JP2018171837A - Chipping-resistant decorative compact - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative compact having excellent chipping resistance.SOLUTION: There is provided a decorative compact having an adherend, an adhesion layer, a design layer and a surface protective layer in this order. In the decorative compact, the adherend and the adhesion layer adhere directly to each other, and 180° peel strength at 23°C and 50% RH specified in JIS Z0237:2009 at an interface between the adherend and the adhesion layer is 30 N/25 mm or higher.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative molded body having chipping resistance.

  Conventionally, for the exterior of general vehicle bodies such as automobiles, trains, buses, airplanes, etc., it has been desired to establish a decoration technique having a design such as a metallic tone using a film or a design tone. Under such circumstances, means for decorating the surface of an adherend of a resin molded body for an automobile exterior has been proposed.

In the decorative molded body having design properties, an adhesive layer may be used to bond the design layer and the adherend. However, in the conventional adhesive layer, since the adhesion strength with the adherend is not sufficient, when the decorative molded body is used for the exterior of a vehicle body such as an automobile, it is used as a stepping stone while the vehicle body is running. There was a problem that peeling (chipping) of the decorative layer derived from occurred.
Regarding chipping resistance, Patent Document 1 includes a film-like substrate made of an olefin-based elastomer and an adhesive layer applied to the adherend side of the substrate, and the thickness of the substrate and its elastic modulus. It has been proposed to use a protective film for automobile exteriors having a decorative function that defines the above.

JP 2004-115657 A

  However, in patent document 1, although the adhesive layer is arrange | positioned at the to-be-adhered body side of a base material, it is the structure which an adhesive layer touches release paper, and prescribes | regulates the elasticity modulus of a base material. However, no study has been made on the adhesion between the pressure-sensitive adhesive layer and the adherend.

  This invention is made | formed in view of such a situation, and makes it a subject to provide the decorative molded object which has the outstanding chipping resistance.

In order to solve the above problems, the present invention provides the following (1).
(1) A decorative molded body having an adherend, an adhesion layer, a design layer, and a surface protective layer in this order, wherein the adherend and the adhesion layer are in direct contact, and the adherend and the adhesion layer are A decorative molded body having a 180 ° peel strength at 23 ° C. and 50% RH as defined in JIS Z0237: 2009 of 30 N / 25 mm or more.

  According to the present invention, a decorative molded body having excellent chipping resistance can be provided.

It is sectional drawing which shows embodiment of the decorative molded body of this invention. It is a schematic diagram of the gravel test apparatus which evaluates the chipping resistance of the decorative molded body obtained in the examples and comparative examples.

[Decorative molded body]
The decorative molded body of the present invention is a decorative molded body having an adherend, an adhesion layer, a design layer, and a surface protective layer in this order, and the adherend and the adhesion layer are in direct contact with each other. The 180 ° peel strength at 23 ° C. and 50% RH as defined in JIS Z0237: 2009 at the interface between the adherend and the adhesion layer is 30 N / 25 mm or more.

  FIG. 1 is a cross-sectional view showing an embodiment of the decorative molded body of the present invention. The decorative molded body 1 in FIG. 1 has an adherend 6 and an adhesion layer 5, a design layer 4, and a surface protective layer 3 constituting the decorative sheet 2 in this order.

  The decorative sheet used for the decorative molded body of the present invention may have an adhesion layer, a design layer, and a surface protective layer in this order, and an anchor layer and a backer layer, which will be described later, between these layers and the surface. And other layers may be included.

<Example of layer structure of decorative sheet>
Specific examples of the decorative sheet include the following configurations (1) to (6). Note that “/” means the boundary of each layer.
(1) Adhesion layer (heat-sensitive adhesive layer or pressure-sensitive adhesive layer) / design layer / surface protective layer (2) Adhesion layer (backer layer combined adhesion layer) / adhesive layer / design layer / surface protective layer (3 ) Adhesion layer (heat-sensitive adhesive layer or pressure-sensitive adhesive layer) / design layer / anchor layer / surface protective layer (4) Adhesion layer (backer layer combined adhesion layer) / adhesive layer / design layer / anchor layer / surface Protective layer (5) Adhesion layer (heat-sensitive adhesive layer or pressure-sensitive adhesive layer) / backer layer / adhesive layer / design layer / surface protective layer (6) Adhesion layer (heat-sensitive adhesive layer or pressure-sensitive adhesive) Layer) / backer layer / adhesive layer / design layer / anchor layer / surface protective layer Among these, the surface protective layer includes the following configurations (p) to (r).
(P) Film simple substance (q) Paint film simple substance (r) Film simple substance / Coating film simple substance “Film simple substance” here means, for example, a function as a support for a decorative sheet and a function to protect a design layer And the like. Examples of the “coating film alone” include a hard coat layer used for improving the scratch resistance of the surface and the like.

