JP6177701B2 - Article surface decorative sheet, decorative molded body, and method for manufacturing article surface decorative sheet - Google Patents

Description

  The present invention relates to a sheet for decorating the surface of an article made of a soft material provided with three-dimensional characters, figures, symbols, patterns, and the like by embossing.

  Background Art A decorative molded body having a leather-like appearance is known as an exterior member of a cellular phone, a mobile device, a home appliance, an interior part such as a vehicle or an aircraft, a building material, or furniture.

  For example, Patent Document 1 below includes a base material layer obtained by impregnating a first polyurethane with a nonwoven fabric in which a fiber bundle of polyester ultrafine fibers is entangled, and a second polyurethane formed on the surface of the base material layer. A silver surface layer, the thickness of the base material layer is 0.5 mm or less, the silver surface layer accounts for 10 to 40% of the total thickness, and the direction in which the nonwoven fabric is most stretched is the MD direction, MD Disclosed is a preform molding sheet in which the ratio of 20% tensile stress in the MD direction to the TD direction (MD / TD) is 1.9 to 2.5 when the direction perpendicular to the surface direction is the TD direction. . Then, a preform molded body that is subjected to injection insert molding is molded using such a preform molding sheet, and insert molding is performed using the obtained preform molded body, thereby adding a leather-like surface. Disclosed is a decorative insert molded body. Moreover, patent document 1 is disclosing that an embossing pattern may be formed in the surface of a silver surface layer by using an embossing machine.

  When an embossed pattern is to be imparted to a sheet having a silver surface layer obtained by the technique disclosed in Patent Document 1, there are the following problems.

  Examples of a method for forming an embossed pattern on a sheet having a silver surface layer include the following methods. First, after forming a coating film of a resin liquid containing a polymer elastic body such as polyurethane on the surface of a release paper having an embossed pattern, a silver surface layer is formed by solidifying the polymer elastic body. And after adhering a silver surface layer to a base material layer, the silver surface layer which has an embossed pattern on the sheet | seat surface is formed by peeling a release paper. However, in the case of such a method, when an embossed pattern having a large unevenness in height is to be formed, the silver layer has to be thickened.

  The second method is to form a smooth silver surface layer by solidifying the polymer elastic body after forming a coating film of a resin liquid containing the polymer elastic body on the smooth release paper surface. And after adhering the formed silver surface layer to a base material layer, the sheet | seat which has a smooth surface silver surface layer laminated | stacked on the base material layer is formed by peeling a release paper. And it heat embosses to the sheet | seat which has a smooth silver surface layer using an embossing roll. However, when heat embossing is performed using an embossing roll having a concavo-convex pattern with a large difference in height, there is a problem that the concavo-convex pattern is difficult to be accurately transferred.

  By the way, a technique for accurately transferring an embossed pattern to a surface layer of a leather-like sheet used for a basketball fabric, a clothing fabric, a shoe fabric, or the like is known. For example, in Patent Document 2 below, a polymer mainly composed of polyurethane that can be softened or melt-molded at a lower temperature than the constituent materials of the other layers is formed on the surface layer constituting the intermediate portion between the fibrous base layer and the finishing layer. Disclosed is a leather-like sheet that can be sharply shaped by use. Specifically, at least one surface of the fibrous base layer has a softening molding temperature of 130 to 185 ° C. and a softening molding temperature that is at least 30 ° C. lower than the softening temperature of the main fibers and the main polymer constituting the base layer. A sheet obtained by laminating a surface layer composed of a polyurethane-based polymer having a polyurethane and a finishing layer composed of a polymer having a softening molding temperature at least 30 ° C. higher than the polymer constituting the surface layer Is embossed at a temperature at which the polymer constituting the surface layer is softened and molded so that the polymer constituting the finishing layer is not fluidly deformed.

JP 2013-209780 A Japanese Patent Laid-Open No. 02-061181

  For example, in the case of an article surface decorative sheet that is used by being bonded to the surface of a molded body, a thinner thickness is required in order to accurately bond it to the curved surface of the molded body. Cited Document 2 discloses forming a resin layer mainly composed of polyurethane having a softening temperature of 130 to 185 ° C. having a thickness of 100 to 2000 μm as a sufficient thickness for providing unevenness by hot embossing. doing. However, in the technique disclosed in the cited document 2, since unevenness is given only to the resin layer mainly composed of polyurethane having a softening molding temperature of 130 to 185 ° C., for example, unevenness with an elevation difference of 150 μm or more is accurately detected. However, there is a problem that the resin layer becomes inevitably thick. In particular, when trying to transfer characters or fine patterns, there is a problem that their outlines are difficult to transfer accurately.

  The present invention provides an article surface decoration that is soft and rich in design, in which a three-dimensional figure, symbol, pattern, character, or other design is clearly embossed in an article surface decorative sheet that requires thinness. The purpose is to provide a decorative sheet.

  One aspect of the present invention is an article surface decorative sheet in which a pattern is embossed, a nonwoven fabric base material, a surface layer having a thickness of 1 to 100 μm including a polymer elastic body, a nonwoven fabric base material, and a surface layer. An intermediate layer having a thickness of 10 to 150 μm containing a hot-melt adhesive for adhering to each other, and the nonwoven fabric substrate includes an entanglement of fiber bundles of ultrafine fibers having a fineness of 0.8 dtex or less, and is formed by embossing Moreover, it is a sheet | seat for articles | goods surface decoration provided with the 1st area | region whose average value of the distance between the fiber bundles in a thickness direction cross section is less than 10 micrometers, and a 2nd area | region which is 10 micrometers or more and 30 micrometers or less. The article surface decorating sheet having such a structure is excellent in thermal transferability because the intermediate layer of 10 to 150 μm contains a hot-melt adhesive. Also, in the area that is highly compressed during hot embossing, not only the surface layer and the intermediate layer, but also the fiber bundles are crushed and densified, so that the uneven pattern is transferred to the nonwoven fabric substrate and the contour is accurate. Expressed. Furthermore, in order to provide a nonwoven fabric base material with a small average value of the distance between the fiber bundles and a high sense of fulfillment, for example, it is crushed even when used as a surface material of articles that are frequently repeatedly pressed with a human finger. It's hard to get it. Therefore, for example, a surface material for displaying braille and direction marks, a surface for displaying three-dimensional symbols used for indicators of various articles, an operation unit, etc. for allowing a visually handicapped person to recognize various information by tactile sensation. It can be preferably used as a material.

Moreover, the ratio of the thickness when measured with a constant pressure thickness measuring device set to 240 gf / cm ² with respect to the thickness measured with a scanning microscope (SEM) of the sheet for decorating the article surface is 90% in the first region. If it is above and it is 80 to 89% in the 2nd field, a sense of fulfillment is higher and it becomes difficult to compress even if it is thin.

Furthermore, hot-melt adhesive preferably has a 0 to 30 ° C. softening temperature higher than the glass transition temperature of the microfine fibers (T _g). In such a case, because the softening temperature T _g of the hot-melt adhesive of the ultrafine fibers is closer, by heat embossing, clearly uneven pattern on the intermediate layer and the nonwoven fabric base material is transferred. Further, when the microfine fibers comprise a modified polyester having a T _g of 100 to 120 ° C. can be accurately represented in without crushing the contour finer characters and patterns.

  Further, the height difference or thickness difference between the first region and the second region is larger than the total thickness of the surface layer and the intermediate layer. Specifically, the height difference between the first region and the second region is larger. When the difference or the difference in thickness is 1.1 times or more of the total thickness of the surface layer and the intermediate layer, the concavo-convex pattern is more clearly transferred to the nonwoven fabric substrate and the contour is Expressed accurately.

