JP2017144683A - Laminate for decorative molding, decorative molding, and method for producing decorative molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate for decorative molding which can exhibit sufficient stretchability and shows little reduction in a haze before and after stretching.SOLUTION: There is provided a laminate 1 for decorative molding including a surface protective layer 2 having a photocurable resin on the outermost surface, where a haze of the surface protective layer 2 is 10% or more, elongation at break at 120°C in a first direction of the laminate 1 for decorative molding is more than 50%, elongation at break at 120°C in a second direction orthogonal to the first direction is more than 50%, and when the haze of the surface protective layer 2 before the laminate 1 for decorative molding is stretched is represented by P and the haze of the surface protective layer after the laminate 1 for decorative molding has been stretched in the first direction or the second direction by 50% is represented by Q, a haze reduction rate represented by (P-Q/P)×100 is 40% or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative molded laminate, a decorative molded body, and a method for manufacturing a decorative molded body.

  Conventionally, when protecting the surface of automobile interior and exterior parts, parts for home appliances, parts for building materials, etc. or decorating (decorating), after processing the molded body by injection molding or vacuum molding, spray the surface of the molded body Applying paint by painting, etc., drying and heat curing were performed. However, in addition to the problem that the discharge of volatile organic solvents worsens the working environment, such painting requires work processes and production facilities for each molded part, and requires repeated coating of paint. There was a problem that the yield of paint was poor and the productivity was low.

  In recent years, resin molded bodies have been used as molded bodies for the purpose of reducing the weight of automobile interior and exterior parts, household appliance parts, building material parts, and the like. In many cases, spray coating is not suitable for decoration (decoration) of a resin molded body, and various methods have been developed to decorate the surface of the resin molded body. Above all, the method of obtaining the decorative molded body by decorating the outermost surface of the molded body with a decorative film has higher design freedom and productivity than the method of applying or printing on the surface using a paint or the like. Has the advantage of being excellent. Moreover, since the decorating method using a decorating film can also decorate the molded object surface which has a three-dimensional unevenness | corrugation, it is used for various uses.

  As a decorative film, a film having only a decorative layer and a film having a decorative 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 said that the decoration film excellent in the feeling of depth and sharpness is obtained by performing the fine embossing on the surface of a hard-coat layer.

  By the way, as a method of decorating the surface of a molded article having three-dimensional irregularities with a decorative film, there is a three-dimensional covering molding (TOM molding) method (Patent Document 3). TOM molding is a molding method under vacuum conditions or reduced pressure conditions, and is a method in which a decorative film and a molded body are pressure-bonded to obtain a decorative molded body. In TOM molding, it is possible to decorate regardless of the material of the molded body. Moreover, a reverse taper part and a terminal winding part can be coat-molded, without providing a vacuum hole in a molded object.

  As a decorative film used for TOM molding, there are a film having only a decorative layer, and a laminated film (laminate) having a decorative layer and an adhesive layer. When obtaining a decorative molded body using a film having only a decorative layer, a method of melting the film itself and bringing the molten film and the molded body into close contact with each other is used. Moreover, when using the laminated | multilayer film which has a decoration layer and an adhesion layer, it is not necessary to fuse a decoration layer, but a laminated film and a molded object are closely_contact | adhered using adhesive force, such as an adhesion layer.

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

  As described above, various decorative films have been developed. However, Patent Documents 1 and 2 do not sufficiently study the use of the decorative film for TOM molding. When the present inventors perform TOM molding using a decorative film as described in Patent Document 1, are cracks generated at the positions where fine particles exist, and does not exhibit sufficient stretchability along the molded body? Or it turned out that it is a thing which does not exhibit sufficient decorating performance (namely, haze value is low). Moreover, the decorating film described in Patent Document 2 is not sufficiently stretchable, leaving room for improvement when it is used for TOM molding.

  Accordingly, the present inventors provide a decorative film (decorative molding laminate) that can exhibit sufficient stretchability and has little decrease in haze before and after stretching in order to solve such problems of the prior art. We proceeded with the study for the purpose of doing this.

As a result of intensive studies to solve the above problems, the present inventors, in a decorative molded laminate having a specific surface protective layer, have a haze of the surface protective layer as a predetermined condition and are decorated. It has been found that by setting the breaking elongation of the molding laminate to a specific condition, a decorative molding laminate can be obtained that has sufficient stretchability and can maintain a high haze value even after stretching. It was.
Specifically, the present invention has the following configuration.