  First, the adhesion layer that is a feature of the decorative molded body of the present invention will be described.

(Adhesion layer)
The adhesion layer is a layer in contact with the adherend in the layer constituting the decorative sheet, and is formed, for example, to improve the adhesion to the adherend.
In the decorative molded body of the present invention, an adhesion layer is interposed between the adherend and the design layer, and the adhesion layer is in direct contact with the adherend.

The adhesion layer is preferably composed of a heat-sensitive or pressure-sensitive resin. In other words, the adhesion layer is preferably a so-called heat-sensitive adhesive layer or pressure-sensitive adhesive layer. Moreover, from the viewpoint of simplicity of the bonding process, the adhesion layer is more preferably a pressure-sensitive adhesive layer.
Examples of heat-sensitive or pressure-sensitive resins include general-purpose acrylic resins, urethane resins, polyester resins, silicone resins, vinyl chloride resins or vinyl acetate resins, or a mixture or copolymer of two or more of these. Is preferably used. Among such resins, acrylic resins are more preferable.
The glass transition temperature Tg of the pressure-sensitive adhesive layer is preferably 0 to 30 ° C, more preferably 5 to 28 ° C, and further preferably 10 to 26 ° C. When the glass transition temperature is less than 0 ° C., the chipping resistance tends to decrease, the heat resistance decreases, and the surface smoothness of the decorative molded body tends to decrease. When it exceeds 30 ° C., the smoothness tends to be improved, but the chipping resistance tends to be lowered due to the decrease in adhesion. When the glass transition temperature is in this range, it becomes easy to balance the chipping resistance of the decorative molded body and the smoothness of the surface at a high temperature of the decorative sheet.
The thickness of the adhesion layer is preferably 1 to 100 μm, and more preferably 10 to 50 μm. When the thickness of the adhesion layer is less than 1 μm, it is difficult to ensure the adhesion force when the adhesion layer becomes thin due to elongation during molding. Further, if it exceeds 100 μm, the cost becomes high. When the thickness of the adhesion layer is in the above range, the adhesion strength between adjacent layers can be easily improved.
The adhesion layer can also serve as a backer layer described later. When the adhesion layer also serves as the backer layer, the adhesion layer is composed of the same kind of thermoplastic resin as the adherend, for example, an ABS resin (acrylonitrile-butadiene-styrene copolymer resin), a polypropylene resin, a polyethylene resin, It is preferably composed of a plastic film made of styrene resin, acrylic resin, vinyl chloride resin, polycarbonate resin or the like.
The thickness of the plastic film before molding is preferably 100 μm or more and less than 1000 μm, and more preferably 150 μm or more and 500 μm or less. When the adhesion layer also serves as the backer layer, it is preferable to have an adhesive layer between the adhesion layer and the design layer (particularly when the design layer is a metal film). As the adhesive constituting the adhesive layer, a general-purpose adhesive can be used.

(Backer layer)
The decorative sheet may have a backer layer between the adhesion layer and the design layer. A backer layer has a role which raises the intensity | strength of a decorating sheet and a decorating molded object, or hold | maintains the shape of a molded object, for example.

  The backer layer is preferably composed of a plastic film. Examples of the plastic film for the backer layer include ABS resin (acrylonitrile-butadiene-styrene copolymer resin), polypropylene resin, polyethylene resin, styrene resin, acrylic resin, vinyl chloride resin, and polycarbonate resin. Etc. can be used.