  In addition, when the nonwoven fabric substrate contains 5 to 40% by mass of a crosslinked non-porous polymer elastic body, the nonwoven fabric substrate is sufficiently coated with a pressure at the time of hot embossing. This is preferable from the viewpoint of increasing the density.

Moreover, the other one aspect | mode of this invention is a manufacturing method of the said article | item surface decorating sheet provided with the following process.
(1) T _g and the nonwoven fabric substrate comprising entangled body of fiber bundle following ultrafine fiber fineness 0.8dtex containing modified polyester is 100 to 120 ° C., the surface layer having a thickness of 1~100μm comprising elastic polymer And a step (2) SEM of preparing a thermal transfer sheet comprising an intermediate layer having a thickness of 10 to 150 μm including a hot-melt adhesive having a softening temperature of 150 ° C. or less for bonding the nonwoven fabric substrate and the surface layer. A first region having a thickness ratio of 90% or more and a second region having a thickness of 80 to 89% when measured with a constant pressure thickness measuring device set to 240 gf / cm ² with respect to the thickness measured in A heat embossing process is provided on the thermal transfer sheet so as to form. Step (1) includes (1a) a step of preparing a nonwoven fabric substrate, (1b) a step of forming a surface layer having a thickness of 1 to 50 μm including a polymer elastic body on the surface of the release paper, and (1c) And (1d) forming a coating film of a solution of a hot melt adhesive on the surface layer formed on the surface of the release paper so that the thickness upon drying is 10 to 150 μm; It is preferable to include a step of pressure bonding the material, adhering the nonwoven fabric substrate and the hot melt adhesive while removing the solvent in the coating film, and removing the release paper to form the heat-transferable sheet.

  According to the present invention, an article surface decorating sheet, which is a soft material that displays characters, figures, symbols, patterns, etc. in a three-dimensional manner and is rich in design in an article surface decorating sheet that is required to be thin. It is done.

Drawing 1 is a mimetic diagram of decoration fabrication object 20 obtained using article surface decoration sheet 10 of an embodiment. FIG. 2 is an SEM image of a thin region of the article surface decorating sheet obtained in Example 1. FIG. 3 is an SEM image of a thin region of the article surface decorating sheet obtained in Comparative Example 1. FIG. 4 is a schematic perspective view of an example of the article surface decorating sheet of the embodiment. FIG. 5 is a schematic cross-sectional view illustrating the heat embossing process.

  An embodiment of an article surface decorative sheet and a decorative molded body according to the present invention will be described.

  FIG. 1 shows an article formed by adhering an article surface decorative sheet 10 to the surface of a molded body 11 via a pressure-sensitive adhesive layer or an adhesive layer (hereinafter collectively referred to as an adhesive layer) 12. It is a schematic diagram of the decorative molded body 20, FIG. 1 (a) is a top surface, FIG.1 (b) shows the schematic diagram of the II 'cross section of Fig.1 (a). As shown in FIG. 1A, the article surface decorating sheet 20 has an embossed pattern having a rectangular outline having a groove-like region B when viewed from above. Moreover, as shown in FIG.1 (b), it has the embossed pattern which formed the substantially plateau-shaped convex part which has the area | region A, the area | region B, and the area | region C from which a compression rate mutually differs when it cross-sectionally views.

  As shown in FIG. 1 (b), the article surface decorating sheet 10 bonds the nonwoven fabric substrate 1, the 1 to 100 μm surface layer 2 containing a polymer elastic body, and the nonwoven fabric substrate 1 and the surface layer 2. An intermediate layer 3 is provided. The intermediate layer 3 is an adhesive layer having a thickness of 10 to 150 μm containing a hot melt adhesive. The article surface decorating sheet 10 is adhered to the molded body 11 via the adhesive layer 12. The nonwoven fabric substrate 1 includes an entangled body of fiber bundles of ultrafine fibers having a fineness of 0.8 dtex or less, and the compressibility of the fiber bundles is increased in the order of region A, region B, and region C.

In the article surface decorating sheet 10, the nonwoven fabric base material 1 is crushed at a high compressibility, and a load of 240 gf / cm ² is applied to the thickness ratio measured with a scanning microscope (SEM) in an unloaded state. It is preferable to maintain the thickness when measured with a constant pressure thickness measuring device by 80% or more. Moreover, it is preferable that the area C where the compressibility of the nonwoven fabric base material 1 is the highest maintains the thickness ratio of 90% or more. Moreover, it is preferable that the area | region A where the compressibility of the nonwoven fabric base material 1 is the lowest maintains the ratio of the said thickness 80 to 89%. Such an article surface decorating sheet has a high degree of fullness and is difficult to be compressed. Therefore, even if it is used as a surface material of an article that is frequently repeatedly pressed with a human finger, it is difficult to be crushed. Further, since the embossed pattern is transferred not only to the surface layer and the intermediate layer but also to the nonwoven fabric substrate, even characters and fine patterns are accurately transferred.

  Moreover, it is preferable that the ratio of the said thickness of the area | region C where the compressibility of the nonwoven fabric base material 1 is the highest is 90% or more, Furthermore, 91% or more. When the ratio of the thickness is less than 90%, the embossed pattern contour is not clear, and the embossed pattern contour changes over time when used as a surface material of an article that can be touched by a human finger. There is a tendency to become blurred.

  It is preferable that the ratio of the said thickness of the area | region A where the compressibility of the nonwoven fabric base material 1 is the lowest is 80 to 89%, Furthermore, it is preferable that it is 82 to 88%. When the ratio of the thickness of the region where the compressibility of the nonwoven fabric substrate 1 is the lowest is such a range, the embossed pattern contour when used as a surface material of an article that can be touched by a human finger Becomes clear.

In addition, the thickness when applying a load of 240 gf / cm ² and measuring with a constant pressure thickness measuring instrument is JIS thickness measuring instrument with a load of 240 gf / cm ² according to JISL1096 (for example, constant pressure thickness measurement manufactured by Ozaki Mfg. Co., Ltd.). Machine). In addition, the thickness measured with a scanning microscope (SEM) in an unloaded state was obtained by taking a cross section of a portion to be measured with a constant pressure thickness measuring instrument with a scanning electron microscope (SEM) and selecting three points on average from the photograph. It is calculated by averaging the thickness at.

  FIG. 2 is an example of an SEM image of the thin region C where the compression ratio of the nonwoven fabric base material of the article surface decorating sheet of the present embodiment is the highest. In FIG. 2, 1a is a fiber bundle of ultrafine fibers having a fineness of 0.8 dtex or less forming a nonwoven fabric substrate, a part of the fiber bundle is contoured, and a dotted line is an auxiliary line.

  As shown in FIG. 2, the fiber bundle is formed so that a plurality of ultrafine fibers are converged. And as for the nonwoven fabric base material containing the entangled body of the fiber bundle of ultrafine fibers, the average value of the distance between the fiber bundles in the cross section in the thickness direction is less than 10 μm in the region C where the compressibility is the highest, and is 0 to 8 μm. It is preferably 10 μm or more and 30 μm or less, and preferably 10 μm or more and 20 μm or less in the region A having the lowest compression rate. By including the nonwoven fabric base material crushed at such a high compression rate, the article surface decorating sheet of the present embodiment is a sheet that has a high sense of fulfillment and is not easily crushed.

