JP2021160164A - Decorative film and decorated molded object - Google Patents

Abstract

To provide a decorative film which exhibits excellent adhesiveness to adherends including a polypropylene resin when a decoration molding is performed under vacuum-heating conditions or under reduced pressure-heating conditions.SOLUTION: This invention relates to a decorative film including a decorative layer and an adhesive layer, wherein the adhesive layer comprises: a block copolymer including a block formed from an isopentane-derived structure; and a terpene-based resin. The decorative film is used for decoration molding under vacuum-heating conditions or under reduced pressure-heating conditions. This invention further relates to a decorated molded object obtained by applying the decorative film to an adherend including a polypropylene resin.SELECTED DRAWING: Figure 1

Description

The present invention relates to a decorative film and a decorative molded product.

Conventionally, when protecting or decorating the surface of automobile interior / exterior parts, home appliance parts, building material parts, etc., the molded body is processed by injection molding or vacuum forming, and then sprayed on the surface of the molded body. Paint was applied by painting, etc., and dried and heat-cured. However, such painting requires not only the problem that the discharge of volatile organic solvent deteriorates the working environment, but also the work process and production equipment for each molded part, and the need for recoating 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 increasingly used as molded bodies for the purpose of reducing the weight of automobile interior / exterior parts, home appliance parts, building material parts, and the like. Spray painting is often unsuitable for decorating a resin molded product, and various methods have been developed to decorate the surface of the resin molded product. Above all, the method of decorating the outermost surface of the molded body with a decorative film to obtain a decorative molded body has a higher degree of freedom in design and productivity than the method of applying or printing on the surface using paint or the like. Has the advantage of being excellent. Further, the decoration method using a decoration film is used for various purposes because it can also decorate the surface of a molded body having three-dimensional unevenness.

For example, Patent Document 1 describes a decorative molding laminate having a base material layer and an adhesive layer, wherein the adhesive layer has a silicone-based pressure-sensitive adhesive layer and an acrylic-based pressure-sensitive adhesive layer. Laminates for use are disclosed. Further, Patent Document 2 discloses a vacuum forming sheet having an adhesive layer on the lower surface of the surface film. Here, an adhesive layer obtained by blending 1.5 to 2.5 equivalents of polyisocyanate with a thermoplastic saturated copolymerized polyester resin and curing the adhesive layer is used.

JP-A-2017-154410 Japanese Unexamined Patent Publication No. 2010-120209

In the decorative molded body, it is naturally required that the adherend and the decorative film are sufficiently adhered to each other and not easily peeled off. However, when decorative molding is performed under vacuum heating conditions or reduced pressure heating conditions, and when a polypropylene resin material is used for the adherend, a conventional adhesive sheet for decorative molding (decorative film) is used. When used, there is a problem that the adhesion of the decorative film to the adherend is not sufficiently exhibited.

Therefore, in order to solve the problems of the prior art, the present inventors are excellent in the adherend containing polypropylene resin when performing decorative molding under vacuum heating conditions or vacuum heating conditions. We proceeded with the study for the purpose of providing a decorative film that exhibits good adhesion.

As a result of diligent studies to solve the above problems, the present inventors have found that in a decorative film having a decorative layer and an adhesive layer, the adhesive layer contains a block composed of an isopentane-derived structure. By blending a block copolymer and a terpene resin, excellent adhesion to an adherend containing a polypropylene resin is exhibited when decorative molding is performed under vacuum heating conditions or reduced pressure heating conditions. We have found that a decorative film can be obtained.
Specifically, the present invention has the following configuration.

