JP6544262B2 - LAMINATE FOR DECORATIVE FORMING, DECORATED MOLDED BODY, AND METHOD FOR MANUFACTURING DECORATED MOLDED BODY - Google Patents

Description

  BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a decorative molding laminate, a decorative molding, and a method of manufacturing the decorative molding.

  Conventionally, in the case of protecting the surface of automobile interior / exterior parts, parts for home appliances, parts for building materials, etc. or decorating (decorating), after processing the formed body by injection molding or vacuum forming, it is sprayed on the surface of the formed body It has been practiced to apply a paint by painting, etc., and to dry and heat cure. However, in addition to the problem that the discharge of the volatile organic solvent worsens the working environment, such coating requires work processes and production facilities for each molded part, and the paint recoating is necessary. There is a problem that the yield of the paint is poor and the productivity is low.

  In recent years, for the purpose of reducing the weight of automobile interior and exterior parts, parts for home appliances, parts for building materials and the like, the use of resin moldings as moldings has progressed. In many cases, spray coating is not suitable for the decoration (decoration) of a resin molded body, and various techniques have been developed to decorate the surface of the resin molded body. Above all, the method of obtaining the decorated molded body by decorating the outermost surface of the molded body with a decorative film has a higher degree of freedom in design than the method of applying or printing on the surface using a paint etc., and productivity Also has the advantage of being superior. Moreover, since the decoration method using a decoration film can also decorate the molded object surface which has three-dimensional unevenness | corrugation, it is used for various uses.

  As a decoration film, the film which has only a decoration layer, and the film which has a decoration layer and a base material layer are known. For example, Patent Documents 1 and 2 disclose a decorative film including a hard coat layer as a photocurable resin layer. In Patent Document 1, a matte texture is imparted to the surface by containing fine particles in the hard coat layer. Moreover, in patent document 2, it is supposed that the decorative film excellent in a feeling of depth and sharpness is obtained by giving fine embossing to the surface of a hard-coat layer.

  By the way, there exists a three-dimensional coating molding (TOM molding) method as a method of decorating the molded object surface which has three-dimensional unevenness | corrugation with a decoration film (patent document 3). TOM molding is a molding method under vacuum conditions or reduced pressure conditions, and is a method of pressing a decorative film and a molding to obtain a decorative molding. In TOM molding, it is possible to decorate regardless of the material of the molded body. In addition, the reverse tapered portion and the end winding portion can be coated and formed without providing a vacuum hole in the molded body.

  As a decorative film used for TOM molding, there are a film having only a decorative layer, and a laminated film (laminated body) having a decorative layer, an adhesive layer, and the like. When obtaining a decorating molded object using the film which has only a decoration layer, the method of fuse | melting film itself and making a molten film and a molded object contact | adhere is used. Moreover, when using the lamination film which has a decoration layer and an adhesion layer, a decoration layer does not need to be melted and it makes adhesion a lamination film and a molded object using adhesiveness, such as an adhesion layer.

Patent No. 5416339 gazette JP, 2014-213578, A Patent No. 3733564

  As described above, various decorative films have been developed, but in Patent Documents 1 and 2, the use of the decorative film in TOM molding has not been sufficiently studied. When TOM molding is performed using the decorative film as described in Patent Document 1 by the present inventors, cracks may occur at the position where the fine particles are present, and sufficient stretchability may not be exhibited along the molded body? It turned out that it is a thing which does not exhibit sufficient decoration performance (that is, haze value is low). Further, the decorative film described in Patent Document 2 is not sufficient in stretchability, and there is room for improvement when it is used for TOM molding.

  Therefore, the present inventors provide a decorative film (laminate for decorative molding) that can exhibit sufficient stretchability and has a small decrease in haze before and after stretching in order to solve the problems of the conventional art. The study went forward with the purpose of

As a result of earnestly examining in order to solve said subject, the present inventors set the haze of a surface protective layer as predetermined conditions in the laminate for decoration molding which has a specific surface protective layer, and it decorates. It is found that by setting the breaking elongation of a forming laminate as a specific condition, a decorative forming laminate having sufficient stretchability and capable of maintaining a high haze value even after stretching can be obtained. The
Specifically, the present invention has the following configuration.

[1] A laminate for decorative molding comprising a surface protective layer having a photocurable resin on the outermost surface, wherein the haze of the surface protective layer is 10% or more, in the first direction of the laminate for decorative molding The breaking elongation at 120 ° C. is more than 50%, and the breaking elongation at 120 ° C. in the second direction orthogonal to the first direction is more than 50%, and the surface protection before stretching the decorative molding laminate Assuming that the haze of the layer is P, and the haze of the surface protective layer after the decorative molding laminate is stretched 50% in the first direction or the second direction is Q, (P−Q / P) × 100 The haze reduction rate represented by these is 40% or less, The laminated body for decorating formation characterized by the above-mentioned.
[2] The decorative molding laminate according to [1], wherein the outermost surface of the surface protective layer has a fine uneven structure.
[3] The decorative molding laminate according to [2], wherein the average height of the projections of the fine uneven structure is 0.1 μm to 50 μm.
[4] The average width of the convex portions of the fine uneven structure is 0.1 μm to 500 μm, and the ten-point average roughness Rz of the outermost surface of the surface protective layer is 1 μm to 30 μm [1] to [3] The laminate for decorative molding according to any one of the above.
[5] The decorative molding laminate according to any one of [1] to [4], further having an adhesive layer.
[6] The decorative molding laminate according to any one of [1] to [5], which is used for decorative molding under vacuum conditions or reduced pressure conditions.
[7] The decorative molding laminate according to any one of [1] to [6], which is used to decorate an automobile member, an electronic device, or a building material.
[8] The decorative molding laminate according to any one of [1] to [7], wherein the draw ratio in at least one direction selected from the first direction and the second direction is 1.5 or more.
[9] A decorated molded body comprising the laminate for decoration molding according to any one of [1] to [8] and a molded article decorated with the laminate for decoration molding.
[10] A decorative forming including a step of laminating a decorative forming laminate on a molded body under vacuum conditions or reduced pressure conditions, and a step of pressure bonding the decorative forming laminate to a molded body by a pressure difference. It is a manufacturing method of a body, and the layered product for decoration molding includes a surface protection layer which has photocuring resin in the outermost surface, and the haze of a surface protection layer is 10% or more, and the number of the layered product for decoration molding The breaking elongation at 120 ° C. in the direction 1 is greater than 50%, and the breaking elongation at 120 ° C. in the second direction orthogonal to the first direction is greater than 50%, and the laminate for decorative formation is stretched Assuming that the haze of the front surface protective layer is P, and the haze of the surface protective layer after the decorative molding laminate is stretched 50% in the first direction or the second direction is Q, (PQ / P) The manufacturing method of the decorating molded object whose haze decreasing rate represented by * 100 is 40% or less .

  According to the present invention, it is possible to obtain a decorative molding laminate having sufficient stretchability and a high haze value, and having a high haze value even after stretching. By using the laminate for decorative molding of the present invention, the productivity of the decorated molded product can be enhanced, and a decorated molded product excellent in design can be produced.