  A measurement method and a calculation method of the average value of the distance between the fiber bundles in the cross section in the thickness direction will be described with reference to FIG. An arbitrary cross section parallel to the thickness direction of the nonwoven fabric substrate as shown in FIG. Then, 10 auxiliary lines are drawn at substantially equal intervals in parallel with the thickness direction of the sheet on the photographed image. Then, the total distance (A) between all the fiber bundles that have passed the 10 auxiliary lines (between the outer circumferences of the fiber bundles) is obtained. And the total of the number of fiber bundles which passed 10 auxiliary lines is calculated | required, and the number which subtracted 10 from the total of the number of fiber bundles is made into the number (B) between fiber bundles. Then, a value obtained by dividing the total distance (A) by the number (B) between the fiber bundles, that is, (A) / (B) is calculated as an average value of the distances between the fiber bundles in the thickness direction. Note that the fiber bundle counting method in the cross-sectional direction counts not only a circular fiber bundle but also an elliptical fiber bundle extending obliquely. However, the fiber bundles that substantially form bundles are counted. And the average value of the distance between fiber bundles on each of arbitrary 10 points is obtained. It is more preferable that all of the average values of the distances between the fiber bundles on each of the arbitrary 10 points are in the above-described range.

  The number of ultrafine fibers forming each fiber bundle is preferably 5 to 1000, more preferably 5 to 200, particularly 10 to 50, and more preferably 10 to 30. Moreover, as an average diameter of a fiber bundle, it is preferable that it is 1-50 micrometers, Furthermore, it is 10-30 micrometers. When the number of ultrafine fibers forming the fiber bundle is too large or the average diameter of the fiber bundle is too large, it is difficult to reduce the average value of the distance between the fiber bundles in the cross section in the thickness direction. In addition, when the number of ultrafine fibers forming the fiber bundle is too small or the average diameter of the fiber bundle is too small, the average value of the distance between the fiber bundles in the cross section in the thickness direction tends to be difficult to adjust. Note that the average diameter of the fiber bundles is an image obtained by photographing a cross section in the thickness direction of the sheet with an SEM, and on average, the outer shape of 100 fiber bundles is specified, and an area equivalent to the area surrounded by the outer shape is defined. It shall mean the diameter of the circle it has.

  The fineness of the ultrafine fiber is 0.8 dtex or less, preferably 0.5 dtex or less, more preferably 0.1 dtex or less, and particularly preferably 0.08 dtex or less. In addition, although a minimum is not specifically limited, It is preferable that it is about 0.01 dtex. When the fineness of the ultrafine fiber exceeds 0.8 dtex, the stretchability of the fiber is lowered, and the fiber bundle forming the nonwoven fabric base material by heat embossing is difficult to be densified. As a result, the contour of the embossed pattern tends to be unclear.

  It is preferable that the fiber bundle forming the nonwoven fabric base is formed from long ultrafine fibers because the distance between the fiber bundles in the cross section in the thickness direction can be easily adjusted as described above. Here, the long fiber means that the short fiber is not cut into a predetermined length. The 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 of the fiber bundle can be sufficiently increased. If the ultrafine fiber is too short, it tends to be difficult to increase the density of the fiber bundle. Although an upper limit is not specifically limited, For example, in the case of the nonwoven fabric manufactured by the spunbond method, the fiber length of several m, several hundred m, several km or more spun continuously may be sufficient. Further, these fibers may be mixed with several kinds of fibers instead of single.

The resin that forms the ultrafine fibers is not particularly limited. Specific examples thereof include, for example, polyester resins such as polyethylene terephthalate (PET), polytrimethylene terephthalate, polybutylene terephthalate (PBT), and polyester elastomer; polyamide 6, polyamide 66, polyamide 610, aromatic polyamide, polyamide elastomer, and the like. Polyamide resins; acrylic resins; olefin resins; fibers formed from synthetic resins having fiber-forming ability such as polyvinyl alcohol resins. These may be used alone or in combination of two or more. Among these, polyester resins and polyamide resins are preferable from the viewpoint of excellent melt spinnability. In particular, a polyester having a glass transition temperature (T _g ) of 100 to 120 ° C., more preferably 105 to 115 ° C. is preferable.

Ultrafine fibers T _g comprises polyester 100 to 120 ° C., in order to have excellent stretchability during softening due to heating at the time of thermal transfer processing, transfer of large uneven pattern height difference is better. When _Tg is less than 100 ° C., solidification after thermal transfer tends to take time.

For example, T _g is obtained by fixing a test piece having a width of 5 mm and a length of 30 mm between chucks with an interval of 20 mm using a dynamic viscoelasticity measuring apparatus (for example, FT Leospectra DDVIV manufactured by Rheology). It is obtained by measuring the dynamic viscoelastic behavior under the conditions of ˜250 ° C., a temperature rising rate of 3 ° C./min, a strain of 5 μm / 20 mm, and a measurement frequency of 10 Hz.

Specific examples of the polyester a T _g is 100 to 120 ° C., for example, polyethylene terephthalate structural units disturb the structure of the linear to modified polyethylene terephthalate containing, as constituent units copolymerizable component, in particular, isophthalic acid, phthalic acid, Examples thereof include a modified polyethylene terephthalate containing an asymmetric aromatic carboxylic acid such as 5-sodium sulfoisophthalic acid or an aliphatic dicarboxylic acid such as adipic acid as a copolymerization component in a predetermined ratio. More specifically, modified polyethylene terephthalate containing 2 to 12 mol% of isophthalic acid unit as a monomer component is preferable.

  The voids between the fibers or fiber bundles of the nonwoven fabric substrate may contain a polymer elastic body as necessary for the purpose of imparting shape stability or providing a sense of fulfillment. The kind of polymer elastic body is not particularly limited. Specific examples thereof include various polyurethanes such as polycarbonate polyurethane, polyester polyurethane, and polyether polyurethane, acrylic elastic bodies, polyurethane acrylic composite elastic bodies, polyvinyl chloride, and synthetic rubber. Among these, polyurethane is preferable from the viewpoint of excellent adhesiveness and mechanical properties. Moreover, you may mix | blend well-known various additives with a polymeric elastic body as needed. The polymer elastic body is preferably a crosslinked polymer elastic body, particularly a crosslinkable polyurethane having a mass reduction rate of 5% by mass or less with respect to immersion in N, N-dimethylformamide (DMF). Since the crosslinked polymer elastic body is less deformed due to elastic recovery after hot pressing, it is easy to adjust the nonwoven fabric base material so that the average value of the distance between the fiber bundles is reduced by subjecting the nonwoven fabric substrate to hot pressing.

  Such a crosslinked polyurethane is preferably formed using an aqueous emulsion of a crosslinkable non-porous polyurethane. Specific examples of such an aqueous emulsion of a crosslinkable polyurethane include, for example, an aqueous emulsion of polycarbonate polyurethane, polyester polyurethane, polyether polyurethane, and polycarbonate / ether polyurethane that forms a crosslinked structure after drying. .

  The content ratio of the polymer elastic body in the nonwoven fabric substrate is preferably 5 to 40% by mass, more preferably 8 to 35% by mass, and particularly preferably 12 to 30% in order to improve the sense of fulfillment.

The apparent density of the nonwoven fabric substrate is 0.50 g / cm ³ or more, more 0.50~0.85g / cm ^3, and particularly preferably from 0.50~0.80g / cm ^3. In the case of such a high apparent density, a high sense of fulfillment is obtained.

  Although the thickness of a nonwoven fabric base material is not specifically limited, 300-1000 micrometers, Furthermore, it is preferable that it is 300-800 micrometers, especially 300-600 micrometers from the point from which a thin article | item surface decoration sheet is obtained.

  The article surface decorating sheet 10 has a surface layer 2 having a thickness of 1 to 100 μm including a polymer elastic body.