[1] A decorative film having a decorative layer and an adhesive layer.
The adhesive layer contains a block copolymer containing a block composed of an isopentane-derived structure and a terpene resin.
A decorative film for decorative molding under vacuum heating conditions or reduced pressure heating conditions.
[2] Block copolymers are
The decorative film according to [1], which is a block copolymer containing a block composed of an isopentane-derived structure and a block composed of a styrene-based polymer.
[3] The terpene resin is at least one selected from the group consisting of terpene resins, aromatic-modified terpene resins and terpene phenol resins.
The softening point of the terpene resin is 60 to 130 ° C.
The decorative film according to [1] or [2], wherein the terpene resin has a number average molecular weight of 300 to 1500.
[4] The decorative film according to any one of [1] to [3], wherein the content of the terpene resin is 40 to 200 parts by mass with respect to 100 parts by mass of the block copolymer.
[5] The decorative film according to any one of [1] to [4], wherein the thickness of the adhesive layer is 0.5 to 20 μm.
[6] A decorative molded body formed by laminating the decorative film according to any one of [1] to [5] to an adherend containing a polypropylene resin.
[7] The decorative molded article according to [6], which is used for automobile members, electronic devices, or building materials.

According to the present invention, it is possible to obtain a decorative film that exhibits excellent adhesion to an adherend containing a polypropylene resin when decorative molding is performed under vacuum heating conditions or reduced pressure heating conditions.

FIG. 1 is a cross-sectional view showing an example of the configuration of a decorative film. FIG. 2 is a cross-sectional view showing an example of the configuration of the decorative molded body.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be based on typical embodiments or specific examples, but the present invention is not limited to such embodiments. In this specification, the numerical range represented by using "~" means a range including the numerical values before and after "~" as the lower limit value and the upper limit value.

(Decorative film)
The present invention relates to a decorative film having a decorative layer and an adhesive layer, which is used for decorative molding under vacuum heating conditions or reduced pressure heating conditions. Here, the adhesive layer contains a block copolymer containing a block composed of an isopentane-derived structure and a terpene-based resin. Since the decorative film of the present invention has the above-mentioned structure, it exhibits excellent adhesion to an adherend containing a polypropylene resin when decorative molding is performed under vacuum heating conditions or reduced pressure heating conditions. Therefore, the decorative film of the present invention is preferably used for bonding to an adherend containing polypropylene resin as a main component.

Conventionally, a polycarbonate resin or an ABS resin has been used as an adherend of a decorative molded product. Therefore, the specific composition of the decorative film for decorating the adherend containing polypropylene resin as a main component has not been sufficiently studied. Therefore, the present inventors have diligently studied the decorative molding of an adherend containing a polypropylene resin as a main component under vacuum heating conditions or vacuum heating conditions. As a result, the present inventors provided a polypropylene resin as a main component by providing an adhesive layer containing a block copolymer containing a block composed of an isopentane-derived structure and a terpene resin in a decorative film. We have succeeded in obtaining a decorative film that exhibits excellent adhesion to the adherend contained in the resin.

FIG. 1 is a cross-sectional view illustrating an example of the configuration of the decorative film of the present invention. As shown in FIG. 1, the decorative film 30 has a decorative layer 21 and an adhesive layer 11. In the decorative film 30, another layer may be provided between the decorative layer 21 and the adhesive layer 11, but in the present embodiment, the decorative layer 21 and the adhesive layer 11 are in direct contact with each other. It is preferable that they are laminated.

The decorative layer 21 may be a single layer, or may be a colored film in which a pigment or dye is kneaded into a base material. Although the decorative layer 21 is drawn as a single layer in FIG. 1, the decorative layer 21 may have a multilayer structure including at least a base material and a decorative layer. When the decorative layer 21 includes a base material and a decorative layer, the decorative layer in the decorative layer 21 is preferably provided on a surface in contact with the adhesive layer 11. Further, the decorative layer may be provided on the outermost surface layer of the decorative film (the opposite surface in contact with the adhesive layer 11). In such a case, the decorative layer is further hardened on the surface layer side separately from the decorative layer. A functional layer such as a coat layer or an antireflection layer may be provided.