FIG. 1 is a cross-sectional view showing an example of the constitution of the laminate for decorative formation of the present invention. FIG. 2 is an enlarged cross-sectional view for explaining the structure of the fine convex portion of the surface protective layer. FIG. 3 is a cross-sectional view for explaining the structure of the decorated molded body of the present invention.

  Hereinafter, the present invention will be described in detail. The description of the configuration requirements described below may be made based on typical embodiments and specific examples, but the present invention is not limited to such embodiments.

(Laminated body for decorative molding)
The present invention relates to a laminate for decorative formation, which includes a surface protective layer having a photocurable resin on the outermost surface. The haze of the surface protective layer is 10% or more. The breaking elongation at 120 ° C. in the first direction of the laminate for decorative formation is greater than 50%, and the breaking elongation at 120 ° C. in the second direction orthogonal to the first direction is greater than 50%. In addition, the haze of the surface protective layer before stretching the laminate for decoration molding is P, and the haze of the surface protective layer after stretching the laminate for decoration molding in the first direction or the second direction by 50%. The haze reduction rate represented by (P−Q / P) × 100 is 40% or less, where Q is Q.

The surface protective layer of the laminate for decoration molding of the present invention has a photocurable resin, and the photocurable resin is present on the outermost surface. By arranging the photocurable resin on the outermost surface, it has a function of physically protecting other layers such as a pressure-sensitive adhesive layer and a molded body which is an adherend. That is, since the surface protection layer of the present invention is a layer having a photocurable resin, it has a function of protecting the surface of a molded product or the like.
In addition, the surface protective layer has a function (a haze value of a predetermined value or more) to scatter transmitted light at a predetermined ratio or more even after stretching. The surface protective layer in the present invention may achieve the above-mentioned physical protection function and light scattering function as a whole by laminating a plurality of layers, or may achieve equivalent functions in a single layer It may be The surface protective layer formed by laminating a plurality of layers can be formed, for example, by coating one side of a substrate with a photocurable resin composition. That is, the surface protective layer may be composed of a substrate and a photocurable resin layer.

Since the layered product for decoration molding of the present invention has the above-mentioned composition, it has sufficient ductility and high haze value. A laminate having high extensibility is preferably used in applications for decorative molding under vacuum conditions or reduced pressure conditions. As a molding method under vacuum conditions or reduced pressure conditions, for example, TOM molding (three-dimensional coating molding) method etc. may be mentioned, and the laminate for decorative molding of the present invention is particularly preferably used in molding methods such as TOM molding .
Furthermore, the laminate for decorative molding of the present invention has a surface protective layer that retains a high haze value even after stretching, and is characterized in that the reduction in haze is small before and after stretching. In general, a laminate for decorative molding is stretched at the time of decoration and attached to the surface of an adherend, so a laminate with a small decrease in haze before and after stretching is suitable as a decorative film, and a molding having excellent designability Body can be molded.

FIG. 1 is a cross-sectional view showing an example of the constitution of the laminate for decorative formation of the present invention. As shown in FIG. 1, the decorative molding laminate 1 of the present invention includes the surface protective layer 2 or consists of the surface protective layer 2. The surface protective layer 2 preferably has a base layer 3 and a photocurable resin layer 5. In this case, the base material layer 3 side is pasted so that it may come to the surface side of the forming object which is a covering object.
In the following, the surface protective layer 2 of the laminate 1 for decorative molding of the present invention will be described focusing on a preferred embodiment having the base material layer 3 and the photocurable resin layer 5, but for decorative molding of the present invention The surface protective layer 2 of the laminate does not necessarily have to have the base layer 3, and the photocurable resin layer 5 may include the function of the base layer 3. In addition, the surface protective layer 2 may be only the base material layer 3.

  When the surface protective layer 2 of the laminate 1 for decoration molding of the present invention has the base material layer 3 and the photocurable resin layer 5, another layer is present between the base material layer 3 and the photocurable resin layer 5. Although it may be provided, it is preferable that the base material layer 3 and the photocurable resin layer 5 are laminated so as to be in direct contact with each other. In addition, another layer may be provided on one surface of the base layer 3 opposite to the surface on which the photocurable resin layer 5 is laminated. For example, a pressure-sensitive adhesive layer may be provided, and a decorative molding laminate may be attached to a molded article to be adhered via such a pressure-sensitive adhesive layer. Alternatively, the surface protective layer 2 may be attached (for example, heat-sealing) to the surface of the molded article, which is the object to be adhered, without interposing the adhesive layer.

The breaking elongation at 120 ° C. in the first direction of the laminate for decorative formation may be greater than 50%, preferably 65% or more, more preferably 80% or more, and 100% or more. It is further preferred that In addition, the breaking elongation at 120 ° C. in the second direction orthogonal to the first direction of the laminate for decorative formation may be greater than 50%, preferably 65% or more, and is 80% or more. Is more preferably 100% or more. Here, the first direction of the decorative-forming laminate is preferably the longitudinal direction of the decorative-forming laminate. The longitudinal direction is the flow direction when forming the surface protective layer, and is also referred to as the MD (Machine Direction). The second direction orthogonal to the first direction is a width direction orthogonal to the flow direction, and is also referred to as a CD direction (Crcss Machine Direction). Thus, when the flow direction of the decorative molding laminate is known, the first direction is taken as the flow direction, but when the flow direction of the decorative molding laminate is not known, the decorative molding laminate Any one direction in the plane direction can be taken as the first direction. Also in this case, the second direction is a direction orthogonal to the first direction.
The present invention is characterized in that the breaking elongations in the first direction and the second direction are large, and because it has such breaking elongations, the shape of a molded article to be adhered during decorative molding It has the characteristic of being easy to stretch following the

  The breaking elongation at 120 ° C. in the first direction and the second direction of the decorative-forming laminate can be measured by the following method. First, the draw ratio in the first direction or the second direction of the decorative molding laminate is from 10 to 100% at 120 ° C. using a TOM molding machine (NGF molding machine manufactured by Urushi Vacuum Co., Ltd.) The molding is carried out using a measurable jig in 10% steps to obtain a molded body. Then, the stretching ratio before breakage occurs in a part of the surface protective layer is taken as the breaking elongation of the laminate for decorative formation. That is, each test is conducted by largely changing the draw ratio by 10%, and the elongation at break of -10% of the draw ratio at which the surface protective layer (the surface of the molded product) is first seen to break is made. For example, each test is conducted by largely changing the draw ratio by 10%, and when elongation is seen for the first time in the surface protective layer (the surface of the molded product) when stretched 90%, the elongation at break is made 80%.

  The decorative molding laminate has sufficient stretchability. The surface protective layer of the decorative molding laminate has sufficient stretchability at the maximum stretched portion (stretching ratio of 50% or more of the laminate longitudinal direction and width direction) of the decorative molding laminate. It means the state where destruction of is not seen.

  The haze before stretching of the surface protective layer is preferably 10% or more, more preferably 15% or more, and still more preferably 20% or more. Further, the haze of the surface protective layer after 50% stretching in the first direction or the second direction is preferably 5% or more, more preferably 10% or more, and further preferably 15% or more. preferable.