[1] A decorative molding laminate including a surface protective layer having a photocurable resin on the outermost surface, wherein the haze of the surface protective layer is 10% or more, and the decorative molding laminate has a first direction. Surface protection before stretching the laminate for decorative molding, with a break elongation at 120 ° C. of greater than 50% and a break elongation at 120 ° C. in the second direction orthogonal to the first direction of greater than 50%. When the haze of the layer is P and the haze of the surface protective layer after extending the decorative molding laminate 50% in the first direction or the second direction is Q, (PQ / P) × 100 A laminate for decorative molding, characterized in that the haze reduction rate represented by the formula is 40% or less.
[2] The decorative molding laminate according to [1], wherein the outermost surface of the surface protective layer has a fine uneven structure.
[3] The laminate for decorative molding according to [2], wherein the average height of the convex portions of the fine concavo-convex structure is 0.1 μm or more and 50 μm or less.
[4] The average width of the convex portions of the fine concavo-convex structure is from 0.1 μm to 500 μm, and the ten-point average roughness Rz of the outermost surface of the surface protective layer is from 1 μm to 30 μm. The laminate for decorative molding according to any one of the above.
[5] The laminate for decorative molding according to any one of [1] to [4], further including an adhesive layer.
[6] The laminate for decorative molding according to any one of [1] to [5], which is used for decorative molding under vacuum conditions or reduced pressure conditions.
[7] The laminate for decorative molding according to any one of [1] to [6], which is used for decorating an automobile member, an electronic device, or a building material.
[8] The decorative molded laminate according to any one of [1] to [7], wherein a draw ratio in at least one direction selected from the first direction and the second direction is 1.5 times or more.
[9] A decorative molded body comprising the decorative molded laminate according to any one of [1] to [8] and a molded product decorated with the decorative molded laminate.
[10] Decorative molding including a step of laminating a decorative molding laminate on a molded body under vacuum or reduced pressure conditions, and a step of pressure-bonding the decorative molding laminate to the molded body by a pressure difference The laminate for decorative molding includes a surface protective layer having a photo-curing resin on the outermost surface, and the haze of the surface protective layer is 10% or more. 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 perpendicular to the first direction is greater than 50%, and the decorative molding laminate is stretched. When the haze of the front surface protective layer is P, and the haze of the surface protective layer after extending the decorative molded laminate 50% in the first direction or the second direction is Q, (PQ / P) Method for producing a decorative molded body having a haze reduction ratio represented by x100 of 40% or less .

  ADVANTAGE OF THE INVENTION According to this invention, it is a laminated body for decorating shaping | molding which has sufficient extending | stretching property and a high haze value, Comprising: Even after extending | stretching, the laminated body for decorative shaping | molding which has a high haze value can be obtained. If the laminated body for decorative molding of this invention is used, the productivity of a decorative molded body can be improved and the decorative molded body excellent in the designability can be produced.

FIG. 1 is a cross-sectional view showing an example of the configuration of the decorative molding laminate of the present invention. FIG. 2 is an enlarged cross-sectional view illustrating the structure of the fine convex portion of the surface protective layer. FIG. 3 is a cross-sectional view illustrating the configuration of the decorative molded body of the present invention.

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

(Delay for decorative molding)
The present invention relates to a decorative molded laminate including 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 molding is larger than 50%, and the breaking elongation at 120 ° C. in the second direction orthogonal to the first direction is larger than 50%. Moreover, the haze of the surface protective layer before extending | stretching the laminated body for decorative shaping | molding is set to P, and the haze of the surface protective layer after extending | stretching the laminated body for decorative shaping | molding 50% in a 1st direction or a 2nd direction. When Q is Q, the haze reduction ratio represented by (PQ / P) × 100 is 40% or less.

The surface protective layer of the laminate for decorative molding of the present invention has a photocurable resin, and this photocurable resin is present on the outermost surface. When the photo-curing resin is disposed on the outermost surface, it has a function of physically protecting other layers such as an adhesive layer and a molded body as an adherend. That is, since the surface protective layer of the present invention is a layer having a photocurable resin, it has a function of protecting the surface of a molded body or the like.
In addition, the surface protective layer has a function of scattering transmitted light at a predetermined ratio or higher (haze value equal to or higher than a predetermined value) 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 achieve a similar function with a single layer. It may be. The surface protective layer formed by laminating a plurality of layers can be formed, for example, by coating a photocurable resin composition on one side of the substrate. That is, the surface protective layer may be composed of a base material and a photo-curing resin layer.

Since the laminate for decorative molding of the present invention has the above configuration, it has sufficient stretchability and high haze value. The laminate having high stretchability is preferably used for decorative molding under vacuum conditions or reduced pressure conditions. Examples of the molding method under vacuum or reduced pressure include a TOM molding (three-dimensional coating molding) method, and the decorative molding laminate of the present invention is particularly preferably used in a molding method such as TOM molding. .
In addition, the decorative molded laminate of the present invention has a surface protective layer that retains a high haze value even after stretching, and is characterized in that there is little decrease in haze before and after stretching. Usually, the laminate for decorative molding is stretched at the time of decorating and stuck to the surface of the adherend, so that the laminate with little decrease in haze before and after stretching is suitable as a decorative film and molded with excellent design. The body can be shaped.

FIG. 1 is a cross-sectional view showing an example of the configuration of the decorative molding laminate of the present invention. As shown in FIG. 1, the decorative molded laminate 1 of the present invention includes a surface protective layer 2 or consists of a surface protective layer 2. The surface protective layer 2 preferably has a base material layer 3 and a photocurable resin layer 5. In this case, it bonds so that the base material layer 3 side may come to the surface side of the molded object which is a to-be-adhered object.
In the following, although the surface protective layer 2 of the laminate 1 for decorative molding of the present invention will be described mainly with respect to a preferable form having the base material layer 3 and the photo-curing resin layer 5, it is used for decorative molding of the present invention. The surface protective layer 2 of the laminated body does not necessarily have the base material layer 3, and the photocurable resin layer 5 may include the function of the base material layer 3. Further, the surface protective layer 2 may be only the base material layer 3.

  When the surface protective layer 2 of the laminate for decorative molding 1 of the present invention has the base material layer 3 and the photocurable resin layer 5, there are other layers 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. Further, another layer may be provided on one surface of the base material layer 3 and on the surface opposite to the surface on which the photocurable resin layer 5 is laminated. For example, an adhesive layer may be provided, and the decorative molding laminate may be attached to a molded body that is an adherend through such an adhesive layer. Alternatively, the surface protective layer 2 may be attached (for example, heat-sealed) to the surface of the molded body that is the adherend without using an adhesive layer.