The decorative film of the present invention is for decorative molding under vacuum heating conditions or vacuum heating conditions. In the present specification, molding under vacuum heating conditions or vacuum heating conditions is so-called TOM molding. The TOM molding method includes a step of laminating the decorative film on the adherend under vacuum heating conditions or vacuum heating conditions, and a step of crimping the decorative film to the adherend due to a pressure difference.

(Adhesive layer)
The decorative film has an adhesive layer. In the present invention, the adhesive layer may be provided on both sides of the decorative layer, but it is preferable that the adhesive layer is provided on either side of the decorative layer.

In the present embodiment, the adhesive layer preferably contains a block copolymer and a terpene resin. Here, the block copolymer includes a block composed of an isopentane-derived structure. The content of the terpene resin is preferably 40 parts by mass or more, more preferably 45 parts by mass or more, and further preferably 50 parts by mass or more with respect to 100 parts by mass of the block copolymer. It is particularly preferable that the amount is 55 parts by mass or more. The content of the terpene resin is preferably 200 parts by mass or less, more preferably 180 parts by mass or less, and further preferably 160 parts by mass or less with respect to 100 parts by mass of the block copolymer. It is preferably 140 parts by mass or less, and particularly preferably 140 parts by mass or less. By setting the content of the terpene resin within the above range, the interlayer adhesion between the adhesive layer and the polypropylene layer can be enhanced, and further, the interlayer adhesion between the adhesive layer and the decorative layer can be enhanced.

The total content of the block copolymer and the terpene resin is preferably 50% by mass or more, more preferably 60% by mass or more, based on the total mass of the adhesive layer. The total content of the block copolymer and the terpene resin may be 100% by mass with respect to the total mass of the adhesive layer. By setting the total content of the block copolymer and the terpene resin in the above range, the decorative film can exhibit excellent adhesion to the adherend containing the polypropylene resin, and further, it can be attached to the adhesive layer. The interlayer adhesion of the decorative layer can be improved.

The block copolymer contained in the adhesive layer preferably contains a block composed of an isopentane-derived structure and a block composed of a styrene-based polymer. In the present specification, the isopentane-derived structure is the following structure. The block composed of the isopentane-derived structure is a block formed by polymerizing the isopentane-derived structure having the above structure. The isopentane-derived structure is preferably a propylene / ethylene copolymer.

The block composed of the styrene polymer is preferably a block composed of the styrene polymer or the α-methylstyrene polymer.

The block copolymer contained in the adhesive layer may include a block composed of an isopentane-derived structure and a block composed of a styrene-based polymer, and a block composed of another polymer. Examples of the block composed of other polymers include a block composed of an ethylene-derived structure, a block composed of a (meth) acrylic acid ester-based polymer, and the like.

In the block copolymer contained in the adhesive layer, when the block composed of the isopentane-derived structure is A and the block composed of the styrene polymer is B, the block copolymer is a diblock having an AB structure. It may be a copolymer, or it may be a triblock copolymer having an ABA structure or a BAB structure. Further, it may be a block copolymer having a repeating structure of each block such as -AB-AB- structure. Further, as described above, it may be a block copolymer further containing a block composed of another polymer.

The block copolymer contained in the adhesive layer may further have a substituent on the polymer chain, and for example, a block copolymer having a substituent having an unsaturated bond may be used as the substituent.

The block copolymer described above may be produced by polymerization by a known method, but a commercially available product may also be used. As commercially available products, for example, Kuraray's Septon 1020, Septon 2002, Septon 4033, Septon HG252 and the like can be used.

The terpene resin contained in the adhesive layer is preferably at least one selected from the group consisting of terpene resins, aromatic-modified terpene resins and terpene phenol resins. More specifically, α-pinene polymer, β-pinene polymer, dipentene polymer, and terpene-based resins obtained by phenol-modifying, aromatic-modifying, hydrogenating-modifying, or hydrocarbon-modifying these can be mentioned.