  In the present invention, the haze of the surface protective layer before stretching the decorative molding laminate is P, and the surface protection after the decorative molding laminate is stretched 50% in the first direction or the second direction. When the haze of the layer is Q, the haze reduction rate represented by (P−Q / P) × 100 is 40% or less. The value of the haze reduction rate is preferably 35% or less, more preferably 30% or less, still more preferably 20% or less, and most preferably 15% or less. As described above, the present invention is characterized in that the haze reduction rate is low, and has a high haze value even after stretching. By setting the haze reduction rate in the above-mentioned range, it is possible to exhibit excellent decorativeness.

  In the present specification, a state in which the decorative molding laminate is stretched by 50% in the first direction or the second direction means the stretching of the decorative molding laminate in the first direction or the second direction. It is synonymous with a magnification of 1.5 times.

  The total light transmittance of the surface protective layer before stretching the decorative molding laminate is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. Further, the total light transmittance of the surface protective layer after the decorative molding laminate is stretched by 50% in the first direction or the second direction is preferably 70% or more, and is 80% or more. Is more preferably 90% or more.

  The haze and the total light transmittance of the surface protective layer are values measured according to JIS K 7136. As a measuring instrument, the haze meter "NDH-5000" made from Nippon Denshoku Industries Co., Ltd. can be mentioned, for example.

  The thickness of the surface protective layer of the laminate for decoration molding of the present invention is preferably 20 μm or more, more preferably 35 μm or more, still more preferably 70 μm or more, and particularly preferably 150 μm or more. preferable. Moreover, it is preferable that the thickness of the surface protective layer of the laminate for decoration molding is 500 micrometers or less. By setting the thickness of the surface protective layer of the laminate for decorative formation within the above range, the surface of the molded product can be easily decorated.

  The present invention may relate to a stretched laminate for decorative molding. Specifically, the present invention may relate to a decorative molding laminate in which the draw ratio in at least one direction selected from the first direction and the second direction is 1.5 or more. In such a decorative molding laminate, the draw ratio in at least one direction selected from the first direction and the second direction is preferably 1.5 times or more, and preferably 2 times or more. More preferable. Furthermore, it is more preferable that the draw ratio in both the first direction and the second direction is within the above range.

  The laminate for decorative molding of the present invention is preferably used to decorate an automobile member, an electronic device or a building material. Since the laminate for decoration molding of the present invention is excellent in stretchability and has a surface protective layer which retains high haze value even after stretching, it is preferably used for the above-mentioned applications. Moreover, since the laminate for decoration molding of the present invention has excellent stretchability, it is excellent in unevenness followability, and a member having an unevenness structure and a curved portion can be easily decorated.

(Photo-cured resin layer)
The surface protective layer of the laminate for decoration molding of the present invention may have a photocurable resin layer. The haze of the photocurable resin layer is preferably 10% or more, more preferably 11% or more, still more preferably 12% or more, still more preferably 13% or more, 14% or more It is most preferable that As described above, the higher the haze of the photocurable resin layer, the better the decoration property. That is, it is preferable that the haze of the photocurable resin layer is high because the surface properties of the molded product are less likely to be visually recognized. In addition, said haze value is a haze value of the photocurable resin layer before extending | stretching the laminated body for decoration molding. In the case where the surface protective layer is composed of a plurality of layers, the haze of the photocurable resin layer is measured for each of the layers other than the photocurable resin layer and the surface protective layer, and the haze value of the surface protective layer is measured. It can be calculated by subtracting the haze value of layers other than the cured resin layer.

  FIG. 2: is an expanded sectional view explaining the structure of the fine convex part of a photocurable resin layer (or surface protective layer). As shown in FIG. 2, it is preferable that one surface of the photocurable resin layer, which is the surface opposite to the surface on the base material layer side, has a micro uneven structure. When the photocurable resin layer has such a fine concavo-convex structure, the surface protective layer can have a high haze value.

  The average height of the projections of the fine relief structure is preferably 0.1 μm or more, more preferably 1 μm or more, and still more preferably 5 μm or more. In addition, the average height of the projections of the fine relief structure is preferably 50 μm or less, more preferably 40 μm or less, and still more preferably 30 μm or less. Here, as shown in FIG. 2, the height of the convex portion 10 of the fine concavo-convex structure is a distance represented by A. The average height is an average value when ten or more heights of the convex portions 10 are measured.

  The average height of the projections of the fine relief structure can be measured by the following method. First, surface observation is performed at a magnification of 200 times using a microlaser microscope (measurement unit VK-X105 controller unit VK-X100 manufactured by KEYENCE CORPORATION), and an image is captured. Next, for the obtained image, the measurement area is set to 100 μm × 100 μm, and the height of the convex portion is measured using analysis software attached to the microlaser microscope. Specifically, each 10 points are measured, and the average value is taken as the measured value.

  The average width of the projections of the fine relief structure is preferably 0.1 μm or more, more preferably 3 μm or more, and still more preferably 5 μm or more. In addition, the average width of the projections of the fine relief structure is preferably 500 μm or less, more preferably 400 μm or less, and still more preferably 300 μm or less. Here, as shown in FIG. 2, the width of the convex portion 10 of the fine concavo-convex structure is a distance represented by B. The average width is an average value when measuring the width of the convex portion 10 at 10 or more points.

  The average width of the projections of the fine relief structure can be measured by the following method. First, surface observation is performed at a magnification of 200 times using a microlaser microscope (measurement unit VK-X105 controller unit VK-X100 manufactured by KEYENCE CORPORATION), and an image is captured. Next, for the obtained image, the measurement area is set to 100 μm × 100 μm, and the diameter of the convex portion is measured using analysis software attached to the microlaser microscope. Specifically, each 10 points are measured, and the average value is taken as the measured value.

  The ten-point average roughness Rz of the outermost surface of the surface protective layer is preferably 1 μm or more and 30 μm or less. When the surface protective layer has a photocurable resin layer, the ten-point average roughness Rz of the outermost surface of the photocurable resin layer is preferably 1 μm to 30 μm. The ten-point average roughness Rz can be measured by the following method. First, using a microlaser microscope (measurement unit VK-X105 controller unit VK-X100 manufactured by KEYENCE CORPORATION), surface observation is performed at a magnification of 200 times, and an image is captured. Next, the surface roughness Rz of the obtained image is calculated using analysis software attached to a microlaser microscope with a measurement area of 100 μm × 100 μm.

  The fine concavo-convex structure as described above can be formed, for example, by applying a photocurable resin for forming a photocurable resin layer on a separator having a fine concavo-convex structure. By curing the photocurable resin after coating, a concavo-convex structure is formed in the photocurable resin layer along the fine concavo-convex structure of the separator. In addition, the case where the fine concavo-convex structure is formed in the above-described process can also be called a transfer process.

  The photocurable resin layer preferably contains a photocurable resin. Examples of the photocurable resin include acrylic ultraviolet curable resin, silicone resin, urethane resin, olefin resin, ester resin, epoxy resin and the like. Among them, acrylic resins, urethane resins and epoxy resins are preferably used, and acrylic resins are particularly preferably used.