The thickness of the backer layer before molding is preferably 100 μm or more and less than 1000 μm, and more preferably 150 to 500 μm.
When the decorative sheet has a backer layer between the adhesion layer and the design layer (particularly when the design layer is a metal film), it is preferable to have an adhesive layer between the backer layer and the design layer. . As the adhesive constituting the adhesive layer, a general-purpose adhesive can be used.

(Adherent)
The decorative molded body of the present invention has an adherend on the surface of the adhesion layer opposite to the design layer. Further, as described above, an adhesion layer is interposed between the adherend and the design layer, and the adhesion layer is in direct contact with the adherend.

The adherend is not particularly limited, and includes a molded body made of metal, glass, ceramics, resin, or the like. In the present invention, it is preferable to use a resin layer from the viewpoints of moldability and adhesion at the interface with the adhesion layer.
In addition, the adherend may be used while being bonded to the decorative sheet as a flat plate, or may be formed in advance in the shape of a molded body, or may be poured into a mold at the time of molding. It is good also as a shape of a forming object.

  Examples of the resin constituting the adherend include ABS resin (acrylonitrile-butadiene-styrene copolymer resin), polypropylene resin, polyethylene resin, styrene resin, acrylic resin, vinyl chloride resin, and polycarbonate. Based resins and the like. Among these, an ABS resin and a polypropylene resin are preferable, and an ABS resin is more preferable.

The adherend may be colored. The coloring is preferably an achromatic color (gray, black) excluding white, and more preferably black.
Moreover, 0.1-5.0 mm is preferable and, as for the thickness before shaping | molding of the to-be-adhered body at the time of vacuum forming, 0.5-3.5 mm is more preferable.

  The adherend and the adhesion layer are in direct contact, and the 180 ° peel strength at 23 ° C. and 50% RH as defined in JIS Z0237: 2009 at the interface between them is 30 N / 25 mm or more. When the 180 ° peel strength is less than 30 N / 25 mm, the chipping resistance is lowered. The 180 ° peel strength is preferably 35 N / 25 mm or more, more preferably 40 N / 25 mm or more, and further preferably 45 N / 25 mm or more. When the 180 ° peel strength is in the range of 30 N / 25 mm or more, the adhesion strength between the adhesion layer and the adherend is high, and the chipping resistance is improved.

(Anchor layer)
It is preferable to have an anchor layer between the surface protective layer and the design layer in order to improve adhesion with the design layer.

The anchor layer can be composed of various resins such as an acrylic resin, a vinyl chloride resin, a vinyl acetate resin, a polyester resin, and a urethane resin.
As the resin constituting the anchor layer, it is preferable to select a resin that enhances the adhesion between the surface protective layer and the metal film. For example, when the surface protective layer is an acrylic resin film, the anchor layer is preferably composed of an acrylic resin. The acrylic resin of the anchor layer is preferably a reaction product of an acrylic polyol as a main agent and an isocyanate compound as a curing agent.

The thickness of the anchor layer before molding is not particularly limited, and is usually about 0.1 to 10 μm.
The anchor layer may contain additives such as an ultraviolet absorber and a light stabilizer.

(Design layer)
The design layer is a layer provided for the purpose of imparting design properties to the decorative sheet. The design formed by the design layer is not particularly limited, and examples thereof include those that impart design properties with metallic luster, and those that impart design properties with a pattern layer (including a solid colored layer).

<Metal film>
When a metallic luster is given by metallic luster, a metal film is usually used.
Examples of the metal constituting the metal film include metals such as indium, tin, aluminum, nickel, copper, silver, gold, platinum, brass, chromium, and zinc, and alloys thereof. Among these, it is preferable to use one or more selected from indium, tin, aluminum, zinc, and alloys thereof. Indium is most preferable from the viewpoint of excellent weather resistance, whitening suppression, and metallic luster balance.

  Examples of the method for forming the metal film include a vacuum deposition method, a sputtering method, and an ion plating method. Among these, the vapor deposition method which can process to all the materials is preferable.

  The thickness of the metal film layer needs to be appropriately adjusted depending on the metal to be used, but is preferably 10 to 300 nm, more preferably 30 to 150 nm, from the viewpoint of metal gloss, weight reduction and material cost. More preferably, it is ˜100 nm.