The softening point of the terpene resin is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, further preferably 70 ° C. or higher, and particularly preferably 75 ° C. or higher. The softening point of the terpene resin may be 100 ° C. or higher. The softening point of the terpene resin is preferably 130 ° C. or lower, more preferably 125 ° C. or lower. The softening point of the terpene resin is a value measured using an automatic softening point measuring device (EX-719PD4, manufactured by FLEX SCIENTIFIC) according to the method described in JIS K2207.

The number average molecular weight of the terpene resin is preferably 300 or more, more preferably 350 or more, and further preferably 400 or more. The number average molecular weight of the terpene resin is preferably 1500 or less, more preferably 1400 or less, and even more preferably 1300 or less. The number average molecular weight of the terpene resin is a value obtained by measuring by gel permeation chromatography (GPC) and converting it using a calibration curve prepared using standard polystyrene having a known molecular weight.

As the terpene resin, a commercially available product may be used. As commercially available products, for example, YS Resin PX 1150, YS Resin PX 1250, YS Resin TO 125, YS Resin TO 105, YS Polystar T 125, YS Polystar T 80, YS Polystar G 125, etc. manufactured by Yasuhara Chemical Co., Ltd. can be used. can.

The adhesive layer may contain additives in addition to the block copolymers and resins described above. Examples of the additive include an antioxidant (or an antioxidant), a silane coupling agent, a tackifier other than a terpene resin, an oil component, a softener, a cross-linking agent, a pigment, a hydrogen extraction type initiator and the like. be able to.

Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, lactone-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and the like. One type of these antioxidants may be used alone, or two or more types may be used in combination.

Examples of the silane coupling agent include a mercapto-based silane coupling agent containing a mercapto group, an epoxy-based silane coupling agent having an epoxy group, a vinyl-based silane coupling agent having a vinyl group, and the like. Among these, it is preferable to use a mercapto-based silane coupling agent in the application of the present invention. Examples of the mercapto-based silane coupling agent include mercaptotrimethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, triethoxy (2-mercaptoethyl) silane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltri. Examples thereof include ethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 4-mercaptobutyltrimethoxysilane, 10-mercaptodecyltriethoxysilane, 11-mercaptoundecyltrimethoxysilane, and 11-mercaptoundecyltriethoxysilane.

Examples of the tackifier other than the terpene resin include petroleum resins such as styrene resin, rosin resin, C5 resin, C9 resin, and C5 / C9 resin.

As the oil component, paraffin-based or naphthenic system oil is preferable, and paraffin-based system oil is more preferably used because rubber is less likely to deteriorate.

Examples of the hydrogen abstraction type initiator include benzophenone compounds such as methyl benzoylate and 4-methylbenzophenone.

The thickness of the adhesive layer is preferably 0.5 μm or more, and more preferably 1 μm or more. The thickness of the adhesive layer is preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less. In the present embodiment, it is possible to reduce the thickness of the adhesive layer in this way.

(Decorative layer)
The decorative film has a decorative layer. Here, the decorative layer may be a single-layer colored film in which a pigment or dye is kneaded into a base material. Further, the decorative layer may be a multilayer film including a base material and a decorative layer.

When the decorative layer is a multilayer film including a base material and a decorative layer, the decorative layer is preferably a layer provided on the surface of the decorative film on the side where the adhesive layer is in contact. Further, the decorative layer may be provided on the outermost layer of the decorative film (the opposite surface in contact with the adhesive layer), and in this case, the outermost layer is further provided with a functional layer such as a hard coat layer or an antireflection layer. May be good.