  The acrylic resin is preferably acrylic acrylate, the urethane resin is urethane acrylate, and the epoxy resin is epoxy acrylate. Acrylic acrylate is a (meth) acrylate polymer having a (meth) acryloyl group in a side chain. The photocurable resin layer may or may not contain a solvent.

  The weight average molecular weight of the photocurable resin is more preferably 20,000 or more and 3,000,000 or less, still more preferably 30,000 or more and 1,000,000 or less, and particularly preferably 50,000 or more and 200,000 or less. By setting the weight average molecular weight of the photocurable resin within the above preferable range, the followability to an adherend can be further enhanced at the time of molding (TOM molding) under vacuum conditions or reduced pressure conditions, and a complicated shape It becomes possible to decorate the adherend of

  The photocurable resin layer is preferably an ultraviolet curable resin. In this case, it is preferable that the ultraviolet curable resin composition for forming a photocurable resin layer contains, for example, an ultraviolet curable resin, a photoinitiator, a leveling agent, a surfactant, a UV absorber, or Halce.

As a photoinitiator, a well-known thing and a commercial item can be used. As a commercial item, photoinitiators, such as Irgacure-184, Irgacure-651 (made by Ciba Specialty Chemicals, Inc.), Darocure-1173 (made by Merck & Co., Inc.), can be used, for example. Of these, Irgacure-184 is preferred. The content of the photoinitiator is preferably 1% by mass or more and 10% by mass or less, when the total mass is 100% by mass of the ultraviolet-curable resin composition.
As the leveling agent, for example, a fluorine-based leveling agent, a silicone-based leveling agent, or an acrylic-based leveling agent can be preferably used. Among these, silicone-based leveling agents and / or fluorine-based leveling agents are particularly preferred.

  The photocurable resin layer may further contain fine particles. As microparticles | fine-particles, an inorganic microparticle can be mentioned, for example, A metal oxide can be illustrated preferably. Moreover, you may also contain a pigment and dye as needed.

As pigments, inorganic pigments (alumina white, titanium oxide, zinc flower, black iron oxide, mica iron oxide, lead white, white carbon, molybdenum white, carbon black, lithium surge, lithopone, barite, cadmium red, cadmium mercury red, Bengal red, molybdenum red, red lead, yellow lead, cadmium yellow, barium yellow, strontium yellow, titanium yellow, titanium black, chromium oxide green, cobalt oxide, cobalt green, cobalt chromium green, ultramarine blue, bitumen blue, cobalt blue, cerulian blue Manganese purple, cobalt purple etc. and organic pigments (shellac, insoluble azo pigment, soluble azo pigment, condensed azo pigment, phthalocyanine blue, dyed lake etc), and also toluidine red, toluidine maroon, hanza ello, benzidine yellow, pyrazolone red etc Insoluble azo pigments, li Soluble azo pigments such as red leopard, pigment scarlet and permanent red 2B, derivatives such as alizarin, indanthrone and thioindigo maroon, phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, quinacridones such as quinacridone red and quinacridone magenta Pigments, perylene pigments such as perylene red and perylene scarlet, isoindolinone pigments such as isoindolinone yellow and isoindolinone orange, imidazolones pigments such as benzimidazolone yellow, benzimidazolone orange and benzimidazolone red , Pyranthrone pigments such as pyranthrone red and pyranthrone orange, thioindigo pigments, condensed azo pigments, diketopyrrolopyrrole pigments, Vance Ron yellow, acylamide yellow, quinophthalone yellow, nickel azo yellow, copper Azomechin'ero, Yellow, Perinone Orange, Anthrone Orange, Dianthraquinonyl Red, and other pigments such as dioxazine violet.
Moreover, as a dye, an acid dye, a basic dye, a direct dye, a reactive dye, a disperse dye, a pigment for food, etc. can be mentioned.

  Additives such as pigment dispersant, antifoaming agent, UV absorber, HALS, antioxidant, antistatic agent, antiwear agent, antiblocking agent, etc. are added to the photocurable resin layer as required. May be

(Base material layer)
The surface protective layer of the laminate for decoration molding of the present invention may have a base material layer. The base material layer is preferably stretchable so as to follow the molded product in the molding step.

  It is preferable that the material which comprises a base material layer is plastics, for example. Examples of the plastic include ABS resin (copolymer of acrylonitrile, butadiene and styrene), AS resin (copolymer of acrylonitrile and styrene), acrylic resin, polyethylene terephthalate, polybutylene terephthalate, nylon, polyacetal, polyphenylene oxide , Phenolic resin, urea resin, melamine resin, liquid crystal polymer, polytetrafluoroethylene, polyvinylidene fluoride, polysulfone, polyether sulfone, polyacetal, polyether ether ketone, polyphenylene sulfide, polyetherimide, polyamide imide, polyamide, polyethylene, polypropylene, Polystyrene, urethane resin and the like are preferable. Among these, ABS resin or acrylic resin is more preferable. The decorative layer may be a colored layer in which carbon (graphite) or the like is blended in these resins.

  It is preferable that the acrylic resin which comprises a base material layer is resin obtained by polymerizing the resin composition which has a monomer component which has a (meth) acryloyl group as a main component. It is preferable that the main component of a monomer component is (meth) acrylic acid ester, and it is preferable that it is methyl methacrylate. As a plastic film obtained using such a resin component, commercial items, such as acryprene HBA001P, HBS010P, and HBA002P, can also be used, for example. In addition, the base material layer may be obtained by extruding a resin component.

  The thickness of the base material layer is, for example, preferably 5 μm to 500 μm, more preferably 10 μm to 400 μm, preferably 20 μm to 300 μm, particularly preferably 30 μm to 250 μm. preferable. When the thickness of the base material layer is within the above-described preferable range, the balance between the formability and physical properties such as rigidity is further excellent.

  Moreover, the base material layer may contain the following components as needed. For example, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di (meth) acrylate, di (meth) acrylate ) Acrylic acid 1,9-nonanediol, diacrylic acid 1,6-hexanediol, poly (butylene glycol) di (meth) acrylate, neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, di- (meth) acrylate (Meth) acrylic acid tripropylene glycol, di (meth) acrylic acid polypropylene glycol, tri (meth) acrylic acid trimethylolpropane, tri (meth) acrylic acid pentaerythritol, tetra (meth) acrylic acid pentaerythritol etc. it can. Furthermore, a component having a carboxyl group, preferably, acrylic acid, methacrylic acid, maleic acid, crotonic acid, β-carboxyethyl acrylate, and / or a component having a hydroxyl group, preferably 2-hydroxyethyl (meth) acrylate, hydroxyloxypropyl (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, chloro-2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydrooctyl (meth) Mention may be made of acrylates and / or copolymerizable unsaturated components, preferably acrylamide, methacrylamide, vinyl acetate, (meth) acrylonitrile, macromers.

  The thickness of the base material layer is preferably 10 μm or more, more preferably 20 μm or more, and still more preferably 30 μm or more. The thickness of the substrate layer is preferably 500 μm or less, more preferably 400 μm or less, and still more preferably 300 μm or less.