The elongation at break at 120 ° C. in the first direction of the decorative molded laminate is preferably 50% or more, preferably 65% or more, more preferably 80% or more, and 100% or more. More preferably it is. Further, the elongation at break at 120 ° C. in the second direction orthogonal to the first direction of the decorative molding laminate is preferably 50% or more, preferably 65% or more, and 80% or more. Is more preferable and 100% or more is even more preferable. Here, the first direction of the decorative molding laminate is preferably the longitudinal direction of the decorative molding laminate. The longitudinal direction is a flow direction when the surface protective layer is formed, and is also referred to as an MD direction (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 (Crcs Machine Direction). Thus, when the flow direction of the decorative molded laminate is known, the first direction is the flow direction, but when the decorative molded laminate flow direction is not known, the decorative molded laminate Any one direction in the plane direction can be set 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 elongation in the first direction and the second direction is large, and since it has such breaking elongation, the shape of the molded body that is the object to be adhered at the time of decorative molding It has a characteristic that it is easy to stretch following the above.

  The breaking elongation at 120 ° C. in the first direction and the second direction of the laminate for decorative molding can be measured by the following methods, respectively. First, using a TOM molding machine (manufactured by Fuse Vacuum Co., Ltd., NGF molding machine), the stretching ratio in the first direction or the second direction of the laminate for decorative molding at 120 ° C. is from 10 to 100%. Using a jig capable of measuring in 10% increments, molding is performed to obtain a molded body. And let the draw ratio before a fracture | rupture arises in a part of surface protective layer be the breaking elongation of the laminated body for decorating shaping | molding. That is, each test is performed by changing the stretch ratio greatly by 10%, and −10% of the stretch ratio at which breakage is first observed in the surface protective layer (molded body surface) is defined as the breaking elongation. For example, each test is performed by changing the stretch ratio greatly by 10%, and when the surface protective layer (molded body surface) is first broken when stretched by 90%, the elongation at break is set to 80%.

  The laminate for decorative molding has sufficient stretchability. The decorative laminate has sufficient stretchability at the maximum stretched portion of the laminate for decorative molding (stretch rate of 50% or more in the laminate longitudinal direction and width direction). The state where no destruction is seen.

  The haze before stretching of the surface protective layer is preferably 10% or more, more preferably 15% or more, and further 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 ratio represented by (PQ / P) × 100 is 40% or less. The value of the haze reduction rate is preferably 35% or less, more preferably 30% or less, further preferably 20% or less, and most preferably 15% or less. Thus, the present invention is characterized by a low haze reduction rate and has a high haze value even after stretching. By setting the haze reduction rate within the above range, excellent decorating properties can be exhibited.

  In addition, in this specification, the state which extended | stretched the laminated body for decoration shaping | molding 50% in the 1st direction or the 2nd direction is the extending | stretching of the 1st direction or 2nd direction of the laminated body for decoration shaping | molding. It is synonymous with a magnification of 1.5.

  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 further preferably 90% or more. Moreover, it is preferable that the total light transmittance of the surface protective layer after extending | stretching the laminated body for decorative shaping | molding 50% to a 1st direction or a 2nd direction is 70% or more, and is 80% or more. Is more preferable, and it is still more preferable that it is 90% or more.

  The haze and total light transmittance of the surface protective layer are values measured according to JIS K 7136. Examples of the measuring device include a haze meter “NDH-5000” manufactured by Nippon Denshoku Industries Co., Ltd.

  The thickness of the surface protective layer of the laminate for decorative molding of the present invention is preferably 20 μm or more, more preferably 35 μm or more, further 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 decorative molding is 500 μm or less. By making the thickness of the surface protective layer of the decorative molded laminate within the above range, the surface of the molded body can be easily decorated well.

  The present invention may relate to a stretched decorative molded laminate. Specifically, it may relate to a decorative molding laminate in which the stretching ratio in at least one direction selected from the first direction and the second direction is 1.5 times or more. In such a decorative molding laminate, the stretching 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 preferred. Moreover, it is more preferable that the draw ratios in both the first direction and the second direction are within the above range.

  The decorative molded laminate of the present invention is preferably used for decorating an automobile member, an electronic device or a building material. The laminate for decorative molding of the present invention is excellent in stretchability and has a surface protective layer that retains a high haze value even after stretching, and thus is preferably used for the above applications. Moreover, since the laminated body for decorative molding of this invention has the outstanding extending | stretching property, it is excellent in uneven | corrugated followable | trackability and can also decorate the member which has an uneven | corrugated structure and a curved part easily.

(Photo-curing resin layer)
The surface protective layer of the decorative molding laminate 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, further preferably 12% or more, still more preferably 13% or more, and 14% or more. Most preferably. The higher the haze of the photo-curing resin layer, the better the decorating property. That is, it is preferable that the photocurable resin layer has a higher haze because the surface properties of the molded body are less visible. In addition, said haze value is a haze value of the photocurable resin layer before extending | stretching the laminated body for decorative shaping | molding. When the surface protective layer is composed of a plurality of layers, the haze of the photocurable resin layer is determined by measuring the haze value of each layer other than the photocurable resin layer and the surface protective layer. It can be calculated by subtracting the haze value of layers other than the cured resin layer.

  FIG. 2 is an enlarged cross-sectional view for explaining the structure of the fine protrusions of the photo-curing 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 fine concavo-convex structure. When the photo-curing resin layer has such a fine uneven structure, the surface protective layer can have a high haze value.