The decorative layer is preferably a printed layer. The printing layer is formed by printing on one surface side of the film-like base material using, for example, an ink containing a thermosetting resin, an ultraviolet curable resin, or the like as a main component. For printing, a known printing method such as inkjet printing or screen printing can be adopted. Examples of the film-like substrate to be printed include ABS resin (polymer of acrylonitrile, butadiene, and styrene), AS resin (polymer of acrylonitrile and styrene), acrylic resin, polyethylene terephthalate, and polybutylene terephthalate. , Nylon, polyacetal, polyphenylene oxide, phenol resin, urea resin, melamine resin, liquid crystal polymer, polytetrafluoroethylene, polyvinylidene fluoride, polysulfone, polyether sulfone, polyacetal, polyether ether ketone, polyphenylene sulfide, polyateimide, polyamideimide , Polycarbonate, polyolefin resin (polyethylene, polypropylene, etc.), polystyrene, urethane resin and the like. It is preferable that these base materials can be stretched so as to follow the adherend in the molding step. A transparent film is usually used as the film-like base material, but a colorant such as carbon (graphite) may be blended in order to impart designability, or a colored layer may be used.

The decorative layer may further have a surface protective layer or a print protective layer in order to protect the print layer. The surface protective layer is preferably a layer that is arranged on the most exposed surface side of the decorative layer and has a function of enhancing scratch resistance and weather resistance. Therefore, the surface protective layer is preferably a layer including a curable resin layer, and more preferably a hard coat layer. Among them, the curable resin is preferably a photocurable resin, and more preferably an ultraviolet curable resin. In this case, the resin composition for forming the surface protective layer preferably contains, for example, a photopolymerization initiator in addition to the ultraviolet curable resin. Further, when the decorative layer is formed by printing, it is easily scratched depending on the ink used. Therefore, a print protective layer such as a hard coat layer may be provided on the ink layer to prevent scratches. ..

The surface protective layer may further contain fine particles. Examples of the fine particles include inorganic fine particles, and metal oxides can be preferably exemplified. Further, if necessary, pigments and dyes may be contained. In addition, the surface protective layer contains additives such as a pigment dispersant, a defoaming agent, an ultraviolet absorber, a hulls, an antioxidant, an antistatic agent, an anti-wear agent, and an anti-blocking agent, if necessary. You may.

The decorative layer may further include a protective film or a separator layer if the outermost layer has an adhesive layer. The protective film and the separator layer are provided to temporarily protect the surface protective layer. For example, it is provided to prevent the surface protective layer and the printing layer from being scratched by the time of use. The protective film is preferably a self-adhesive film made of an ethylene-vinyl acetate copolymer, or a slightly adhesive film in which a urethane-based and / or acrylic-based adhesive layer having removability is laminated on a PET film or the like. The separator layer preferably has, for example, a structure in which a release layer such as silicone is provided on the surface of the base material layer as described above. Such a separator layer is peeled off during a manufacturing process or use, and is removed from a decorative film or a decorative molded product.

Examples of the structure of the surface side layer include the following layer structure. If necessary, an adhesive layer may be provided between the layers in order to bond the layers.
(1) A structure consisting of only a base material layer (2) A structure in which a decorative layer and a surface protective layer are provided in this order (3) A structure in which a decorative layer and a base material layer are provided in this order (4) ) A configuration in which the base material layer and the decorative layer are provided in this order (5) A configuration in which the decorative layer, the base material layer, and the surface protective layer are provided in this order (6) The above-mentioned (1) to ( A configuration in which a protective film is further provided on the outermost surface of the configuration of 5) (7) A configuration in which an adhesive layer and a separator layer are further provided on the outermost surface of the configurations (1) to (5) described above.

When a pressure-sensitive adhesive layer is provided for adhering each layer, a known pressure-sensitive adhesive can be used as the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer. Examples of the pressure-sensitive adhesive include natural rubber-based pressure-sensitive adhesives, synthetic rubber-based pressure-sensitive adhesives, acrylic-based pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives. The pressure-sensitive adhesive may be solvent-based, solvent-free, emulsion-based, or water-based.

(Manufacturing method of decorative film)
The method for producing a decorative film of the present invention includes a step of forming an adhesive layer by applying an adhesive composition onto the decorative layer and drying or curing the adhesive composition.