(Adhesive layer)
The laminate for decoration molding of the present invention may further have an adhesive layer. A well-known adhesive can be utilized as an adhesive which comprises an adhesion layer. Examples of the pressure-sensitive adhesive include natural rubber-based pressure-sensitive adhesives, synthetic rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives and silicone-based pressure-sensitive adhesives. The pressure-sensitive adhesive may be any of solvent-based, solvent-free, emulsion-based and water-based. Among these, in view of transparency, weather resistance, durability, cost and the like, acrylic pressure-sensitive adhesives are preferable, and solvent-based acrylic pressure-sensitive adhesives are particularly preferable.

  Other assistants may be added to the adhesive as required. Other assistants include antioxidants, tackifiers, silane coupling agents, UV absorbers, light stabilizers such as hindered amine compounds, thickeners, pH adjusters, binders, crosslinking agents, adhesive particles, Defoamers, preservatives and fungicides, pigments, inorganic fillers, stabilizers, wetting agents, wetting agents and the like can be mentioned.

  As the tackifier, for example, aliphatic (C5) petroleum resin, aromatic (C9) petroleum resin, copolymerized (C5 / C9) petroleum resin, dicyclopentadiene (DCPD) petroleum resin, coumarone indene Resin, acrylic resin, styrene resin, rosin, rosin ester resin, terpene resin, aromatic modified terpene resin, terpene phenol resin, hydrogenated resin of these, and the like can be mentioned.

  The content of the tackifier in the adhesive is preferably 50 parts by mass or less with respect to 100 parts by mass of the adhesive.

The thickness of the adhesive layer is preferably 10 μm or more and 100 μm or less, and more preferably 20 μm or more and 80 μm or less. When the thickness of the adhesive layer is in the above range, it is possible to achieve both sufficient adhesiveness and economic efficiency.
The adhesive strength of the adhesive layer measured based on JIS Z 0237 is preferably 10 N / 25 mm or more and 100 N / 25 mm or less, and more preferably 25 N / 25 mm or more and 75 N / 25 mm or less.

  Moreover, you may contain the following component as needed for adhesive force improvement. For example, components having a carboxyl group, preferably acrylic acid, methacrylic acid, maleic acid, crotonic acid, crotonic acid, β-carboxyethyl acrylate, and / or components having a hydroxyl group, preferably 2-hydroxyethyl (meth) acrylate , Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, chloro-2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydro Mention may be made of octyl (meth) acrylate and / or copolymerizable unsaturated components, preferably acrylamide, methacrylamide, vinyl acetate, (meth) acrylonitrile, macromers.

(Separator layer)
The decorative laminate for decoration of the present invention may further have a separator layer. The separator layer is a layer that temporarily protects the adhesive layer until the laminate for decoration of the present invention is attached to the adherend. The separator layer is preferably one obtained by providing a release layer such as silicone on the surface of a resin film such as polyethylene terephthalate (PET), polyethylene, polypropylene or the like.

<Separator layer on the light curing resin layer side>
The laminate for decoration molding of the present invention may have a separator layer on the photocurable resin layer side. In the present invention, the separator layer on the photocurable resin layer side preferably has a concavo-convex structure, and preferably has a large number of fine recesses.

  When the separator layer has fine recesses, the average depth of the fine recesses is preferably 0.1 μm or more, more preferably 1 μm or more, and still more preferably 5 μm or more. The average depth of the fine recesses is preferably 50 μm or less, more preferably 40 μm or less, and still more preferably 30 μm or less. In addition. The average depth is an average value when ten or more recesses are measured. In addition, the average depth of the fine recessed part of a separator layer is the value measured by the method similar to the measurement of the average height of the convex part of a photocurable resin layer.

  When the separator layer has fine recesses, the average width of the fine recesses is preferably 0.1 μm or more, more preferably 3 μm or more, and still more preferably 5 μm or more. The average width of the fine recesses is preferably 500 μm or less, more preferably 400 μm or less, and still more preferably 300 μm or less. In addition, an average width is an average value at the time of measuring the width | variety of a recessed part ten or more. In addition, the average width | variety of the micro recessed part of a separator layer is the value measured by the method similar to the measurement of the average width of the convex part of a photocurable resin layer.

When the separator layer has fine recesses, the average cross-sectional area of the fine recesses is preferably 0.01 μm ² or more. The average cross-sectional area is more preferably 9 μm ² or more, further preferably 25 μm ² or more. Further, the average cross-sectional area of the fine recesses is preferably 250 mm ² or less, more preferably 160 mm ² or less, and still more preferably 90 mm ² or less.

  The separator layer on the light curing resin layer side is preferably made of resin. The resin is preferably a thermoplastic resin. Specifically, polyolefin, polyvinyl chloride, polyvinyl alcohol, polyester, polycarbonate, polystyrene or polyacrylonitrile can be mentioned. Among them, polyester is preferably used, and polyethylene terephthalate (PET) is particularly preferably used.

<Separator layer on the substrate layer side>
The laminate for decoration molding of the present invention may further have a separator layer on the substrate layer side. In addition, it is a case where the layered product for decoration molding of the present invention has an adhesion layer, and when an adhesion layer is laminated in order of a photocuring resin layer, a substrate layer, and an adhesion layer, exposure of an adhesion layer A separator layer on the substrate layer side is provided on the surface.

  The separator layer is preferably a layer made of resin and not containing a paper base. By using such a separator layer, foreign matter such as paper-derived dust does not get caught between the laminate and the molded body, and biting of the foreign matter can be effectively suppressed.

  It is preferable that the layer which comprises a separator layer is a resin layer, and it is preferable that the resin layer is comprised from the thermoplastic resin. Specifically, examples of the intermediate layer include polyolefin films, polyvinyl chloride films, polyvinyl alcohol films, polyester films, polycarbonate films, polystyrene films or polyacrylonitrile films. Among them, polyester films are preferably used, and polyethylene terephthalate (PET) films are particularly preferably used.

The release agent layer contains a release agent. As the release agent, for example, a general-purpose addition type or condensation type silicone release agent is used. In particular, an addition-type silicone release agent having high reactivity is preferably used. Specific examples of the silicone-based release agent include BY24-162 and SD-7234 manufactured by Toray Dow Corning Silicone Co., Ltd., KS-3600 manufactured by Shin-Etsu Chemical Co., Ltd., KS-774, X62-2600 and the like. Can be mentioned. In addition, a silicone resin which is an organic silicon compound having a SiO ₂ unit and a (CH ₃ ) ₃ SiO _1/2 unit or a CH ₂ CHCH (CH ₃ ) SiO _1/2 unit in a silicone-based release agent preferable. Specific examples of the silicone resin include BY24-843, SD-7292, SHR-1404, etc. manufactured by Toray Dow Corning Silicone Co., Ltd., KS-3800, X92-183, etc. manufactured by Shin-Etsu Chemical Co., Ltd.

  Auxiliary additives such as a catalyst and an adhesion improver can be added to the release agent layer. Preferred examples of the catalyst include platinum-based and tin-based catalysts. Further, as the adhesion improver, any material can be used particularly as long as the adhesion is improved, and preferably a silane coupling agent can be mentioned.