  The average height of the convex portions of the fine concavo-convex structure is preferably 0.1 μm or more, more preferably 1 μm or more, and further preferably 5 μm or more. The average height of the convex portions of the fine concavo-convex structure is preferably 50 μm or less, more preferably 40 μm or less, and further 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 convex portions of the fine concavo-convex structure can be measured by the following method. First, using a micro laser microscope (measurement unit VK-X105 controller unit VK-X100 manufactured by KEYENCE Inc.), surface observation is performed at a magnification of 200 times to capture an image. 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 micro laser microscope. Specifically, 10 points are measured, and the average value is taken as the measured value.

  The average width of the convex portions of the fine concavo-convex structure is preferably 0.1 μm or more, more preferably 3 μm or more, and further preferably 5 μm or more. The average width of the convex portions of the fine concavo-convex structure is preferably 500 μm or less, more preferably 400 μm or less, and further 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 the width of the convex portion 10 is measured at 10 or more locations.

  The average width of the convex portions of the fine concavo-convex structure can be measured by the following method. First, using a micro laser microscope (measurement unit VK-X105 controller unit VK-X100 manufactured by KEYENCE Inc.), surface observation is performed at a magnification of 200 times to capture an image. Next, with respect to 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 micro laser microscope. Specifically, 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 or more and 30 μm or less. The ten-point average roughness Rz can be measured by the following method. First, using a micro laser microscope (measurement unit VK-X105 controller unit VK-X100 manufactured by KEYENCE Inc.), surface observation is performed at a magnification of 200 times to capture an image. Next, for the obtained image, the surface roughness Rz is calculated using analysis software attached to the micro laser microscope with a measurement area of 100 μm × 100 μm.

  The fine concavo-convex structure as described above can be formed, for example, by coating a photocurable resin that forms 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 a fine concavo-convex structure is formed by the above 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 resins, silicone resins, urethane resins, olefin resins, ester resins, and epoxy resins. Among these, acrylic resins, urethane resins, and epoxy resins are preferably used, and acrylic resins are particularly preferably used.

  It is preferable that the acrylic resin is 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 the side chain. The photo-curing resin layer may or may not contain a solvent.

  The weight average molecular weight of the photocurable resin is more preferably from 20,000 to 3,000,000, further preferably from 30,000 to 1,000,000, and particularly preferably from 50,000 to 200,000. By setting the weight average molecular weight of the photo-curing resin within the above-mentioned preferable range, it is possible to further improve the followability to the adherend during molding under vacuum or reduced pressure conditions (TOM molding), and a complicated shape. It becomes possible to decorate the adherend.

  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, Halth and the like.

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

  The photocurable resin layer may further contain fine particles. Examples of the fine particles include inorganic fine particles, and a metal oxide can be preferably exemplified. Moreover, you may contain a pigment and dye as needed.

As pigments, inorganic pigments (alumina white, titanium oxide, zinc white, black iron oxide, mica-like iron oxide, lead white, white carbon, molybdenum white, carbon black, resurge, lithopone, barite, cadmium red, cadmium mercury red, Bengala, molybdenum red, red lead, yellow lead, cadmium yellow, barium yellow, strontium yellow, titanium yellow, titanium black, chromium oxide green, cobalt oxide, cobalt green, cobalt chrome green, ultramarine blue, bituminous blue, cobalt blue, cerulean blue , Manganese purple, cobalt violet, etc.) and organic pigments (shellac, insoluble azo pigments, soluble azo pigments, condensed azo pigments, phthalocyanine blue, dyed lakes, etc.), toluidine red, toluidine maroon, hansa yellow, benzidine yellow, pyrazolone red, etc. Insoluble azo pigments, Soluble red pigments such as red, heliobordeaux, pigment scarlet and permanent red 2B, derivatives such as alizarin, indanthrone and thioindigo maroon, phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, and 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, imidazolone pigments such as benzimidazolone yellow, benzimidazolone orange and benzimidazolone red , Pyranthrone pigments such as pyranthrone red, 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.
Examples of the dye include acid dyes, basic dyes, direct dyes, reactive dyes, disperse dyes, and food dyes.

  Additives such as pigment dispersants, antifoaming agents, UV absorbers, hals, antioxidants, antistatic agents, antiwear agents, and antiblocking agents are added to the photocurable resin layer as necessary. May be.

(Base material layer)
The surface protective layer of the decorative molding laminate of the present invention may have a base material layer. It is preferable that the base material layer be stretchable in a form that follows the molded product in the molding process.

  The material constituting the base material layer is preferably plastic, for example. Examples of the plastic include ABS resin (acrylonitrile, butadiene and styrene copolymer), AS resin (acrylonitrile and styrene copolymer), acrylic resin, polyethylene terephthalate, polybutylene terephthalate, nylon, polyacetal, and polyphenylene oxide. , Phenol resin, urea resin, melamine resin, liquid crystal polymer, polytetrafluoroethylene, polyvinylidene fluoride, polysulfone, polyethersulfone, polyacetal, polyetheretherketone, polyphenylene sulfide, polyetherimide, polyamideimide, polycarbonate, 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 with these resins.

  The acrylic resin constituting the base material layer is preferably a resin obtained by polymerizing a resin composition whose main component is a monomer component having a (meth) acryloyl group. The main component of the monomer component is preferably a (meth) acrylic acid ester, and is preferably methyl methacrylate. As a plastic film obtained using such a resin component, for example, commercially available products such as acryloprene HBA001P, HBS010P, and HBA002P can be used. Moreover, the base material layer may be obtained by extruding a resin component.

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

  Moreover, a base material layer may contain the following component 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) ) 1,9-nonane acrylate, 1,6-hexanediol diacrylate, polybutylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, di (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. Further, 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, human loxypropyl (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, chloro-2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydrooctyl (meth) Examples include acrylate and / or copolymerizable unsaturated components, preferably acrylamide, methacrylamide, vinyl acetate, (meth) acrylonitrile, and macromers.