The adhesive composition can be applied by existing methods. When an adhesive composition produced by dissolving in a solvent is used, it can be formed into a sheet by coating with a knife coater or the like and then drying the solvent in a drying oven. On the other hand, when the pressure-sensitive adhesive produced by the kneading method by heating is used, it is possible to form a sheet by using a hot melt coder that can soften the adhesive composition by heating in advance.

(Decorative molded body)
The present invention also relates to a decorative molded body formed by laminating a decorative film to an adherend containing a polypropylene resin. In the decorative molded body, the adherend and at least the decorative film (or the decorative layer in the case of in-mold molding) are integrated via the adhesive layer, and at least the surface of the adherend is at least. A part is covered with a decorative film (or a decorative layer).

FIG. 2 is a cross-sectional view illustrating an example of the configuration of the decorative molded body. As shown in FIG. 2, the decorative molded body 100 has a structure in which the decorative film 30 is laminated on the adherend 50. As shown in FIG. 2, the decorative film 30 has a decorative layer 21 and an adhesive layer 11, and the adhesive layer 11 is directly bonded to the adherend 50.

The adherend contains polypropylene resin. Here, the adherend contains polypropylene resin as a main component. Specifically, the content of the polypropylene resin in the adherend is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more. The content of the polypropylene resin in the adherend may be 100% by mass, and the adherend may be made of polypropylene resin.

The shape of the adherend containing the polypropylene resin is not particularly limited, and may be plate-shaped or may have a three-dimensional three-dimensional shape. Further, the adherend may have an uneven structure on a part of the surface thereof.

The decorative molded body is preferably for automobile members, electronic devices or building materials. The present invention may relate to an automobile member, an electronic device or a building material including the above-mentioned decorative molded body. Examples of automobile parts include parts such as bodies, bumpers, spoilers, mirrors, wheels, emblems, and interior materials. Further, examples of the electronic device include an electronic device such as a home electric appliance and a liquid crystal display device such as a personal computer. Examples of building materials include furniture and building materials. Further, the adherend may be a road material (for example, a traffic sign, a soundproof wall, etc.), a tunnel material (for example, a side wall plate, etc.), a musical instrument, a container, an office product, a sports product, a toy, or the like.

(Manufacturing method of decorative molded product)
The method for producing the decorative molded product preferably includes a step of attaching the decorative film to the adherend. The method for producing the decorative molded product is preferably molding under vacuum heating conditions or vacuum heating conditions, and the above-mentioned decorative film is suitable for decorative molding under vacuum heating conditions or vacuum heating conditions. It is an adhesive sheet.

In the present specification, molding under vacuum heating conditions or vacuum heating conditions is so-called TOM molding. In the TOM molding method, a step of laminating a laminated adhesive sheet for decorative molding on an adherend under vacuum heating conditions or vacuum heating conditions and a pressure difference cause the laminated adhesive sheet for decorative molding to be attached to an adherend. Includes crimping process. Further, in TOM molding, a step of heating the surface of the laminated adhesive sheet for decorative molding to 100 ° C. or higher and 180 ° C. or lower may be included before the step of crimping the laminated adhesive sheet for decorative molding to the adherend. preferable. By heating to 100 ° C. or higher and 180 ° C. or lower, the decorative film is softened, and it becomes easier to follow the shape of the adherend. In this case, it is preferable to use an infrared heater for heating.

In this specification, molding under vacuum heating conditions or reduced pressure heating conditions does not include a method of bringing the laminated body and the molded body into close contact with each other by using a molded body having vacuum holes. .. Specifically, molding under vacuum heating conditions or vacuum heating conditions can be carried out by using the "vacuum forming apparatus" described in Japanese Patent No. 3733564.

The features of the present invention will be described in more detail with reference to Examples and Comparative Examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limited by the specific examples shown below.