  The type of the polymer elastic body for forming the surface layer is not particularly limited. Specific examples thereof include various polyurethanes such as polycarbonate polyurethane, polyester polyurethane and polyether polyurethane, acrylic elastic bodies, polyurethane acrylic composite elastic bodies, polyvinyl chloride elastic bodies, synthetic rubbers and the like. These polymer elastic bodies may be used alone or in combination of two or more. Among these, polyurethane is preferable from the viewpoint of excellent adhesiveness, mechanical properties such as wear resistance and bending resistance. Further, the polymer elastic body may contain various known additives and colorants as necessary. In addition, in the article surface decorative sheet of the present embodiment, in order to improve the design, in particular, a metallic pigment such as silver or a colorant exhibiting vivid coloring such as red, blue, and yellow is used. It is preferable to make it contain in a surface layer from the point which is excellent in the designability.

  The surface layer is preferably formed using a one-pack type non-crosslinkable polymer elastic body. Since the cross-linked polymer elastic body is difficult to be plasticized in the subsequent thermal transfer process, the embossing property is lowered. The surface layer may be provided with an anchor coat layer for the purpose of enhancing adhesiveness, or may have a laminated structure in which a top coat layer is provided on the surface.

  The thickness of the surface layer is 1 to 100 μm, preferably 15 to 80 μm, and more preferably 20 to 50 μm. When the thickness of the surface layer is less than 1 μm, the heat resistance of the surface of the obtained article surface decorating sheet tends to be lowered or the wear resistance tends to be lowered. Moreover, when the thickness of a surface layer exceeds 100 micrometers, an article | item surface decorating sheet becomes thick and the designability falls.

  The surface layer 2 is bonded to the nonwoven fabric substrate 1 through an intermediate layer 3 having a thickness of 10 to 150 μm containing a hot-melt adhesive. An intermediate layer having a thickness of 10 to 150 μm containing such a hot-melt adhesive is excellent in formability at the time of hot embossing when producing an article surface decorative sheet.

  The hot-melt adhesive used for forming the intermediate layer is not particularly limited as long as it is a conventionally known hot-melt adhesive that melts by heating and then re-solidifies by cooling. Used without. Specific examples include hot melt adhesives such as polyurethane, polyester, polyolefin, acrylic, vinyl acetate, polystyrene, and epoxy. Moreover, as a hot-melt-type adhesive agent, any of a crosslinked type, a semi-crosslinked type, and a non-crosslinked type may be sufficient, but a crosslinked type is preferable from the viewpoint of excellent adhesiveness. In addition, a hot-melt urethane adhesive having a softening temperature of 150 ° C. or lower and further 130 ° C. or lower is particularly preferable from the viewpoint of excellent shapeability at the time of hot embossing of the obtained article surface decorative sheet. The softening temperature is measured, for example, by preparing a dry film of 50 μm, then increasing the temperature at a constant temperature while applying a constant load, and specifying the temperature at which it begins to grow sharply or the temperature at which it cuts sharply. be able to.

Further, the softening temperature of the hot melt adhesive is 0 to 30 ° C. than the T _g of the ultrafine fibers, further preferably higher 10 to 20 ° C.. In such a case, because the softening temperature T _g of the hot-melt adhesive of the ultrafine fibers is closer, by heat embossing, made clearly uneven pattern on the intermediate layer and the nonwoven fabric base material is likely to be transferred. When the softening temperature of the hot-melt adhesive is too high, the transferability to the intermediate layer is reduced, and when the temperature of hot embossing is excessively increased for clear transfer to the intermediate layer, the ultrafine fibers are The texture is lowered by fusing to form a film. In addition, when the softening temperature of the hot melt adhesive is too low, the transferability to the nonwoven fabric substrate is lowered, and when the temperature of the heat embossing is excessively increased to clearly transfer to the nonwoven fabric substrate, There is a possibility that the hot-melt adhesive may be melted or decomposed.

  The thickness of the intermediate layer is 10 to 150 μm, preferably 20 to 130 μm, and more preferably 30 to 120 μm. When the thickness of the intermediate layer is less than 10 μm, the transferability at the time of hot embossing is lowered. In addition, when the thickness of the intermediate layer exceeds 150 μm, the heat resistance of the article surface decorative sheet tends to decrease or the mechanical properties tend to decrease, and the article surface decorative sheet also becomes thick. Therefore, it is not preferable.

  The thickness of each layer varies somewhat depending on each region due to the difference in pressure applied in the press step for hot embossing, but in this embodiment, the region with the lowest compression rate, that is, the thickest region. Based on the average thickness.

  The thickness of the article surface decorating sheet of the present embodiment is not particularly limited, but the region having the lowest compression rate, that is, the thickness of the thickest region is 300 to 1000 μm, and further 300 to 600 μm includes a curved surface. Even in the case of decorating the surface of an article, it is preferable from the point of obtaining an article surface decorating sheet that can be accurately bonded.

  Further, the total thickness of the surface layer and the intermediate layer is preferably 40 to 180 μm, more preferably 50 to 100 μm. If the total thickness of the surface layer and the intermediate layer is too thin, surface characteristics such as wear resistance will be insufficient, and if the total thickness of the surface layer and the intermediate layer is too thick, the surface of the article There exists a tendency for the whole decorating sheet to become thick too much, and the designability falls or it becomes difficult to stick together.

  Further, the difference in height between the first region having a high compression rate formed by embossing and the second region having a low compression rate, that is, the difference in thickness between the first region and the second region is 100 to 500 μm, Furthermore, it is preferable that it is 150-400 micrometers. When the height difference is too small, the contour formed by the embossing becomes unclear, and those having a large height difference tend to be difficult to manufacture.

  Further, the difference in height or thickness between the first region and the second region is larger than the total thickness of the surface layer and the intermediate layer. Specifically, the first region and the second region If the height difference or thickness difference is 1.1 times or more, more preferably 2 times or more, with respect to the total thickness of the surface layer and the intermediate layer, the uneven pattern is formed even on the nonwoven fabric substrate. This is preferable because it is more clearly transferred and the contour is accurately expressed.

  In addition, as a pattern formed, a figure, a symbol, a pattern, a character, etc. are not specifically limited. Moreover, the part which forms a pattern or a character may be a recessed part or a convex part. FIG. 4 shows a schematic perspective view of an example of the article surface decorating sheet 25 formed as described above. In the article surface decorative sheet 25 of FIG. 4, 26 is a first region, 27 is a second region, and the second region is formed so that the letter “A” and the arrow symbol are raised. Yes.

  As shown in FIG. 1, the article surface decorating sheet 10 is used by adhering to the surface of the molded body 11, for example. In this case, by providing the adhesive layer 12 on the back surface of the article surface decorating sheet 10, it can be bonded to the surface of the molded body. A decorative molded body having an embossed pattern with a three-dimensional feeling is manufactured by bonding an article surface decorative sheet to the surface of the molded body.

  Further, the article surface decorative sheet of the present embodiment is used as a preform molded body or a sheet to be used for injection insert molding, and can be integrated into the surface simultaneously with the molding of the molded body. A decorative molded body having a certain embossed pattern is produced.

  The article surface decorating sheet of the present embodiment is an application requiring thinness, for example, a surface material of an article that is frequently repeatedly pressed with a human finger, more specifically, an elevator or various types It is preferably used as a skin material to be bonded to a push button of a home appliance, a surface of an information terminal device, a keyboard of a PC, or the like. Moreover, it is preferably used as a surface material or the like for displaying Braille or direction marks for allowing a visually handicapped person to recognize various types of information by touch.