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

(Adhesive layer)
The laminate for decorative molding of the present invention may further have an adhesive layer. As the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, a known pressure-sensitive adhesive can be used. Examples of the pressure sensitive adhesive include natural rubber pressure sensitive adhesive, synthetic rubber pressure sensitive adhesive, acrylic pressure sensitive adhesive, urethane pressure sensitive adhesive, and silicone pressure sensitive adhesive. The pressure-sensitive adhesive may be any of a solvent system, a solventless system, an emulsion system, and an aqueous system. Among these, from the viewpoints of transparency, weather resistance, durability, cost and the like, an acrylic pressure-sensitive adhesive is preferable, and a solvent-based acrylic pressure-sensitive adhesive is particularly preferable.

  Other auxiliary agents may be added to the adhesive as necessary. Other auxiliary agents include antioxidants, tackifiers, silane coupling agents, UV absorbers, hindered amine compounds and other light stabilizers, thickeners, pH adjusters, binders, crosslinking agents, adhesive particles, Examples include antifoaming agents, antiseptic / antifungal agents, pigments, inorganic fillers, stabilizers, wetting agents, wetting agents and the like.

  Examples of tackifiers include aliphatic (C5) petroleum resins, aromatic (C9) petroleum resins, copolymerized (C5 / C9) petroleum resins, dicyclopentadiene (DCPD) petroleum resins, and coumarone indene. Examples thereof include resins, acrylic resins, styrene resins, rosins, rosin ester resins, terpene resins, aromatic modified terpene resins, terpene phenol resins, and hydrogenated resins thereof.

  It is preferable that content of the tackifier in an adhesive is 50 mass parts or less with respect to 100 mass parts of adhesives.

The thickness of the adhesive layer is preferably from 10 μm to 100 μm, and more preferably from 20 μm to 80 μm. When the thickness of the adhesive layer is within the above range, both sufficient adhesiveness and economy can be achieved.
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, a component having a carboxyl group, preferably acrylic acid, methacrylic acid, maleic acid, crotonic acid, crotonic acid, β-carboxyethyl acrylate, and / or a component having a hydroxyl group, preferably 2-hydroxyethyl (meth) acrylate , Humanoxypropyl (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 of the present invention may further have a separator layer. The separator layer is a layer that temporarily protects the adhesive layer until the decorative laminate of the present invention is attached to an adherend. The separator layer is preferably one in which a release layer such as silicone is provided on the surface of a resin film such as polyethylene terephthalate (PET), polyethylene, or polypropylene.

<Separator layer on the photocurable resin layer side>
The laminate for decorative molding of the present invention may have a separator layer on the photocurable resin layer side. In this invention, it is preferable that the separator layer by the side of a photocurable resin layer has a concavo-convex structure, and it is preferable that it has many fine recessed parts.

  When the separator layer has fine concave portions, the average depth of the fine concave portions is preferably 0.1 μm or more, more preferably 1 μm or more, and further 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 further preferably 30 μm or less. Note that. The average depth is an average value when ten or more recess depths 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 concave portions, the average width of the fine concave portions is preferably 0.1 μm or more, more preferably 3 μm or more, and further 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 further 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 10 or more places. In addition, the average width | variety of the fine recessed part of a separator layer is the value measured by the method similar to the measurement of the average width | variety of the convex part of a photocurable resin layer.

When a separator layer has a fine recessed part, it is preferable that the average cross-sectional area of a fine recessed part is 0.01 micrometer < ² > or more. The average cross-sectional area is more preferably 9 μm ² or more, and further preferably 25 μm ² or more. The average cross-sectional area of the fine recesses is preferably 250 mm ² or less, more preferably 160 mm ² or less, and further preferably 90 mm ² or less.

  The separator layer on the photocurable resin layer side is preferably made of resin. The resin is preferably a thermoplastic resin. Specific examples include polyolefin, polyvinyl chloride, polyvinyl alcohol, polyester, polycarbonate, polystyrene, and polyacrylonitrile. Among these, polyester is preferably used, and polyethylene terephthalate (PET) is particularly preferably used.

<Separator layer on the base material layer side>
The decorative molding laminate of the present invention may further have a separator layer on the base material layer side. In addition, when the laminated body for decorative molding of the present invention has an adhesive layer, and the adhesive layer is laminated in the order of the photocurable resin layer, the base material layer, and the adhesive layer, the adhesive layer is exposed. A separator layer on the substrate layer side is provided on the surface.

  The separator layer is preferably made of resin and does not include a paper base material. By using such a separator layer, foreign matters such as paper-derived dust are not sandwiched between the laminate and the molded body, and the biting of foreign matters can be effectively suppressed.

  The layer constituting the separator layer is preferably a resin layer, and the resin layer is preferably composed of a thermoplastic resin. Specifically, examples of the intermediate layer include a polyolefin film, a polyvinyl chloride film, a polyvinyl alcohol film, a polyester film, a polycarbonate film, a polystyrene film, and a polyacrylonitrile film. Among these, a polyester film is preferably used, and a polyethylene terephthalate (PET) film is 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 release agent include BY24-162 and SD-7234 manufactured by Toray Dow Corning Silicone, KS-3600, KS-774, and X62-2600 manufactured by Shin-Etsu Chemical Co., Ltd. Is mentioned. Further, the silicone release agent may contain a silicone resin which is an organosilicon compound having a SiO ₂ unit and a (CH ₃ ) ₃ SiO _1/2 unit or CH ₂ ═CH (CH ₃ ) SiO _1/2 unit. preferable. Specific examples of the silicone resin include BY24-843, SD-7292, SHR-1404, etc. manufactured by Toray Dow Corning Silicone, KS-3800, X92-183, manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

  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. Any adhesion improver can be used as long as adhesion is improved, and a silane coupling agent can be preferably used.