<Picture layer>
The pattern layer (including the entire solid colored layer) is not particularly limited, but for example, a red, yellow, carbon, wood grain, marble pattern, etc. Examples thereof include a fabric pattern imitating a pattern, a tiled pattern, a brickwork pattern, and the like. These may be formed by multicolor printing by superimposing process colors of normal red, yellow, blue, and black, or may be formed by printing with special colors performed by preparing individual color plates. . In particular, from the viewpoint of expressing a design with high saturation, it is preferable to perform multicolor printing by superimposing process colors.
Although it does not restrict | limit especially as thickness of a pattern layer, Usually, it is about 0.1-30 micrometers. Preferably it is 1-20 micrometers. The picture layer may be formed of one layer or may be formed of a plurality of layers of two or more layers. The printing method for forming the pattern layer is not particularly limited, and examples thereof include gravure printing, offset printing, silk screen printing, printing by transfer from a transfer sheet, and ink jet printing.
As the ink used for the pattern layer, a binder and a colorant such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, and a curing agent are appropriately mixed. The binder is not particularly limited, and examples thereof include polyurethane resins (acrylic urethane copolymer resins, etc.), vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, and chlorinated polypropylene. Resin, acrylic resin, polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin, etc., any one can be used alone or in combination of two or more Used as a mixture.
Colorants include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, isoindolinone yellow, phthalocyanine Organic pigments or dyes such as blue, metallic pigments composed of scaly foil pieces such as aluminum and brass, pearlescent pigments composed of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate, and the like are used.

(Surface protective layer)
A surface protective layer has a role as a support body of the decorating sheet used for this invention, and the role which protects a design layer, for example. What consists of the above-mentioned film simple substance and / or what consists of a coating-film simple substance etc. are mentioned.

Layers consisting of a single film include polyolefin resins such as polyethylene and polypropylene, polyvinyl resins such as polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene / vinyl acetate copolymers, ethylene / vinyl alcohol copolymers, and polyethylene. Polyester resins such as terephthalate, polyethylene naphthalate, polybutylene terephthalate, acrylic resins such as poly (meth) methyl acrylate and poly (meth) ethyl acrylate, styrene resins such as polystyrene, nylon 6 or nylon 66, etc. Examples thereof include a plastic film made of a resin such as a polyamide-based resin.
Among these, an acrylic resin film excellent in transparency, light resistance, and moldability is preferable.

  The thickness of the layer consisting of a single film is not particularly limited, but is preferably 50 to 250 μm, more preferably 60 to 200 μm, and more preferably 70 to 200 μm from the viewpoint of the balance between moldability and design layer protection. More preferably, it is 150 μm.

  It is preferable that the layer which consists of the said coating-film simple substance contains the hardened | cured material of curable resin composition. Examples of the cured product of the curable resin composition include a cured product of the thermosetting resin composition and a cured product of the ionizing radiation curable resin composition, and among these, a cured product of the ionizing radiation curable resin composition is preferable.

  The thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating. Examples of the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. In the thermosetting resin composition, a curing agent is added to these curable resins as necessary.

The ionizing radiation curable resin composition is a composition containing a compound having an ionizing radiation curable functional group (hereinafter also referred to as “ionizing radiation curable compound”). Examples of the ionizing radiation curable functional group include an ethylenically unsaturated bond group such as a (meth) acryloyl group, a vinyl group, and an allyl group, an epoxy group, and an oxetanyl group.
As the ionizing radiation curable resin, a compound having an ethylenically unsaturated bond group is preferable. In addition, from the viewpoint of suppressing damage to the resin layer in the process of producing a metallic decorative molded body, the ionizing radiation curable resin is more preferably a compound having two or more ethylenically unsaturated bond groups. More preferred are polyfunctional (meth) acrylate compounds having two or more ethylenically unsaturated bond groups. As the polyfunctional (meth) acrylate compound, any of a monomer and an oligomer can be used.
The ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams can also be used.

  The thickness of the layer consisting of a single coating film is preferably 0.5 to 30 μm, more preferably 1 to 20 μm, and still more preferably 3 to 10 μm.