<Manufacturing of adhesive composition>
Adhesive composition (A-1)
100 parts by mass of block copolymer (Septon 1020 manufactured by Kuraray Co., Ltd.) having a structure represented by the following structural formula, 60 mass by mass of terpene resin (YS resin PX 1150 manufactured by Yasuhara Chemical Co., Ltd., softening point 115 ° C., number average molecular weight 1000) A part, 0.6 parts by mass of an antioxidant (IRGANOX1010 manufactured by BASF) was dissolved in toluene so that the solid content concentration became 30% by mass to obtain an adhesive composition (A-1).

Adhesive composition (A-2)
The solid content concentration is 30 mass in the same manner as in the method for producing the adhesive composition (A-1) except that a resin having a structure represented by the following structural formula (manufactured by Kuraray Co., Ltd., Septon 2002) is used as the block copolymer. %% Adhesive composition (A-2) was obtained.

Adhesive composition (A-3)
The solid content concentration is 30 mass in the same manner as in the method for producing the adhesive composition (A-1) except that a resin having a structure represented by the following structural formula (Kuraray Co., Ltd., Septon 4033) is used as the block copolymer. %% Adhesive composition (A-3) was obtained.

Adhesive composition (A-4)
The terpene resin (Yasuhara Chemical Co., Ltd., YS resin PX 1150, softening point 115 ° C., number average molecular weight 1000) was changed to terpen resin (Yasuhara Chemical Co., Ltd., YS resin PX 800, softening point 80 ° C. number average molecular weight 700). An adhesive composition (A-4) having a solid content concentration of 30% by mass was obtained in the same manner as in the method for producing the adhesive composition (A-3) except that the addition amount was changed to 100 parts by mass.

Adhesive composition (A-5)
Changed terpene resin (Yasuhara Chemical Co., Ltd., YS resin PX 1150, softening point 115 ° C, number average molecular weight 1000) to aromatic modified terpene resin (Yasuhara Chemical Co., Ltd., YS resin TO 125, softening point 125 ° C, number average molecular weight 800) An adhesive composition (A-5) having a solid content concentration of 30% by mass was obtained in the same manner as in the method for producing the adhesive composition (A-3).

Adhesive composition (A-6)
Other than changing the terpene resin (Yasuhara Chemical Co., Ltd., YS Resin PX 1150, softening point 115 ° C, number average molecular weight 1000) to terpene phenol resin (Yasuhara Chemical Co., Ltd., YS Polystar T 80, softening point 80 ° C, number average molecular weight 500) Obtained an adhesive composition (A-6) having a solid content concentration of 30% by mass in the same manner as in the method for producing the adhesive composition (A-3).

Adhesive composition (B-1)
Adhesive composition (Septon 8004, manufactured by Kuraray Co., Ltd.) except that a hydrogenated polybutadiene resin (manufactured by Kuraray Co., Ltd., Septon 8004) represented by the following structural formula, which does not have an isopentane-derived structure, was used instead of the block copolymer having an isopentan-derived structure. An adhesive composition (B-1) having a solid content concentration of 30% by mass was obtained in the same manner as in the production method of A-1).

Adhesive composition (B-2)
Adhesion with a solid content concentration of 30% by mass in the same manner as the method for producing the adhesive composition (A-3) except that a styrene resin (manufactured by Mitsui Chemicals, FTR8100, number average molecular weight 800) was used instead of the terpene resin. The agent composition (B-2) was obtained.

Adhesive composition (C-1)
In a reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a thermometer and a reflux cooling tube, nbutyl acrylate (BA) and 2-hydroxyethyl acrylate (2HEA) were added so that the mass ratio was 80:20. It was blended and 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in the solution as a radical polymerization initiator. The monomer components were randomly copolymerized by heating the solution to 60 ° C. to obtain a copolymer solution. To 100 parts by mass of the solid content of the copolymer obtained above, 0.11 part by mass of a xylylene diisocyanate compound (Takenate D-110N, manufactured by Mitsui Chemicals, Inc.) was added as a cross-linking agent to obtain a solid content concentration. Ethyl acetate was added so that the content was 30% by mass to obtain an adhesive composition (C-1).