  Next, an example of the manufacturing method of an article surface decorating sheet is demonstrated.

(1) Step of preparing a nonwoven fabric base material including an intertwined fiber bundle of ultrafine fibers having a fineness of 0.8 dtex or less In this step, first, a long fiber web made of sea-island type composite fibers is produced by melt spinning. For example, there is a method in which a sea-island type composite fiber is melt composite-spun, and the sea-island type composite fiber is collected on a net without being cut using a so-called spunbond method to form a web. The sea component of the sea-island type composite fiber is extracted or decomposed and removed at an appropriate later stage. By this decomposition removal or extraction removal, a fiber bundle of ultrafine fibers having a fineness of 0.8 dtex or less is formed.

  The spunbond method is preferably used for spinning and web formation of sea-island type composite fibers. Specifically, sea-island type composite fibers are continuously ejected from individual nozzle holes onto a conveyor belt-shaped mobile net using a composite spinning nozzle in which a large number of nozzle holes are arranged in a predetermined pattern. And depositing while cooling using a high-speed air stream. By such a method, a long fiber web is formed. The web formed on the net is preferably subjected to a fusion treatment. Form stability is imparted by the fusing process. As a specific example of the fusion process, for example, a hot press process can be cited. As a heat press process, the method of using a calender roll and applying a predetermined pressure and temperature, for example, can be employed.

  As the resin that forms the island component of the sea-island type composite fiber, the fiber that forms the ultrafine fiber described above is used. On the other hand, as the thermoplastic resin that constitutes the sea component of the sea-island composite fiber, a thermoplastic resin that is different from the resin that constitutes the island component in solubility in a solvent or decomposability in a decomposing agent is selected. Specific examples of the thermoplastic resin constituting the sea component include, for example, polyethylene, polypropylene, polystyrene, ethylene propylene copolymer, ethylene vinyl acetate copolymer, styrene ethylene copolymer, styrene acrylic copolymer, and polyvinyl alcohol. Resin etc. are mentioned. Of these, polyvinyl alcohol resins, particularly ethylene-modified polyvinyl alcohol resins, are preferred because they are easily contracted by wet heat or hot water.

The temperature of the hot press treatment for fusing the formed web is preferably 10 ° C. or more lower than the melting point of the component constituting the sea component of the sea-island composite fiber. If the temperature of the hot press treatment is 10 ° C or more lower than the melting point of the sea component, formation of entanglement defects or needle holes when entangled webs after stacking while maintaining good web form stability Can be made into a high-quality nonwoven fabric. The web basis weight after thermal pressing, is preferably in the range of 20 to 60 g / m ^2. By being in the range of 20 to 60 g / m ² , good form retention can be maintained in the subsequent web entanglement treatment.

  Next, a web entangled sheet is formed by stacking and entangling about 4 to 100 webs obtained. The web entangled sheet is formed by performing an entanglement treatment on the web using a known nonwoven fabric manufacturing method such as needle punching or high-pressure water flow treatment. Below, the entanglement process by a needle punch is demonstrated in detail as a typical example.

First, a silicone oil agent or a mineral oil oil agent such as a needle breakage prevention oil agent, an antistatic oil agent or an entanglement improving oil agent is applied to the web. Then, the entanglement process which entangles a fiber three-dimensionally with a needle punch is performed. By performing the needle punching, a web entangled sheet having a high apparent density and hardly causing the fibers to come off can be obtained. The basis weight of the web entangled sheet is appropriately selected according to the target thickness. Specifically, for example, a range of 500 to 2000 g / m ² is preferable from the viewpoint of excellent handleability.

  Next, if necessary, the apparent density and the entanglement degree of the web entangled sheet are increased by thermally shrinking the web entangled sheet. In addition, the web entangled sheet containing a long fiber shrink | contracts greatly by heat shrink compared with the web entangled sheet containing a short fiber. The apparent density of the web entangled sheet that has been subjected to the heat shrinkage treatment may be further increased by heating rolls or hot pressing.

  The change in the basis weight of the web entangled sheet due to the heat shrinkage treatment is 1.1 times (mass ratio) or more, further 1.3 times or more and 2.0 times or less, compared with the basis weight before the shrinkage treatment. Is preferably 1.6 times or less.

  In addition, you may provide a polymeric elastic body to a web entanglement sheet before or after the ultrafine fiberization process mentioned later as needed.

  Examples of the method for imparting the polymer elastic body to the web entangled sheet include a method of impregnating the web entangled sheet with a solution or emulsion of the polymer elastic body and then coagulating the polymer elastic body. As a method of impregnating the web entangled sheet with the solution or emulsion of the polymer elastic body, a process of immersing the solution or emulsion in the web entangled sheet so as to be in a predetermined impregnated state and squeezing with a press roll or the like is performed once. Or the dip nip method performed several times is used preferably. As other methods, a bar coating method, a knife coating method, a roll coating method, a comma coating method, a spray coating method, or the like may be used.

  The polymer elastic body is fixed to the web entangled sheet by impregnating the web entangled sheet with a solution or emulsion of the polymer elastic body and solidifying the polymer elastic body. In order to crosslink the crosslinkable polymer elastic body, it is preferable to perform a curing treatment by heat treatment after solidification and drying.

  The polymer elastic solution or emulsion is not limited to the effects of the present invention. Colorants such as dyes and pigments, coagulation regulators, antioxidants, ultraviolet absorbers, fluorescent agents, antifungal agents, and penetrating agents. Contains anti-foaming 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. May be.

  The sea-island composite fibers in the web-entangled sheet are converted into ultrafine fiber bundles by extracting or decomposing and removing sea components with water or a solvent. In the case of a sea-island type composite fiber using a water-soluble resin such as a polyvinyl alcohol-based resin as a sea component, the sea component is removed by a hot water heat treatment with water, an alkaline aqueous solution, an acidic aqueous solution or the like.

  Through the above-described steps, a nonwoven fabric substrate including an entangled body of fiber bundles of ultrafine fibers having a fineness of 0.8 dtex or less is prepared. The nonwoven fabric substrate thus obtained is usually adjusted to the desired thickness by slicing or grinding.

  (2) A step of forming a surface layer having a thickness of 1 to 50 μm containing a polymer elastic body on the surface of the release paper

  In this step, first, a sheet containing a polymer elastic body serving as a surface layer is formed on the surface of the release paper.

  The method of forming a sheet containing a polymer elastic body to be a surface layer on the surface of the release paper is not particularly limited, for example, after applying a solution or emulsion of the polymer elastic body on the release paper, to dry and solidify, Examples thereof include a so-called dry surface forming method, and a method of forming a polymer elastic film melted on a release paper using a T-die and cooling to solidify.

  (3) A hot melt adhesive solution coating film is formed on the surface layer formed on the surface of the release paper so that the dry thickness is 10 to 150 μm, and the nonwoven fabric substrate is pressure-bonded to the coating film. And forming a heat-transfer sheet by removing the release paper by adhering the nonwoven fabric substrate and the hot melt adhesive while removing the solvent in the coating film.

  A resin component containing a hot melt adhesive for forming an intermediate layer having a thickness of 10 to 150 μm is applied to the surface of a sheet containing a polymer elastic body, which is a surface layer formed on a release paper.

  The properties of the hot melt adhesive are usually solid at room temperature. Therefore, the formed intermediate layer is solid. Such a hot-melt adhesive is usually applied by adjusting the viscosity so that a solventless solid hot-melt adhesive can be applied. However, when a molten hot-melt adhesive is applied to a polymer elastic sheet for forming the surface layer, the polymer elastic sheet receives a thermal history. Therefore, in order to avoid such a heat history, it is preferable to form a coating film using a solution type hot melt adhesive in which a solid hot melt adhesive is dissolved in a solvent.