The surface protective layer may be a single film, a single coating film, or a combination thereof as long as it plays the above-described role, and is on the surface opposite to the adhesion layer side of the design layer. Use.
The surface protective layer may contain additives such as ultraviolet absorbers and light stabilizers. Moreover, the coloring agent etc. may be contained from the viewpoint of the designability mentioned above. Furthermore, a silica filler or the like may be contained from the viewpoint of improving scratch resistance and imparting a matte feeling.

  Since the decorative molded body of the present invention has excellent chipping resistance, it is preferably used for the exterior of a vehicle body. Here, the vehicle body is not particularly limited as long as chipping resistance is required, and examples thereof include automobiles, bicycles, trains, trucks, buses, airplanes, and the like that accompany movement on roads, airways, and the like.

<Method for producing decorative sheet>
The method for producing a decorative sheet used in the decorative molded body of the present invention includes a step of forming a design layer on the surface protective layer and a step of forming an adhesion layer on the design layer.

(Design layer formation process)
The design layer forming step is a step of forming a design layer on the surface protective layer. The design layer is formed as described above.

(Adhesion layer forming process)
The adhesion layer forming step is a step of forming an adhesion layer on the design layer. As a method for forming the adhesion layer, it can be formed by a known method.

(Anchor layer formation process)
The method for producing a decorative sheet used for the decorative molded body may further include an anchor layer forming step. The anchor layer forming step is a step of providing an anchor layer between the design layer and the surface protective layer. Examples of the method for forming the anchor layer include known methods such as gravure coating, bar coating, roll coating, reverse roll coating, and comma coating.

<Method for producing decorative molded body>
The decorative molded body can be manufactured by molding using the decorative sheet used in the present invention and the adherend described above.

  For example, a decorative molded body can be manufactured by bonding an adhesion layer of a decorative film and an adherend serving as a constituent member of the decorative molded body. That is, it is a step of bonding the design layer and the adherend through the adhesion layer. The bonding method can be formed by a known method. This is preferable because a laminating method using heat and pressure by a roll transfer device or the like can be simplified. In particular, regarding the laminating temperature at the interface between the adhesion layer and the adherend, it is important to manufacture while accurately monitoring the temperature. When using an adherend having a glass transition temperature higher than that of the adhesion layer, the JIS at the interface between the adherend and the adhesion layer described above is controlled by controlling the laminating temperature so as to be higher than the glass transition temperature of the adherend. It becomes easy to make it the range of 180 degree peel strength in 23 degree C 50% RH prescribed | regulated to Z0237: 2009.

In addition, for example, a decorative molded body can be manufactured by vacuum forming having the following steps (y1) to (y2).
(Y1) A laminated body in which the surface on the adhesion layer side of the decorative sheet is adhered to the adherend is produced.
(Y2) The surface of the laminate on the adherend side is arranged facing the mold and vacuum-formed.

Furthermore, a decorative molded body can be produced by in-mold molding having the following steps (z1) to (z2).
(Z1) The decorative sheet is placed in an in-mold mold. At this time, of the pair of molds (male mold and female mold) constituting the in-mold molding mold, the inner surface of the mold on the resin injection side and the surface on the adhesion layer side based on the design layer of the decorative sheet The decorative sheet is arranged so that and face each other. Note that the inside of the mold refers to the gap side formed between a pair of molds.
(Z2) A resin is injected and injected into an in-mold molding die to mold a resin molded body that is an adherend, and the molded body and the decorative sheet are brought into close contact with each other.

Furthermore, a decorative molded body can be produced by insert molding having the following steps (u1) to (u2).
(U1) The decorative sheet is previously vacuum-formed into a molded product surface shape (off-line pre-molding) with a vacuum forming die, and then an excess portion is trimmed as necessary to obtain a molded sheet.
(U2) The molded sheet is inserted into an injection mold, the resin is injected and injected, and the resin molded body as the adherend and the decorative sheet are brought into close contact with each other.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, this invention is not limited to the form as described in an Example.

1. Evaluation and measurement Various characteristics (chipping resistance, 180 ° peel strength between adherend and adhesion layer, surface smoothness) related to the decorative molded bodies obtained in Examples and Comparative Examples, glass transition temperature of adhesive layer The temperature of the surface protective layer during roll transfer was evaluated according to the following procedure. The results are shown in Table 1.