(Method of producing laminate for decorative molding)
The step of producing the decorative molding laminate of the present invention includes the step of forming a surface protective layer having a photocurable resin on the outermost surface, and in the step, a light beam (ultraviolet rays or electrons) is formed on the outermost surface of the surface protective layer. It is preferable to include the step of irradiating a line). In addition, when the surface protective layer is a layer having a photocurable resin layer and a base material layer, after laminating the photocurable resin layer and the base material layer, a step of irradiating a light beam (ultraviolet light or electron beam) is included. Is preferred. Furthermore, in the manufacturing process of the laminate for decorative molding, a step of applying a coating liquid for forming a photocurable resin layer on the separator layer on the photocurable resin layer side, and laminating a base material layer on the photocurable resin layer It is preferable to have a process. Alternatively, the step of coating the photocurable resin layer forming solution on the separator layer on the photocurable resin layer side may be simultaneous with the step of laminating the substrate. The step of irradiating a light beam (ultraviolet light or electron beam) is preferably provided after the step of laminating the base material layer, and in the step of irradiating a light beam (ultraviolet light or electron beam), the separator layer side of the photocurable resin layer side It is preferable to irradiate from.

In the step of irradiating a light beam (ultraviolet light), it is preferable to irradiate ultraviolet light with a wavelength of 200 nm or more and 400 nm or less so that the illuminance is 50 mW / cm ² or more. The illuminance is preferably at 70 mW / cm ² or more, and more preferably 100 mW / cm ² or more. Further, the illuminance is preferably at 3000 mW / cm ² or less, more preferably 1000 mW / cm ² or less. The integrated light amount is preferably 100 mJ / cm ² or more, and more preferably 300 mJ / cm ² or more. Further, the integrated light quantity is preferably at 10000 mJ / cm ² or less, more preferably 3000 mJ / cm ² or less. As an irradiator which performs such irradiation, it is preferable to use at least one selected from a high pressure mercury ultraviolet irradiator, a metal halide ultraviolet irradiator and an electrodeless ultraviolet irradiator. By making irradiation conditions into the said range, the component amount of the monomer component which comprises a photocurable resin layer can be reduced. Moreover, it can suppress that a photocurable resin layer yellows with an ultraviolet-ray by making irradiation conditions into the said range.

(Molding under vacuum or reduced pressure conditions (TOM molding))
It is preferable that the laminate for decoration molding of the present invention is used for applications of decorating a molded body under vacuum conditions or reduced pressure conditions. Since the laminate for decorative molding of the present invention has sufficient stretchability and high haze value, and is a laminate for decorative molding with little decrease in haze even after stretching, it is possible to produce a decorative molded product It is possible to obtain a decorated molded body which can enhance the properties and is excellent in design.

  In the present specification, molding under vacuum conditions or reduced pressure conditions is what is called so-called TOM molding. The TOM forming method includes the steps of laminating the decorative forming laminate on a formed body under vacuum conditions or reduced pressure conditions, and pressing the decorative forming laminate on the formed body by pressure difference. The decorative molding laminate used herein has the above-described configuration, and includes a surface protective layer having a photocurable resin on the outermost surface. The haze of the surface protective layer is 10% or more, and the breaking elongation at 120 ° C. in the first direction of the laminate for decorative formation is 50% or more, and in the second direction orthogonal to the first direction The breaking elongation at 120 ° C. is 50% or more. In addition, the haze of the surface protective layer before stretching the decorative molding laminate is P, and the surface of the decorative protective laminate is stretched 50% in the first direction or the second direction. When the haze is Q, the haze reduction rate represented by (PQ / P) × 100 is 40% or less.

  In the present specification, molding under vacuum conditions or reduced pressure conditions does not include a method for bringing a laminate into close contact with a molded body by using a molded body provided with vacuum holes. Specifically, molding under vacuum conditions or reduced pressure conditions can be carried out using the "vacuum molding apparatus" described in Japanese Patent No. 3733564.

  Moreover, in the method for producing a decorated molding according to the present invention, the step of heating the surface of the decorating-forming laminate to 100 ° C. or more and 180 ° C. or less after the step of pressing the decorating-forming laminate onto the molding. Is preferred. In this case, it is preferable to use an infrared heater for heating.

(Decorated molded body)
The present invention also relates to a decorated molded body including the above-described decorative molding laminate and the molded body decorated with the decorative molding laminate. The decorative molded body is obtained by sticking a decorative molding laminate on a part or the entire surface of the molded body. That is, in the decorated molded body, the photocurable resin layer is laminated via the base material layer.

  FIG. 3: is sectional drawing explaining the structure of the decorating molded body 100. As shown in FIG. FIG. 3: has shown a mode that the molded object 50 which has a recessed part in the surface was decorated with the layered product 1 for decoration molding. As shown in FIG. 3, in forming under vacuum conditions or reduced pressure conditions, even if the formed body 50 is not provided with vacuum holes, it is possible to cover and mold the reverse taper portion and the end winding portion. Moreover, it can be decorated regardless of the material of the product. Thereby, it can decorate also about the molded object surface which has complicated three-dimensional unevenness, and it can obtain the decorative molded object 100 with high designability.

  Examples of the molded body 50 include metal materials such as ED steel plate, Mg alloy, stainless steel (SUS), and aluminum alloy, and resin molded bodies, but resin molded bodies are preferable. For example, ABS resin (copolymer of acrylonitrile, butadiene and styrene), AS resin (copolymer of acrylonitrile and styrene), AAS resin (copolymer of acrylonitrile, acrylic and styrene), acrylic resin, polyethylene Terephthalate, polybutylene terephthalate, nylon, polyacetal, polyphenylene oxide, phenol resin, urea resin, melamine resin, liquid crystal polymer, polytetrafluoroethylene, polyvinylidene fluoride, polysulfone, polyether sulfone, polyacetal, polyether ether ketone, polyphenylene sulfide , Polyetherimide, polyamide imide, polycarbonate, polyethylene, polypropylene, polystyrene, urethane resin, vinylidene chloride resin, salt It can be preferably used vinyl resin. These resins may be blended. For example, polycarbonate-containing resins can be preferably exemplified. As polycarbonate containing resin, resin (PC · PBT) in which polycarbonate and polybutylene terephthalate are blended, resin (PC · ABS) in which polycarbonate and ABS resin are blended, resin (PC · PET) in which polycarbonate and PET are blended Etc. can be particularly preferably used. In addition, as the polyolefin resin, polypropylene (PP) can be particularly preferably used.

  The decorative molded body obtained by the present invention is, for example, an automobile member (for example, a component such as a body, a bumper, a spoiler, a mirror, a wheel, an interior material, etc. and made of various materials), a member for two-wheeled vehicles, railway vehicles It can be used as a member. In addition, the decorated molded body can also be used as an electronic device such as a home appliance, or a building material such as furniture or a building material. Furthermore, the decorated molding may also be used for road materials (eg, traffic signs, sound barriers, etc.), tunnel materials (eg, side wall plates, etc.), musical instruments, containers, office supplies, sports goods, toys, etc. it can.

  The features of the present invention will be more specifically described below with reference to examples and comparative examples. The materials, amounts used, proportions, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as limited by the specific examples shown below.