  A coating film is formed on the surface of the sheet for forming the surface layer formed on the release paper using a solution-type hot melt adhesive, and before the solvent in the solution is completely dried, By bonding the prepared nonwoven fabric base material and removing the solvent by drying, the nonwoven fabric base material and the surface layer are integrated. At this time, if necessary, the hot-melt adhesive may be hot-pressed at a temperature at which the hot-melt adhesive is not cured. And after a hot-melt-type adhesive agent and a nonwoven fabric base material are adhere | attached, a thermal transfer sheet is formed by peeling a release paper from a surface layer.

In addition, the thickness measured with the scanning microscope (SEM) of a no-load state with respect to the thickness when a heat-transfer sheet | seat before heat embossing applies a load of 240 gf / cm < ² > and measured with a constant pressure thickness measuring device. The ratio of is not particularly limited, but is preferably 80 to 89%, more preferably 80 to 85%. Moreover, the average value of the distance between the fiber bundles in the cross section in the thickness direction is preferably 10 μm to 30 μm, and more preferably 20 μm to 30 μm.

(4) The first region where the thickness ratio measured by a constant pressure thickness measuring device set to 240 gf / cm ² with respect to the thickness measured by SEM is 90% or more, and the first region which is 80 to 89%. Heat embossing the heat-transferred sheet so as to form two regions

The first area where the thickness ratio when measured with a constant pressure thickness measuring device set to 240 gf / cm ² with respect to the thickness measured with the SEM is 90% or more on the thermal transfer sheet, and 80 to 89% An article surface decoration sheet is obtained by forming a certain 2nd field.

  Specifically, for example, a heated transfer sheet 5 as shown in FIG. 5 (a), a heated embossing roll 6 and a heated smooth roll having an uneven embossing pattern on the surface as shown in FIG. 5 (b). The article surface decorating sheet 10 as shown in FIG.

The temperature and pressure of the embossing roll are the first in which the ratio of the thickness when measured with a constant pressure thickness measuring device set to 240 gf / cm ² with respect to the thickness measured with the SEM is 90% or more. There is no particular limitation as long as the region and the second region of 80 to 89% are formed. For example, as the temperature of the embossing roll, a temperature below the melting point and the like in the above T _g of the ultrafine fibers. Moreover, as a height difference of an embossing roll, an embossing roll with a large height difference which is 100-500 micrometers is used preferably.

The conditions for hot embossing are the first region where the thickness ratio measured by a constant pressure thickness measuring instrument set to 240 gf / cm ² with respect to the thickness measured by SEM is 90% or more, and 80 to 89% There is no particular limitation as long as the second region can be formed. Specifically, for example, the surface temperature is 100 to 180 ° C., the press pressure is 0.1 to 1.0 MPa, the press time is 1 to 3 m / min, and the temperature is 130 to 150 ° C., the press pressure is 0.1. Roll pressing is performed under the conditions of 2 to 0.5 MPa, pressing time of 1 to 3 m / min, in particular, temperature of 130 to 150 ° C., pressing pressure of 0.4 to 0.8 MPa, pressing time of 1 to 3 m / min. Such a method is preferably used. Further, the surface temperature is preferably 10 to 30 ° C., more preferably 15 to 25 ° C. higher than the softening temperature of the hot melt adhesive, from the viewpoint of excellent transferability. In the case of a roll press, the processing speed is preferably about 0.5 to 5 m / min, more preferably about 1 to 3 m / min, for example. In addition, when press temperature and press pressure are too high, it is unpreferable from the point that a fiber may fuse | melt and form a film.

  The article surface decorating sheet of this embodiment is obtained as described above. According to the article surface decorating sheet of the present embodiment, even a fine character or pattern is accurately transferred with unevenness having a large difference in elevation.

  The article surface decorating sheet thus obtained is cut into a predetermined bonding shape and integrated with the surface of the article such as a molded body. Bonding to the surface of the molded body is a method in which an adhesive layer is formed on the back surface of the article surface decorative sheet and bonded to the surface of the molded body or various articles, or a preform used for injection insert molding. It is used as a molded body or a sheet, and is integrated by a method of integrating the molded body main body with the surface simultaneously with the molding. In this way, a decorative molded body having a three-dimensional embossed pattern on the surface is obtained.

  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 as the thermoplastic resin of the sea component (content 8.5 mole% of ethylene units, polymerization degree 380, saponification degree 98.7 mol%), with T _g is 110 ° C. As the thermoplastic resin of the island component A certain isophthalic acid-modified polyethylene terephthalate (content of isophthalic acid unit: 6.0 mol%) was melted individually. Then, each molten resin was supplied to a plurality of spinning nozzles in which a large number of nozzle holes were arranged in parallel so as to form a cross-section in which 25 island components having a uniform cross-sectional area were distributed in the sea component. . At this time, it supplied, adjusting pressure so that the mass ratio of a sea component and an island component might become sea component / island component = 25/75. And it was made to discharge from the nozzle hole set to the nozzle | cap | die temperature of 260 degreeC.

Then, the molten fiber discharged from the nozzle hole is drawn by an air jet / nozzle type suction device in which the air pressure is adjusted so that the average spinning speed is 3700 m / min, and the fineness is 2.1 dtex. Sea island type long fiber was spun. The spun sea-island long fibers were continuously deposited on the movable net while sucking from the back of the net. The amount of deposition was adjusted by adjusting the moving speed of the net. And in order to suppress fuzz on the surface, the sea-island type long fibers deposited on the net were lightly pressed with a 42 ° C. metal roll. Then, the sea-island long fibers were peeled from the net, and hot-pressed at a linear pressure of 200 N / mm by passing between a metal roll with a lattice pattern with a surface temperature of 75 ° C. and a back roll. In this way, a long fiber web having a basis weight of 34 g / m ² in which the fibers on the surface were temporarily fused in a lattice shape was obtained.

Next, after spraying an oil agent mixed with an antistatic agent on the surface of the obtained long fiber web, 10 sheets of the long fiber web are overlapped using a cross wrapper device, and the total basis weight is 340 g / m ² . A web was prepared, and a needle breakage oil was sprayed. And the three-dimensional entanglement process was carried out by needle punching the overlap web. Specifically, a 6 barb needle with a distance of 3.2 mm from the needle tip to the first barb was used, and needle punching was performed alternately at 3300 punches / cm ² from both sides of the laminate at a needle depth of 8.3 mm. . The area shrinkage rate by this needle punching treatment was 68%, and the basis weight of the entangled web after needle punching was 415 g / m ² .

The resulting entangled web was densified by a wet heat shrinkage treatment as follows. Specifically, water at 18 ° C. is uniformly sprayed on the entangled web by 10% by mass, and left in a state where no tension is applied for 3 minutes in an atmosphere at a temperature of 70 ° C. and a relative humidity of 95%. The apparent fiber density was improved by heat and heat shrinkage. The area shrinkage rate by the wet heat shrinkage treatment was 45%, the basis weight of the densified entangled web was 750 g / m ² , and the apparent density was 0.52 g / cm ³ . The apparent density was adjusted to 0.60 g / cm ³ by dry-heat roll pressing to further densify the entangled web.

  Next, the densified entangled web was impregnated with nonporous crosslinkable polyurethane having a mass reduction rate of 0.5% by mass with respect to DMF immersion as follows. A densified entangled web was impregnated with a cross-linked aqueous polyurethane emulsion (solid content concentration 30%) containing a polycarbonate / ether polyurethane. And the water | moisture content was dried with the drying furnace of 150 degreeC, and also the polyurethane was bridge | crosslinked. A polyurethane entangled web composite having a polyurethane / entangled web mass ratio of 18/82 was thus formed.