1-1. Chipping resistance The chipping resistance test was conducted according to the standard number SAE J-400, the standard name Test for Chip Resistance of Surface Coatings, and a gravel test. FIG. 2 is a schematic diagram of a gravel test apparatus for evaluating chipping resistance of the decorative molded bodies obtained in Examples and Comparative Examples. No. 7 crushed stone 21 (50 g) on the decorative molded body 10 obtained in Examples and Comparative Examples on the test support 22 (material: ceramic) at −20 ° C. and 23 ° C. using the Gravelo test apparatus 20. Was irradiated for 1 second at an injection pressure of 0.4 MPa from the position of the distance of 350 mm in the vertical direction of the decorative molded body 10, and then the film peeling of the decorative molded body 10 was confirmed. The evaluation criteria are as follows.
<Evaluation criteria>
○: Observed by visual observation, no film peeling.
X: Observed visually and the film is peeled off.
1-2. Peeling strength 23 ° C. and 50% RH as defined in JIS Z0237: 2009 below at the interface between the adherend of the decorative molded body (test plate: size 10 cm × 10 cm) obtained in Examples and Comparative Examples and the adhesion layer 180 ° peel strength was measured using a 5565 type testing machine (Instron).
When peeling off the test plate, hold the end of the tape so that the back of the tape overlaps, turn it back 180 °, and peel off 25 mm from the test plate. One end of the peeled test plate is fixed to one chuck of the tensile tester, and the tape is fixed to the other chuck. Next, the tester is operated at 5.0 ± 0.2 mm / s. After starting the measurement, the first 25 mm length measurement is ignored. Thereafter, the measured adhesive strength values of a length of 50 mm peeled off from the test plate are averaged and used as a peel strength value.
1-3. Surface smoothness The decorative molded bodies obtained in the examples and comparative examples are allowed to stand for 500 hours in an environment of 80 ° C., and the degree of smoothness of the surface of the decorative molded bodies can be measured under the illumination of a fluorescent lamp. The spot was visually observed from all angles. The evaluation criteria are as follows.
○: A sharp image is reflected on the surface of the molded product, and the surface is smooth.
X: The image reflected on the surface of the molded product is distorted and the surface smoothness is inferior.
1-4. Glass transition temperature Tg of adhesive layer
The adhesive layer composition was applied to a release treatment surface of a 38 μm thick polyester film (trade name: E7304, manufactured by Toyobo Co., Ltd.) subjected to silicone release treatment, and dried so that the thickness after drying was 40 μm. A layer (pressure sensitive adhesive layer) was formed. The adhesive layer was peeled from the release sheet, and tensile dynamic viscoelasticity measurement was performed using a dynamic viscoelasticity measuring apparatus (manufactured by UBM, Rheogel-E4000) under the following conditions. The peak temperature of the obtained loss tangent tan δ was defined as the glass transition temperature Tg.
Measurement temperature range: -50 ° C to 100 ° C
Temperature increase rate: 3 ° C / min
Frequency: 10Hz
1-5. Temperature of surface protective layer The temperature (actual temperature) of the surface protective layer of the decorative sheet when the adherend was bonded to the adhesion layer of the decorative sheet using a roll transfer machine was measured using a thermocouple.

2. Preparation of decorative sheet and decorative molded body [Example 1]
On the surface protective layer made of an acrylic resin film having a thickness of 125 μm, an anchor layer forming coating solution having the following formulation was applied and dried to form an anchor layer having a thickness of 2 μm.
<Anchor layer forming coating solution>
Acrylic polyol (Arakawa Chemical Industries, trade name Aracoat DA105) 3.0 parts by mass Isocyanate compound (Arakawa Chemical Industries, trade name Aracoat CL1) 1.0 parts by weight

  Next, a 70 nm thick metal film made of indium was formed as a design layer on the anchor layer by vacuum vapor deposition.