Example 1
(Laminated body 1)
The release agent layer side of a separator having many recesses with an average depth of 3 μm in the recesses, an average width of 15 μm in the recesses, and an average cross-sectional area of 225 μm ² in the release agent layer (Acryprene HBA 001 P, pencil hardness An electron radiation curable resin 1 (UV1) was applied (wet lamination) to a thickness of 8 μm between the film and the film (2H, thickness 125 μm). This thickness is the total thickness from the top to the opposite side. Thereafter, electron radiation curable resin 1 was cured by irradiating electron radiation having a wavelength of 365 nm from the separator side with a high pressure mercury lamp so that the illuminance was 100 mW / cm ² and the integrated light quantity was 500 mJ / cm ² . Thus, a photocurable resin layer was obtained. Thereafter, the separator was peeled off to obtain a laminate 1 including a surface protective layer in which the base material layer and the photocurable resin layer were laminated in this order. The haze of the laminate 1 and the ten-point average roughness Rz of the outermost surface of the laminate are as shown in Table 1.

  As electron radiation curable resin composition 1 (UV1), Z-975L (manufactured by Aika Kogyo Co., Ltd.) was used.

Comparative Example 1
(Laminated body 2)
An acrylic film (manufactured by Mitsubishi Rayon Co., Ltd., Acriprene HBA 001 P, pencil hardness 2 H, thickness 125 μm) was used as a substrate. An electron radiation curable resin 2 (UV2) was coated on one surface side of this substrate using a bar coater so that the thickness after curing was 5 μm. Next, the substrate and the electron radiation curable resin composition 2 were placed in a hot air oven at 100 ° C., and the coated electron radiation curable resin composition 2 was dried for 1 minute. Thereafter, electron radiation having a wavelength of 365 nm is irradiated with a high pressure mercury lamp so that the illuminance is 100 mW / cm ² and the integrated light quantity is 500 mJ / cm ^2, and the electron radiation curable resin 2 is cured to cure the photocurable resin layer. Formed. Thus, a laminate 2 in which the base material layer and the photocurable resin layer were laminated in this order was obtained. The haze of the laminate 2 and the ten-point average roughness Rz of the outermost surface of the laminate are as shown in Table 1.

  In addition, as electron radiation curable resin composition 2 (UV2), 30 parts by mass of acrylic acrylate (weight average molecular weight: 78000), 30 parts by mass of toluene, 8.5 parts by mass of ethyl acetate, and a photoinitiator A mixture of 1 part by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals Inc., Irgacure 184) and 30 parts by mass of inorganic particles having a primary average particle diameter of 500 nm was used.

Comparative Example 2
(Laminated body 3)
An acrylic film (manufactured by Mitsubishi Rayon Co., Ltd., Acriprene HBA 001 P, pencil hardness 2 H, thickness 125 μm) was used as a substrate. An electron radiation curable resin 3 (UV3) was coated on one side of this substrate using a bar coater so that the thickness after curing was 5 μm. Next, the base material and the electron radiation curable resin composition 3 were placed in a hot air oven at 100 ° C., and the coated electron radiation curable resin composition 3 was dried for 1 minute. Thereafter, electron radiation having a wavelength of 365 nm is irradiated with a high pressure mercury lamp so that the illuminance is 100 mW / cm ² and the integrated light quantity is 500 mJ / cm ^2, and the electron radiation curable resin 3 is cured to cure the photocurable resin layer. Formed. Thus, a laminate 3 in which the base material layer and the photocurable resin layer were laminated in this order was obtained. The haze of the laminate 3 and the ten-point average roughness Rz of the outermost surface of the laminate are as shown in Table 1.

  In addition, as electron radiation curable resin composition 3 (UV3), 30 parts by mass of acrylic acrylate (weight average molecular weight: 78000), 30 parts by mass of toluene, 8.5 parts by mass of ethyl acetate, and a photoinitiator A mixture of 1 part by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals Inc., Irgacure 184) and 30 parts by mass of inorganic fine particles having a primary average particle diameter of 40 nm was used.

Comparative Example 3
(Laminated body 4)
An acrylic film (manufactured by Mitsubishi Rayon Co., Ltd., Acriprene HBA 001 P, pencil hardness 2 H, thickness 125 μm) was used as a substrate. On one side of this substrate, electron radiation curable resin 4 (UV4) substantially free of particles was applied using a bar coater so that the thickness after curing was 5 μm. Next, the substrate and the electron radiation curable resin composition 4 were placed in a hot air oven at 100 ° C., and the coated electron radiation curable resin composition 4 was dried for 1 minute. Thereafter, electron radiation having a wavelength of 365 nm is irradiated with a high pressure mercury lamp so that the illuminance is 100 mW / cm ² and the integrated light quantity is 500 mJ / cm ^2, and the electron radiation curable resin 5 is cured to cure the photocurable resin layer. Formed. Thus, a laminate 4 in which the base material layer and the photocurable resin layer were laminated in this order was obtained. The haze of the laminate 4 was measured.

  In addition, as electron radiation curable resin composition 4 (UV4), it is 30 parts by mass of acrylic acrylate (weight average molecular weight: 78000), 60 parts by mass of toluene, 8.5 parts by mass of ethyl acetate, and a photoinitiator. A mixture of 1 part by mass of 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Specialty Chemicals Inc., Irgacure 184) was used.

Comparative Example 4
(Laminated body 5)
The release agent layer side of a separator having irregularities of 0.5 μm in average depth and 0.5 μm in average depth of depressions on the surface of release agent layer and acrylic film (Acryprene HBA001P, manufactured by Mitsubishi Rayon Co., pencil hardness is 2H, thickness 125 μm) In the meantime, electron radiation curable resin 1 (UV1) was applied (wet lamination) so as to have a thickness of 8 .mu.m. The thickness of the electron radiation curable resin 1 is the total thickness including the concave and the convex. Thereafter, electron radiation with a wavelength of 365 nm is irradiated from the separator side with a high pressure mercury lamp so that the illuminance is 100 mW / cm ² and the integrated light quantity is 500 mJ / cm ^2, and the electron radiation curable resin 1 is cured. A cured resin layer was formed. Thereafter, the separator was peeled off to obtain a laminate 5 comprising a surface protective layer in which the base material layer and the photocurable resin layer were laminated in this order. The haze of the laminate 5 and the ten-point average roughness Rz of the outermost surface of the laminate are as shown in Table 1.

  As electron radiation curable resin composition 1 (UV1), Z-975L (manufactured by Aika Kogyo Co., Ltd.) was used.

(Evaluation)
(Haze of surface protective layer)
According to JIS K 7136, the haze of the laminate 1 of Example 1, the laminate 2 of Comparative Example 1, the laminate 3 of Comparative Example 2, the laminate 4 of Comparative Example 3 and the laminate 5 of Comparative Example 4 is The color was measured using a haze meter "NDH-5000" manufactured by Color Industrial Co., Ltd.

