and the sample C10 (see Table 11).

This point will be described with reference to the drawings.
In the case where the protective layer side adhesive layer 15 is formed on the veneer 131 side of the decorative sheet 13 and is bonded to the surface protective layer 16 on the clear sheet 162 side using the laminating apparatus in the same manner as in Example 1, Sample E12 to Sample When the surface protective layer 16 is formed with a sufficient thickness of twice or more than the depth of the groove portion 139 of the thrust plate 131 as in E22, the protective layer side adhesive layer 15 is formed up to the inside of the groove portion 139. Therefore, generation | occurrence | production of a bubble can be suppressed (refer FIG.17 and FIG.18).
On the other hand, when the surface protective layer 16 is formed with a thickness less than twice the depth of the groove portion 139 of the veneer 131 as in the sample C9 and sample C10, the protective layer side extends to the inside of the groove portion 139. It is considered that the adhesive layer 15 is not formed and bubbles are generated (see FIGS. 19 and 20).
A sealing layer is provided between the veneer 131 and the protective layer side adhesive layer 15, but the sealing layer is sufficiently smaller than the thickness of the veneer 131, the protective layer side adhesive layer 15, and the like. Therefore, it is omitted in FIGS.

  Further, as shown in FIG. 15, a printing region 12 made of ink is formed on the surface protective layer 16 of the decorative sheet 1 of this example. Therefore, the decorative sheet 1 can exhibit an excellent design property that combines the design property of the decorative sheet 13 and the design property of the printing region 12. Furthermore, the printing region 12 can be formed with a desired color, pattern, and shape by printing. Therefore, the decorative sheet 1 can meet various design requirements.

  As described above, according to this example, even when applied to a cosmetic molded product that requires deep drawing, the generation of bubbles from the porous decorative sheet is suppressed, and the generation of surface irregularities is suppressed. It is possible to provide decorative sheets and cosmetic molded products (sample E12 to sample E22) that are excellent in design properties and can meet various requirements for design properties.

(Example 3)
In this example, it is an example of a decorative sheet in which a printing region is formed between a hard coat sheet and a clear sheet.
As shown in FIG. 21, the decorative sheet 107 of this example is formed by forming a curved portion 199 on the decorative sheet 107 and injection molding the base resin 2 on the back surface side 19 of the decorative sheet 107 as in the first embodiment. This is for producing the decorative molded article 3.

As shown in FIG. 22, the decorative sheet 107 of this example is similar to the first example, in order from the back surface side 19 in which the base resin is injected and integrated, in order from the back surface side 19, the porous decorative sheet. 13, the sealing layer 14, the protective layer side adhesive layer 15, and the transparent surface protective layer 16 are laminated and integrated.
Also in the decorative sheet 1 of this example, a printing region is formed on the surface protective layer 16 as in the first embodiment. In Example 1, the printing area was formed between the clear sheet of the surface protective layer and the protective layer side adhesive layer, but in this example, as shown in FIG. 22, the hard coat sheet 161 and the clear sheet 162 A printing region 12 is formed between the two. Other configurations are the same as those of the first embodiment.

In the decorative sheet 107 of this example, a laminated sheet for forming the surface protective layer was produced as follows.
First, a hard coat sheet 161 made of polymethyl methacrylate (PMMA) and a clear sheet 162 made of a composite resin material (PC: PBT = 70: 30; weight ratio) of polycarbonate (PC) and polybutylene terephthalate (PBT). Got ready. Next, ink was printed on the surface of the clear sheet 162 by inkjet printing to form the print region 12.

Next, the clear sheet 162 was attached to the hard coat sheet 161 with the surface on which the print region 12 was formed by an adhesive. In this way, a laminated sheet having the printing region 12 between the hard coat sheet 161 and the clear sheet 162 was produced.
Using this laminated sheet, the decorative sheet 107 can be produced as shown in FIG. 22 in the same manner as in Example 1.

  The decorative sheet 107 of this example can be formed with the same configuration as in Examples 1 and 2 except that the formation position of the printing region 12 is changed. Therefore, the decorative sheet 107 of this example and the decorative molded product 3 (see FIG. 21) produced using the same can exhibit the same functions and effects as those of Examples 1 and 2.

DESCRIPTION OF SYMBOLS 1 Decorative sheet 11 Base material side adhesive layer 111 Base material joining layer 112 Adhesive layer 13 Decoration sheet 14 Sealing layer 15 Protection layer side adhesive layer 16 Surface protective layer 161 Hard coat sheet 162 Clear sheet 19 Back surface side

Claims (6)

A decorative sheet that is used by being integrated with a base resin by forming a curved portion by vacuum molding or hot press molding, and then injection molding the base resin on the back side in a mold,
The decorative sheet is formed by laminating and integrating a base material side adhesive layer, a porous decorative sheet, a protective layer side adhesive layer, and a transparent surface protective layer in order from the back surface side.
The protective layer side adhesive layer is formed by curing a moisture-curing transparent polyurethane adhesive,
The surface protective layer is mainly composed of polymethyl methacrylate, or a composite resin of polycarbonate and polybutylene terephthalate, or a composite resin of polycarbonate and polyethylene terephthalate, and has a glass transition point of 90 to 130 ° C.
The surface protective layer has a thickness of 300 to 1000 μm,
A decorative sheet, wherein a printing region made of ink is formed on the surface protective layer.   The decorative sheet according to claim 1, wherein the printing region is formed by ink jet printing or gravure printing.   3. The transparent protective sheet according to claim 1, wherein the surface protective layer comprises, in order from the back side, a composite resin composed of polycarbonate and polybutylene terephthalate or a composite resin composed of polycarbonate and polyethylene terephthalate as a main component, and polymethyl. A decorative sheet comprising a transparent hard coat sheet mainly composed of methacrylate.   The decorative sheet according to any one of claims 1 to 3, wherein the printing region is formed on the protective layer side adhesive layer side surface of the surface protective layer.   The decorative sheet according to claim 3, wherein the printing area is formed between the hard coat sheet and the clear sheet. The decorative sheet is vacuum-formed or press-molded to form a curved portion in the decorative sheet, the decorative sheet is then placed in a mold, and a base resin is injection-molded on the back side of the decorative sheet. A decorative molded article,
A cosmetic molded article comprising the decorative sheet according to any one of claims 1 to 5.