(Manufacturing method of decorative molded laminate)
The step of producing the decorative molding laminate of the present invention includes a step of forming a surface protective layer having a photocurable resin on the outermost surface. In this step, light (ultraviolet or electron) is applied to the outermost surface of the surface protective layer. It is preferable to include a step of irradiating (line). Moreover, when a surface protective layer is a layer which has a photocurable resin layer and a base material layer, after laminating | stacking a photocurable resin layer and a base material layer, the process of irradiating a light ray (an ultraviolet ray or an electron beam) is included. Is preferred. Furthermore, the manufacturing process of the decorative molded laminate includes a step of applying a photocurable resin layer-forming coating solution on the photocurable resin layer-side separator layer, and a step of laminating a base material layer on the photocurable resin layer. It is preferable to have a process. Alternatively, the photocurable resin layer forming solution coating on the photocurable resin layer side separator layer and the base material lamination step may be performed simultaneously. The step of irradiating the light beam (ultraviolet ray or electron beam) is preferably provided after the step of laminating the base material layer. In the step of irradiating the light ray (ultraviolet ray or electron beam), the separator layer side on the photocurable resin layer side It is preferable to irradiate from.

In the step of irradiating with light (ultraviolet rays), it is preferable to irradiate ultraviolet rays having 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 quantity 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 that 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))
The decorative molding laminate of the present invention is preferably used for decorating a molded article under vacuum conditions or reduced pressure conditions. Since the laminate for decorative molding of the present invention is a laminate for decorative molding that has sufficient stretchability and a high haze value, and has little decrease in haze even after stretching, production of a decorative molded body The decorative molded body which can improve property and was excellent in design property can be obtained.

  In the present specification, molding under vacuum conditions or reduced pressure conditions is so-called TOM molding. The TOM molding method includes a step of laminating the decorative molding laminate on the molded body under vacuum or reduced pressure conditions, and a step of pressure-bonding the decorative molding laminate to the molded body by a pressure difference. The decorative molding laminate used here has the above-described configuration, and includes a surface protective layer having a photo-curing 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 decorative molding laminate is 50% or more, and the second direction perpendicular to the first direction is used. The breaking elongation at 120 ° C. is 50% or more. Further, the haze of the surface protective layer before stretching the decorative molding laminate is P, and the surface protective layer after stretching the decorative molding laminate 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 a vacuum condition or a reduced pressure condition does not include a construction method in which a laminated body and a molded body are brought into close contact with each other by using a vacuum body provided with a vacuum hole. Specifically, the molding under a vacuum condition or a reduced pressure condition can be performed by using a “vacuum molding apparatus” described in Japanese Patent No. 3733564.

  Moreover, in the manufacturing method of the decorative molded body of the present invention, after the step of pressure-bonding the decorative molded laminate to the molded body, the step of heating the surface of the decorative molded laminate to 100 ° C. or higher and 180 ° C. or lower. It is preferable to contain. In this case, it is preferable to use an infrared heater for heating.

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

  FIG. 3 is a cross-sectional view illustrating the configuration of the decorative molded body 100. FIG. 3 shows a state in which the molded body 50 having a concave portion on the surface is decorated with the decorative molding laminate 1. As shown in FIG. 3, in molding under a vacuum condition or a reduced pressure condition, the reverse taper portion and the end winding portion can be covered and molded without providing a vacuum hole in the molded body 50. Moreover, it can decorate regardless of the material of a product. Thereby, it can decorate also about the molded object surface which has a complicated three-dimensional unevenness | corrugation, and the decorative molded object 100 with high designability can be obtained.

  Examples of the molded body 50 include metal materials such as ED steel plates, Mg alloys, stainless steel (SUS), and aluminum alloys, and resin molded bodies, but resin molded bodies are preferable. For example, ABS resin (acrylonitrile, butadiene and styrene copolymer), AS resin (acrylonitrile, styrene copolymer), AAS resin (acrylonitrile, acrylic and styrene copolymer), acrylic resin, polyethylene Terephthalate, polybutylene terephthalate, nylon, polyacetal, polyphenylene oxide, phenol resin, urea resin, melamine resin, liquid crystal polymer, polytetrafluoroethylene, polyvinylidene fluoride, polysulfone, polyethersulfone, polyacetal, polyetheretherketone, polyphenylenesulfide , Polyetherimide, polyamideimide, polycarbonate, polyethylene, polypropylene, polystyrene, urethane resin, vinylidene chloride resin, salt It can be preferably used vinyl resin. These resins may be blended. For example, a polycarbonate-containing resin can be preferably exemplified. Polycarbonate-containing resins include polycarbonate / polybutylene terephthalate blended resin (PC / PBT), polycarbonate / ABS resin blended resin (PC / ABS), and polycarbonate / PET blended resin (PC / PET). Etc. can be used particularly preferably. 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, parts such as a body, a bumper, a spoiler, a mirror, a wheel, an interior material, and various materials), a member for a two-wheeled vehicle, and a railway vehicle It can be used as a member. In addition, the decorative molded body can also be used as a building material such as electronic equipment such as home appliances, furniture, and building materials. Furthermore, the decorative molded body can also be used for road materials (for example, traffic signs, soundproof walls, etc.), tunnel materials (for example, side walls), musical instruments, containers, office supplies, sports equipment, toys, etc. it can.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