  Next, an epoxy-based crosslinking agent (manufactured by Soken Chemical Co., Ltd., trade name: E-) with respect to 100 parts by mass of an acrylic adhesive (manufactured by Soken Chemical Co., Ltd., trade name: SK Dyne 1838, solid content 21% by mass) as the main agent. (AX, solid content 5 mass%) 0.15 mass part was mixed, and the composition for adhesive bond layers was obtained. The adhesive layer composition was applied to a release treatment surface of a 38 μm thick polyester film (trade name: E7304, manufactured by Toyobo Co., Ltd.) subjected to silicone release treatment, and dried so that the thickness after drying was 40 μm. A layer (pressure-sensitive adhesive layer) was formed to obtain a decorative sheet.

  Next, on the pressure-sensitive adhesive layer of the obtained decorative sheet, an adherend (ABS resin film having a thickness of 3.0 mm) is placed on a roll transfer machine (manufactured by Navitas, model number: RH-300) at a set temperature of 200 ° C., The decorative molded body used in Example 1 was obtained by pasting together at a speed of 10 mm / sec and one pass.

[Example 2]
A decorative molded body of Example 2 was obtained in the same manner as Example 1 except that the set temperature of the roll transfer machine was changed to 180 ° C.

[Example 3]
A decorative molded body of Example 3 was obtained in the same manner as in Example 1 except that the adhesive layer was formed from the following adhesive layer composition (main agent: SK Dyne 2094).
-Adhesive layer composition Acrylic pressure-sensitive adhesive (manufactured by Soken Chemical Co., Ltd., trade name: SK Dyne 2094, solid content 25% by mass) 100 parts by weight of epoxy cross-linking agent (manufactured by Soken Chemical Co., Ltd., trade name: E-AX, solid content 5% by mass) 0.27 parts by mass.

[Comparative Example 1]
A decorative molded body of Comparative Example 1 was obtained in the same manner as in Example 1 except that the set temperature of the roll transfer machine was changed to 160 ° C.

[Comparative Example 2]
A decorative molded body of Comparative Example 2 was obtained in the same manner as in Example 1 except that the adhesive layer was formed from the following adhesive layer composition (main agent: SK Dyne 1717).
-Adhesive layer composition Acrylic pressure-sensitive adhesive (manufactured by Soken Chemical Co., Ltd., trade name: SK Dyne 1717, solid content 45% by mass) 100 parts by weight of epoxy cross-linking agent (manufactured by Soken Chemical Co., Ltd., trade name: E-AX, solid content 5 mass%) A composition in which 0.32 mass parts was mixed.

  From the results of Table 1, the decorative molded bodies of Examples 1 to 3 having a peel strength at 23 ° C. and 50% RH of the interface between the adherend and the adhesive layer of 34.4 to 38.8 N / 25 mm are It can be confirmed that the chipping property is excellent.

  The decorative molded body of the present invention can be suitably used for vehicle body exteriors such as automobiles that require chipping resistance.

1: decorative molded body 2: decorative sheet 3: surface protective layer 4: design layer 5: adhesion layer 6: adherend 10: decorative molded body 20: gravel test apparatus 21: No. 7 crushed stone 22: test support body

Claims (8)

  A decorative molded body having an adherend, an adhesion layer, a design layer, and a surface protective layer in this order, wherein the adherend and the adhesion layer are in direct contact with each other at the interface between the adherend and the adhesion layer. A decorative molded body having a 180 ° peel strength of 30 N / 25 mm or more at 23 ° C. and 50% RH as defined in JIS Z0237: 2009.   The decorative molded body according to claim 1, wherein the adhesion layer is a pressure-sensitive adhesive layer.   The pressure-sensitive adhesive layer includes an acrylic resin, a urethane resin, a polyester resin, a silicone resin, a vinyl chloride resin, a vinyl acetate resin, or a mixture or copolymer of two or more thereof. Item 3. A decorative molded article according to item 1 or 2.   The decorative molded body according to any one of claims 1 to 3, wherein a glass transition temperature Tg of the pressure-sensitive adhesive layer is 0 to 30 ° C.   The decorative molded body according to any one of claims 1 to 4, wherein the design layer is a metal film or a pattern layer.   The decorative molded body according to claim 5, wherein the metal film is a layer composed of at least one selected from indium, tin, aluminum, zinc, and alloys thereof.   The decorative molded body according to claim 1, wherein the surface protective layer is an acrylic film.   The decorative molded body according to any one of claims 1 to 7, which is used for a vehicle body exterior.