(Surface unevenness)
The surface unevenness of the laminate 1 of Example 1, the laminate 2 of Comparative Example 1, the laminate 3 of Comparative Example 2, the laminate 4 of Comparative Example 3 and the laminate 5 of Comparative Example 4 is visually observed, and the surface feeling is confirmed.
○: The surface reflection is suppressed.
Δ: The surface reflection is slightly suppressed.
X: The surface reflection can not be suppressed.

(10-point average roughness Rz)
The top surface of the laminate 1 of Example 1, the laminate 2 of Comparative Example 1, the laminate 3 of Comparative Example 2, the laminate 4 of Comparative Example 3 and the laminate 5 of Comparative Example 4 is subjected to a microlaser microscope Surface observation was performed at a magnification of 200 times using a measurement unit VK-X105 manufactured by KEYENCE and a controller unit VK-X100), and an image was captured. With respect to the obtained image, a ten-point average roughness Rz was measured using analysis software attached to a microlaser microscope with a measurement area of 100 μm × 100 μm.

(Formability evaluation test)
For the laminate 1 of Example 1, the laminate 2 of Comparative Example 1, the laminate 3 of Comparative Example 2, the laminate 4 of Comparative Example 3 and the laminate 5 of Comparative Example 4 Using an NGF molding machine, decorative molding (molding temperature: 120 ° C.) was performed under the condition that the draw ratio in the longitudinal direction and width direction of the laminate is 50% or more, to obtain a decorative molded body. As the adherend, a rainproof incoming wire cover (part number: WP9171 [manufactured by Panasonic Corporation]) was used. The formability of the above-mentioned decorated molded body was evaluated according to the following evaluation criteria.
○: No breakage of the laminate was observed at the maximum stretched portion of the laminate (stretching magnification of 50% or more in the laminate longitudinal direction and width direction).
Fair: Although breakage of the laminate was partially observed at the maximum stretching part of the laminate (stretching magnification of 50% or more in the longitudinal direction and width direction of the laminate), there is no problem in practical use.
X: Breaking of the laminate was observed at the maximum stretched portion of the laminate (stretching magnification of 50% or more in the laminate longitudinal direction and width direction).

(Breaking elongation)
A laminate 1 of Example 1, a laminate 2 of Comparative Example 1, a laminate 3 of Comparative Example 2, a laminate 4 of Comparative Example 3 and a laminate 5 of Comparative Example 4 are formed into a TOM forming machine (manufactured by Cloth Application Vacuum Co., Ltd.) Using an NGF molding machine, molding is performed using a jig that can measure the stretching ratio in the longitudinal direction or width direction of the laminate for decoration molding from 10 to 100% in 10% increments at 120 ° C. , To obtain a molded body. And the draw ratio before breakage arises in a part of surface protective layer was made into the breaking elongation of the layered product for decoration formation. Those with no breakage even at a draw ratio of 100% were evaluated as ">100". For example, the test was carried out while changing the draw ratio by 10% each time, and when breakage was first seen on the surface of the molded product when drawing 90%, the breaking elongation was made 80%.

(Haze reduction rate)
After stretching the laminate 1 of Example 1, the laminate 2 of Comparative Example 1, the laminate 3 of Comparative Example 2, the laminate 4 of Comparative Example 3 and the laminate 5 of Comparative Example 4 in one direction by 50%, respectively The haze was measured according to JIS K 7136 using a haze meter "NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd.
Thereafter, the haze reduction rate was calculated by the following formula from the haze P before stretching and the haze Q after stretching.
Haze reduction rate (%) = (P−Q / P) × 100

(Total light transmittance)
The total light transmittance of the laminate 1 of Example 1, the laminate 2 of Comparative Example 1, the laminate 3 of Comparative Example 2, the laminate 4 of Comparative Example 3 and the laminate 5 of Comparative Example 4 in accordance with JIS K 7136 It was measured using a haze meter "NDH-5000" manufactured by Nippon Denshoku Kogyo Co., Ltd. Furthermore, the laminate 1 of Example 1, the laminate 2 of Comparative Example 1, the laminate 3 of Comparative Example 2, the laminate 4 of Comparative Example 3 and the laminate 5 of Comparative Example 4 are each stretched by 50% in one direction. The total light transmittance after the measurement was also measured by the same method.

  The laminate obtained in the examples had a high haze before stretching and was excellent in decoration. Moreover, it turns out that the layered product obtained by the Example has high breaking elongation, and the change rate of the haze before and behind extending | stretching is suppressed low.

Reference Signs List 1 laminate for decorative molding 2 surface protective layer 3 base material layer 5 light curing resin layer 10 convex portion 50 molded body 100 decorative molded body

Claims (8)

A laminate for decorative molding, comprising a surface protection layer having a photocurable resin on the outermost surface,
The haze of the surface protective layer is 10% or more.
The outermost surface of the surface protective layer has a microrelief structure, and the average height of the projections of the microrelief structure is 0.1 μm to 50 μm,
The breaking elongation at 120 ° C. in the first direction of the laminate for decorative formation is greater than 50%, and the breaking elongation at 120 ° C. in the second direction orthogonal to the first direction is greater than 50% ,
The haze of the surface protective layer before stretching the decorative molding laminate is P, and the haze of the surface protective layer after stretching the decorative molding laminate in the first direction or the second direction by 50% The haze reduction rate represented by (PQ / P) x 100 is 40% or less, when it is set as Q, The laminate for decorating shaping | molding characterized by the above-mentioned. The average width of the convex portion of the fine unevenness is at 0.1μm or 500μm or less, the decorative molding according to claim 1 ten-point average roughness Rz of the outermost surface is 1μm or more 30μm or less of the surface protective layer Laminates. Decorative molding laminate according to claim 1 or 2 further comprising an adhesive layer. The laminate for decoration molding according to any one of claims 1 to 3 , which is used for decoration molding under vacuum conditions or reduced pressure conditions. The laminate for decorative molding according to any one of claims 1 to 4 , which is used to decorate an automobile member, an electronic device or a building material. The laminate for decorative formation according to any one of claims 1 to 5 , wherein a draw ratio in at least one direction selected from the first direction and the second direction is 1.5 or more. A decorative formed body comprising the laminate for decorative formation according to any one of claims 1 to 6 and a molded body decorated with the laminate for decorative formation. Laminating the decorative molding laminate on a compact under vacuum or reduced pressure conditions;
And a step of pressing the laminate for decorative formation onto a molded body by pressure difference, which is a method for producing a decorative molded body,
The decorative molding laminate includes a surface protective layer having a photocurable resin on the outermost surface,
The haze of the surface protective layer is 10% or more.
The outermost surface of the surface protective layer has a microrelief structure, and the average height of the projections of the microrelief structure is 0.1 μm to 50 μm,
The breaking elongation at 120 ° C. in the first direction of the laminate for decorative formation is greater than 50%, and the breaking elongation at 120 ° C. in the second direction orthogonal to the first direction is greater than 50% ,
The haze of the surface protective layer before stretching the decorative molding laminate is P, and the haze of the surface protective layer after stretching the decorative molding laminate in the first direction or the second direction by 50% The manufacturing method of the decorating molded object whose haze decreasing rate represented by (PQ / P) x100 is 40% or less, when setting it as Q. FIG.

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