<Example 1>
(Laminate 1)
Average depth 3μm of recesses in the release agent layer surface, the average width 15μm recess, the average cross-sectional area 225 .mu.m ² release agent layer side of the separator having a large number of concave portions and acrylic film of the recess (Mitsubishi Rayon Co., Ltd., Akuripuren HBA001P, pencil hardness 2H and a thickness of 125 μm), the electron radiation curable resin 1 (UV1) was applied (wet laminate) to a thickness of 8 μm. This thickness is the total thickness from the top to the opposite side. Thereafter, the electron radiation curable resin 1 was cured by irradiating the separator with a high-pressure mercury lamp with electron radiation having a wavelength of 365 nm so that the illuminance was 100 mW / cm ² and the integrated light amount was 500 mJ / cm ² . In this way, a photocurable resin layer was obtained. Then, the separator was peeled off to obtain a laminate 1 composed of a surface protective layer in which a base material layer and a photocurable resin layer were laminated in this order. Table 1 shows the haze of the laminate 1 and the ten-point average roughness Rz of the outermost surface of the laminate.

  In addition, as the electron radiation curable resin composition 1 (UV1), Z-975L (made by Aika Kogyo Co., Ltd.) was used.

<Comparative Example 1>
(Laminate 2)
An acrylic film (manufactured by Mitsubishi Rayon Co., Ltd., Acryprene HBA001P, pencil hardness 2H, thickness 125 μm) was used as the substrate. On one side of this substrate, the electron radiation curable resin 2 (UV2) 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 2 were placed in a 100 ° C. hot air oven, and the applied electron radiation curable resin composition 2 was dried for 1 minute. Thereafter, the photo-curing resin layer is formed by irradiating the electron radiation having a wavelength of 365 nm 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 to cure the electron radiation curable resin 2. Formed. Thus, the laminated body 2 by which the base material layer and the photocurable resin layer were laminated | stacked in this order was obtained. Table 1 shows the haze of the laminate 2 and the ten-point average roughness Rz of the outermost surface of the laminate.

  The electron radiation curable resin composition 2 (UV2) is 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 Co., Ltd., Irgacure 184) and 30 parts by mass of inorganic particles having a primary average particle diameter of 500 nm was used.

<Comparative example 2>
(Laminate 3)
An acrylic film (manufactured by Mitsubishi Rayon Co., Ltd., Acryprene HBA001P, pencil hardness 2H, thickness 125 μm) was used as the substrate. On one side of this substrate, the electron radiation curable resin 3 (UV3) was applied 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 applied electron radiation curable resin composition 3 was dried for 1 minute. Thereafter, the photo-curing resin layer is formed by irradiating electron radiation having a wavelength of 365 nm 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 curing the electron radiation curable resin 3. Formed. Thus, the laminated body 3 by which the base material layer and the photocurable resin layer were laminated | stacked in this order was obtained. Table 1 shows the haze of the laminate 3 and the ten-point average roughness Rz of the outermost surface of the laminate.

  The electron radiation curable resin composition 3 (UV3) is 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 Co., Ltd., 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>
(Laminate 4)
An acrylic film (manufactured by Mitsubishi Rayon Co., Ltd., Acryprene HBA001P, pencil hardness 2H, thickness 125 μm) was used as the substrate. On one side of the substrate, an 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 100 ° C. hot air oven, and the applied electron radiation curable resin composition 4 was dried for 1 minute. Thereafter, the photo-curing resin layer is formed by irradiating the electron radiation having a wavelength of 365 nm 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 to cure the electron radiation curable resin 5. Formed. Thus, the laminated body 4 by which the base material layer and the photocurable resin layer were laminated | stacked in this order was obtained. The haze of the laminate 4 was measured.

  The electron radiation curable resin composition 4 (UV4) 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 (Ciba Specialty Chemicals, Irgacure 184) was used.

<Comparative Example 4>
(Laminate 5)
The release agent layer side of the separator having an unevenness with an average depth of 0.5 μm and an average width of 0.5 μm on the surface of the release agent layer and an acrylic film (manufactured by Mitsubishi Rayon Co., Ltd., Acryprene HBA001P, pencil hardness 2H, thickness 125 μm) In between, the electron radiation curable resin 1 (UV1) was applied (wet laminate) so as to have a thickness of 8 μm. The thickness of the electron radiation curable resin 1 is the total thickness including the concave portions and the convex portions. After that, the electron radiation having 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 amount is 500 mJ / cm ^2, and the electron radiation curable resin 1 is cured. A cured resin layer was formed. Then, the separator was peeled off to obtain a laminate 5 composed of a surface protective layer in which a base material layer and a photocurable resin layer were laminated in this order. Table 1 shows the haze of the laminate 5 and the ten-point average roughness Rz of the outermost surface of the laminate.

  In addition, as the electron radiation curable resin composition 1 (UV1), Z-975L (made by Aika Kogyo Co., Ltd.) was used.

(Evaluation)
(Haze of surface protective layer)
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 in accordance with JIS K 7136. It measured using color industry Co., Ltd. haze meter "NDH-5000".

(Surface unevenness)
The surface irregularities of the laminated body 1 of Example 1, the laminated body 2 of Comparative Example 1, the laminated body 3 of Comparative Example 2, the laminated body 4 of Comparative Example 3, and the laminated body 5 of Comparative Example 4 are visually observed to give a feeling of surface. confirmed.
○: Reflection on the surface is suppressed.
Δ: Reflection on the surface is somewhat suppressed.
X: Reflection on the surface is not suppressed.