  Next, the polyurethane entangled web composite is immersed in hot water at 95 ° C. for 20 minutes to extract and remove sea components contained in the sea-island long fibers, and dried in a drying furnace at 120 ° C. to obtain a thickness. A nonwoven substrate of about 1000 μm was obtained.

The mass ratio of polyurethane / fiber entangled body of the obtained nonwoven fabric base material was 22/78, and its apparent density was 0.53 g / cm ³ . Further, the fineness of the ultrafine single fiber of the fiber entangled body was 0.08 dtex.

  And the obtained nonwoven fabric base material was divided | segmented into 2 to the thickness direction, and was ground to 370 micrometers.

  On the other hand, a DMF solution of non-crosslinkable silicon-modified polycarbonate polyurethane was applied as a surface layer on the release paper, and dried to form a surface layer sheet having a thickness of 30 μm.

  Then, a DMF solution of a polycarbonate hot-melt adhesive having a solid content of about 50% was applied to the surface layer sheet so that the thickness after drying was 50 μm. The softening temperature of the polycarbonate hot melt adhesive was 120 ° C.

  And the nonwoven fabric base material was bonded together to the coating film of the DMF solution of the polyurethane-type hot-melt-type adhesive formed on the surface layer sheet, and the solvent in the coating film was dried while lightly pressing. In this way, a heat transfer sheet was obtained. The thickness of the obtained thermal transfer sheet was 411 μm.

  Then, a flat plate press having a convex portion having a square outer shape with a height difference of 600 μm and a side of 15 mm is used to transfer the pattern as shown in FIG. 1 to the obtained thermal transfer sheet. Then, by embossing at a surface temperature of 150 ° C., a pressing pressure of 3 MPa, and a pressing time of 5 seconds, an article surface decorative sheet having an embossed pattern with a height difference of 179 μm as shown in FIG. Obtained.

And about the thinnest area | region (area | region equivalent to C of FIG. 1) and the thickest area | region (area | region equivalent to A of FIG. 1) of the obtained article | item surface decorating sheet, those thickness is based on JISL1096. The thickness was 223 μm as measured with a JIS thickness measuring instrument (constant pressure thickness measuring machine manufactured by Ozaki Seisakusho Co., Ltd.) having a load of 240 gf / cm ² . On the other hand, the thickness of the same part measured by SEM was 232 μm. As a result, the ratio of the thickness when measured with a constant pressure thickness measuring instrument to the thickness measured with the SEM was 96.1%.

  Moreover, 200 times SEM images of the cross sections in the thickness direction of the thinnest region and the thickest region of the obtained article surface decoration sheet were taken. And the average value of the distance between the fiber bundles in a thickness direction cross section was calculated | required by the method as shown below.

  For example, as shown in FIG. 2, ten auxiliary lines parallel to the thickness direction were drawn at an interval of about 80 μm in the range of 861 μm in the width direction of the thermal transfer sheet. And the sum total of the distance between fiber bundles (distance between the outer periphery of a fiber bundle) between the outlines of the several fiber bundle which each line passes was calculated | required for every line. And the distance sum (A) of the distance between fiber bundles in 10 lines was determined. On the other hand, the total number of ultrafine fiber bundles on 10 lines was determined, and the number of fiber bundles (B) obtained by subtracting 10 from the total number was determined. Then, the average value of the distances between the ultrafine fiber bundles was calculated by dividing the total distance (A) by the number of interfiber bundles (B). As a result, the average value of the distance between the ultrafine fiber bundles in the thinnest region of the obtained article surface decorative sheet was 2.70 μm, and the average value of the distance between the ultrafine fiber bundles in the thickest region was 18.75 μm. .

  And the transcription | transfer property of the uneven | corrugated pattern of the obtained surface decoration sheet of articles | goods, and the difficulty to the pattern crushing were evaluated as follows. The results are summarized in Table 1.

<Evaluation of transferability>
The deep drawing shape (edge, sharpness, depth) was visually determined in three stages according to the following criteria.
First grade: The grain depth was deep, and a deep drawing shape was included from the grain top to the bottom.
Second grade: The grain depth was deep, and a deep drawing shape was included from the height 2/3 of the grain top to the bottom.
Third grade: The grain depth was shallow, and a deep drawing shape was included from the height of half the grain top to the bottom.

<Evaluation of shape durability>
An actual wearing test was carried out by pasting on five mobile phones for two months, and the result of visual confirmation of changes in appearance was evaluated according to the following three criteria.
A: No change in appearance.
B: There is a slight change in appearance.
C: Appearance change is remarkable.

[Example 2]
In Example 1, instead of using isophthalic acid-modified polyethylene terephthalate having a T _g of 110 ° C. as the island component thermoplastic resin, the isophthalic acid modified polyethylene having a T _g of 120 ° C. as the island component thermoplastic resin. A thermal transfer sheet was obtained in the same manner as in Example 1 except that terephthalate was used, and an article surface decorative sheet was obtained. And it evaluated similarly. The results are shown in Table 1.

[Example 3]
In Example 1, instead of using isophthalic acid-modified polyethylene terephthalate whose T _g is 110 ° C. as the island component thermoplastic resin, isophthalic acid modified polyethylene whose T _g is 100 ° C. as the island component thermoplastic resin. A thermal transfer sheet was obtained in the same manner as in Example 1 except that terephthalate was used, and an article surface decorative sheet was obtained. And it evaluated similarly. The results are shown in Table 1.

[Example 4]
In Example 1, instead of using a polyurethane / fiber entangled mass ratio of 22/78, a non-woven fabric substrate having an apparent density of 0.69 g / cm ³ in which the polyurethane / fiber entangled mass ratio was 29/71 was used. Obtained the heat-transfer sheet | seat similarly to Example 1, and obtained the article | item surface decoration sheet. And it evaluated similarly. The results are shown in Table 1.

[Example 5]
In Example 1, instead of coating the surface layer sheet with a polyurethane hot melt adhesive so that the thickness after drying is 50 μm, the polyurethane hot melt type so that the thickness after drying is 10 μm. A heat transfer sheet was obtained in the same manner as in Example 1 except that the adhesive was applied, and an article surface decorative sheet was obtained. And it evaluated similarly. The results are shown in Table 1.

[Example 6]
In Example 1, instead of applying a polyurethane hot-melt adhesive to the surface layer sheet so that the thickness after drying becomes 50 μm, the polyurethane hot-melt type so that the thickness after drying becomes 150 μm. A heat transfer sheet was obtained in the same manner as in Example 1 except that the adhesive was applied, and an article surface decorative sheet was obtained. And it evaluated similarly. The results are shown in Table 1.

[Example 7]
In Example 1, instead of forming a surface layer sheet having a thickness of 30 μm after drying on the release paper, the surface layer sheet was formed to have a thickness of 15 μm after drying. Similarly, a thermal transfer sheet was obtained, and an article surface decorative sheet was obtained. And it evaluated similarly. The results are shown in Table 1.

[Example 8]
In Example 1, instead of forming a surface layer sheet having a thickness of 30 μm after drying on the release paper, the surface layer sheet was formed to have a thickness of 50 μm after drying. Similarly, a thermal transfer sheet was obtained, and an article surface decorative sheet was obtained. And it evaluated similarly. The results are shown in Table 1.