(10-point average roughness Rz)
The outermost surface of the laminated body 1 of Example 1, the laminated body 2 of Comparative Example 1, the laminated body 3 of Comparative Example 2, the laminated body 4 of Comparative Example 3, and the laminated body 5 of Comparative Example 4 was subjected to micro laser microscope (Inc. Using a KEYENCE measuring unit VK-X105, controller unit VK-X100), surface observation was performed at a magnification of 200 times to capture an image. For the obtained image, the measurement area was 100 μm × 100 μm, and the 10-point average roughness Rz was measured using analysis software attached to the microlaser microscope.

(Formability evaluation test)
About the laminated body 1 of Example 1, the laminated body 2 of the comparative example 1, the laminated body 3 of the comparative example 2, the laminated body 4 of the comparative example 3, and the laminated body 5 of the comparative example 4, a TOM molding machine (manufactured by Fuse Vacuum Co., Ltd.) , NGF molding machine) was subjected to decorative molding (molding temperature 120 ° C.) under the condition that the stretching ratio in the longitudinal direction and the width direction of the laminate was 50% or more, to obtain a decorative molded body. As the adherend, a rainproof cover (product number: WP9171 [manufactured by Panasonic Corporation]) was used. About the said decorative molded object, the moldability was evaluated according to the following evaluation criteria.
A: No breakage of the laminate was observed at the maximum stretched portion of the laminate (stretching ratio in the longitudinal direction of the laminate and the width direction of 50% or more).
Δ: Some breakage of the laminate was observed at the maximum stretched portion of the laminate (stretch ratio in the longitudinal direction and the width direction of 50% or more), but there was no practical problem.
X: Breakage of the laminate was observed at the maximum stretched portion of the laminate (stretching ratio in the longitudinal direction of the laminate and the width direction of 50% or more).

(Elongation at break)
The laminated body 1 of Example 1, the laminated body 2 of Comparative Example 1, the laminated body 3 of Comparative Example 2, the laminated body 4 of Comparative Example 3, and the laminated body 5 of Comparative Example 4 were formed by a TOM molding machine (manufactured by Fuse Vacuum Co., Ltd., Using an NGF molding machine), molding is performed at 120 ° C. using a jig that can measure in 10% increments from 10 to 100% in the longitudinal or width direction of the laminate for decorative molding. A molded body was obtained. And the draw ratio before a fracture | rupture arises in a part of surface protective layer was made into the breaking elongation of the laminated body for decorating shaping | molding. Those that did not break even at a draw ratio of 100% were evaluated as “> 100”. For example, the test was conducted while changing the draw ratio by 10%, and when breakage was first observed on the surface of the molded body when stretched by 90%, the elongation at break was set to 80%.

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

(Total light transmittance)
The total light transmittance of the laminated body 1 of Example 1, the laminated body 2 of Comparative Example 1, the laminated body 3 of Comparative Example 2, the laminated body 4 of Comparative Example 3, and the laminated body 5 of Comparative Example 4 conforms to JIS K 7136. Measured using a Nippon Denshoku Industries Co., Ltd. haze meter “NDH-5000”. 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 laminates obtained in the examples had high haze before stretching and excellent decorating properties. Moreover, it turns out that the laminated body obtained by the Example has high elongation at break, and the haze change rate before and behind extending | stretching is suppressed low.

DESCRIPTION OF SYMBOLS 1 Layered body for decorative molding 2 Surface protective layer 3 Base material layer 5 Photocurable resin layer 10 Convex part 50 Molded body 100 Decorated molded body

Claims (10)

A decorative molded laminate including 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 decorative molding laminate 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 after stretching the decorative laminate by 50% in the first direction or the second direction is defined as P, which is the haze of the surface protective layer before stretching the decorative laminate. Is a laminate for decorative molding, wherein the haze reduction rate represented by (PQ / P) × 100 is 40% or less.   The decorative molding laminate according to claim 1, wherein an outermost surface of the surface protective layer has a fine uneven structure.   The laminate for decorative molding according to claim 2, wherein an average height of the convex portions of the fine concavo-convex structure is 0.1 µm or more and 50 µm or less.   The average width of the convex portions of the fine concavo-convex structure is 0.1 µm or more and 500 µm or less, and the ten-point average roughness Rz of the outermost surface of the surface protective layer is 1 µm or more and 30 µm or less. The laminate for decorative molding according to item.   The laminate for decorative molding according to any one of claims 1 to 4, further comprising an adhesive layer.   The laminate for decorative molding according to any one of claims 1 to 5, which is used for decorative molding under vacuum conditions or reduced pressure conditions.   The laminate for decorative molding according to any one of claims 1 to 6, which is used for decorating an automobile member, an electronic device or a building material.   The laminate for decorative molding according to any one of claims 1 to 7, wherein a draw ratio in at least one direction selected from the first direction and the second direction is 1.5 times or more.   A decorative molded body comprising the laminate for decorative molding according to any one of claims 1 to 8 and a molded body decorated with the laminate for decorative molding. A step of laminating a decorative molded laminate on a molded body under vacuum or reduced pressure conditions;
A method for producing a decorative molded body including a step of pressure-bonding the laminate for decorative molding to a molded body by pressure difference,
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 breaking elongation at 120 ° C. in the first direction of the decorative molding laminate 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 after stretching the decorative laminate by 50% in the first direction or the second direction is defined as P, which is the haze of the surface protective layer before stretching the decorative laminate. Is the manufacturing method of the decorative molded object whose haze reduction rate represented by (PQ / P) x100 is 40% or less.

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