[Example 9]
In Example 1, instead of impregnating the nonwoven fabric base material with a non-porous polyurethane having a mass reduction rate of 0.5% by mass with respect to DMF immersion, a foamed polyurethane having a mass reduction rate with respect to DMF of 100% by mass was obtained. A nonwoven fabric base material having a mass ratio of foamed polyurethane / fiber entanglement of 18/82 was formed by impregnating with a DMF solution of polyurethane for forming (solid content 20%) and wet coagulating. Except for the above changes, a heat transfer sheet was obtained in the same manner as in Example 1, and an article surface decorating sheet was obtained. And it evaluated similarly. The results are shown in Table 1.

[Comparative Example 1]
In Example 1, instead of using isophthalic acid-modified polyethylene terephthalate having a T _g of 110 ° C. as the island component thermoplastic resin, polyethylene terephthalate having a T _g of 130 ° C. was used as the island component thermoplastic resin. Except for the above, a heat transfer sheet was obtained in the same manner as in Example 1, and an article surface decorative sheet was obtained. And it evaluated similarly. The results are shown in Table 1. Moreover, the SEM photograph of the cross section of the obtained article | item surface decoration sheet is shown in FIG.

[Comparative Example 2]
In Example 1, instead of applying a polyurethane-based hot melt adhesive having a softening temperature of 120 ° C. to the surface layer sheet, it is not a hot melt adhesive.
A thermal transfer sheet was obtained in the same manner as in Example 1 except that a one-component polycarbonate adhesive with a softening temperature of 150 ° C. was applied, and an article surface decorative sheet was obtained. And it evaluated similarly. The results are shown in Table 1.
[Comparative Example 3]
In Example 1, instead of applying a polyurethane hot-melt adhesive to the surface layer sheet so that the thickness after drying becomes 50 μm, the polyurethane hot-melt type so that the thickness after drying becomes 8 μm. A heat transfer sheet was obtained in the same manner as in Example 1 except that the adhesive was applied, and an article surface decorative sheet was obtained. And it evaluated similarly. The results are shown in Table 1.

From Table 1, the article surface decorating sheets of Examples 1 to 9 according to the present invention all had a transferability of 2nd grade or more and excellent shape durability. In addition, instead of using the isophthalic acid-modified polyethylene terephthalate having a T _g of 110 ° C., the article surface decorating sheet of Example 2 using the isophthalic acid-modified polyethylene terephthalate having a T _g of 120 ° C. is a fiber bundle. The stretchability was slightly lower, the distance between the fiber bundles in the first region was slightly larger, and the transferability was second grade. In addition, the article surface decorative sheet of Example 5 in which the thickness of the intermediate layer was changed from 50 μm to 10 μm also had a transferability of second grade. Furthermore, the article surface decorating sheet of Example 9 in which 18% of porous polyurethane was contained in a nonwoven fiber substrate also had a slightly larger distance between fiber bundles and a transferability of second grade. On the other hand, T _g polyethylene terephthalate article surface decorative sheet of Comparative Example 1 using that isophthalic acid-modified is 130 ° C., the lower stretch of the fiber bundle, the fiber bundle between the length of the second region is large, transferability Was grade 3. Moreover, the article surface decorative sheet of Comparative Example 2 using a one-pack polycarbonate adhesive having a softening temperature of 150 ° C., which is not a hot melt adhesive, as the intermediate layer had a transferability of third grade. Further, the article surface decorative sheet of Comparative Example 3 having an intermediate layer thickness of 8 μm was remarkably low because the transferability was tertiary.

  The article surface decorating sheet of the present invention is an application requiring thinness, for example, a surface material of an article that is frequently repeatedly pressed by a human finger, and more specifically, elevators and various home appliances. It is preferably used as a skin material to be bonded to a push button of a product, the surface of an information terminal device or a keyboard of a PC. Moreover, it is preferably used as a surface material or the like for displaying Braille or direction marks for allowing a visually handicapped person to recognize various information by tactile sensation.

DESCRIPTION OF SYMBOLS 1 Nonwoven fabric base material 1a Extra fine single fiber 1b Fiber bundle 2 Surface layer 3 Intermediate layer 6 Embossing roll 7 Heating smooth roll 10,25 Article surface decoration sheet 11 Molded body main body 12 Adhesive layer 20 Decorated molded body A, 27 2 area C, 26 1st area

Claims (10)

An article surface decorating sheet embossed with a pattern,
A non-woven fabric substrate, a surface layer of 1 to 100 μm containing a polymer elastic body, and an intermediate layer of 10 to 150 μm in thickness containing a hot-melt adhesive that bonds the non-woven fabric substrate and the surface layer. ,
The nonwoven fabric base material includes an entanglement of fiber bundles of ultrafine fibers having a fineness of 0.8 dtex or less,
An article comprising a first region formed by the embossing and having an average distance between the fiber bundles in a cross section in the thickness direction of less than 10 μm and a second region of 10 μm or more and 30 μm or less. Surface decoration sheet. The ratio of the thickness when measured with a constant pressure thickness measuring device set to 240 gf / cm ² with respect to the thickness measured with a scanning microscope (SEM),
2. The article surface decorating sheet according to claim 1, which is 90% or more in the first region and 80 to 89% in the second region. The hot-melt adhesive, the article surface decorative sheet according to claim 1 or 2 having 0 to 30 ° C. softening temperature higher than the glass transition temperature (T _g) of the ultrafine fibers. The ultrafine fibers, the article surface decorative sheet according to claim 3, including a modified polyester having a T _g of 100 to 120 ° C..   The height difference or thickness difference between the first region and the second region is larger than the total thickness of the surface layer and the intermediate layer, according to any one of claims 1 to 4. Article surface decoration sheet.   The article according to claim 5, wherein a difference in height or thickness between the first region and the second region is 1.1 times or more with respect to a total thickness of the surface layer and the intermediate layer. Surface decoration sheet.   The article | item surface decorating sheet of any one of Claims 1-6 containing 5-40 mass% of the non-porous polymeric elastic body by which the said nonwoven fabric base material was bridge | crosslinked. (1) T _g and the nonwoven fabric substrate comprising entangled body of fiber bundle following ultrafine fiber fineness 0.8dtex containing modified polyester is 100 to 120 ° C., the surface layer having a thickness of 1~100μm comprising elastic polymer And an intermediate layer having a thickness of 10 to 150 μm including a hot-melt adhesive having a softening temperature 0 to 30 ° C. higher than the T _g for bonding the nonwoven fabric substrate and the surface layer. A preparation process;
(2) The first region where the thickness ratio measured by a constant pressure thickness measuring device set to 240 gf / cm ² with respect to the thickness measured by SEM is 90% or more, and the first region which is 80 to 89%. And a step of subjecting the thermal transfer sheet to a heat embossing treatment so as to form two regions. The step (1)
(1a) preparing the nonwoven fabric substrate;
(1b) forming a surface layer having a thickness of 1 to 50 μm including the polymer elastic body on the surface of the release paper;
(1c) forming a coating film of the hot melt adhesive solution on the surface layer formed on the surface of the release paper so that the thickness upon drying is 10 to 150 μm;
(1d) The non-woven fabric substrate is pressure-bonded to the coating film, the non-woven fabric substrate and the hot-melt adhesive are bonded while removing the solvent in the coating film, and the release paper is removed. The manufacturing method of the article | item surface decorating sheet of Claim 8 provided with the process of forming a thermal transfer sheet.   The manufacturing method of the article | item surface decorating sheet of Claim 8 or 9 whose surface temperature of the embossing type | mold used for the said heat embossing process is 10-30 degreeC higher than the softening temperature of the said hot-melt-type adhesive agent.