Adhesive composition (C-2)
As an acid component, terephthalic acid: isophthalic acid: adipic acid was blended so that the mass ratio was 30:30:40, and as a glycol component, 1,4-butanediol and 1,6-hexanediol had a mass ratio of 1,4-butanediol. The mixture was blended at a ratio of 25:75 and heated in the presence of a catalyst (tetrabutyl titanate) to obtain a thermoplastic saturated copolyester resin. The thermoplastic saturated copolymer polyester resin obtained above was dissolved in a solvent (methyl ethyl ketone), diluted and stirred so as to be a solution having a solid content concentration of 30% by mass. Next, 2 parts by mass of polyisocyanate (manufactured by Nippon Polyurethane Industry, "Coronate HX" (hexamethylene diisocyanate), solid content concentration 100% by mass) was added to the solution with respect to 100 parts by mass of the thermoplastic saturated copolymer resin. An adhesive composition (C-2) was obtained.

<Making decorative film>
(Example 1)
The adhesive composition (A-1) prepared above was applied to an acrylic film (manufactured by Kuraray, Parapure HI grade 75 μm) using a knife coater so that the thickness of the adhesive layer after drying was 5 μm. Then, it was dried at 100 ° C. for 3 minutes to volatilize and dry the solvent toluene. Next, a glassine-based paper pattern (G6W 60 g / m ² manufactured by Oji Tac Co., Ltd.) was attached to the adhesive layer side with a hand roller to obtain a decorative film provided with the paper pattern.

(Example 2)
A decorative film was obtained in the same manner as in Example 1 except that the adhesive composition (A-1) was changed to the adhesive composition (A-2).

(Example 3)
A decorative film was obtained in the same manner as in Example 1 except that the adhesive composition (A-1) was changed to the adhesive composition (A-3).

(Example 4)
A decorative film was obtained in the same manner as in Example 1 except that the adhesive composition (A-1) was changed to the adhesive composition (A-4).

(Example 5)
A decorative film was obtained in the same manner as in Example 1 except that the adhesive composition (A-1) was changed to the adhesive composition (A-5).

(Example 6)
A decorative film was obtained in the same manner as in Example 1 except that the adhesive composition (A-1) was changed to the adhesive composition (A-6).

(Example 7)
A decorative film was obtained in the same manner as in Example 3 except that the thickness of the adhesive layer after drying was changed to 1 μm.

(Example 8)
A decorative film was obtained in the same manner as in Example 3 except that the thickness of the adhesive layer after drying was changed to 20 μm.

(Comparative Example 1)
A decorative film was obtained in the same manner as in Example 1 except that the adhesive composition (A-1) was changed to the adhesive composition (B-1).

(Comparative Example 2)
A decorative film was obtained in the same manner as in Example 1 except that the adhesive composition (A-1) was changed to the adhesive composition (B-2).

(Comparative Example 3)
A decorative film was obtained in the same manner as in Example 1 except that the adhesive composition (A-1) was changed to the adhesive composition (C-1).

(Comparative Example 4)
A decorative film was obtained in the same manner as in Comparative Example 1 except that the adhesive composition (A-1) was changed to the adhesive composition (C-2).

(Adhesion evaluation)
<Manufacturing of decorative molded products>
Using the decorative films obtained in each Example and Comparative Example, a decorative molded body was produced by the TOM method. First, a plate-shaped molded product made of a decorative film from which the release paper has been peeled off and a polypropylene resin having a thickness of 100 mm × 100 mm × 2.0 mm (Sumitomo Chemical Co., Ltd., Sumikasen (registered trademark) -L GA401) is formed into the molded product. It was set in a TOM molding machine (NGF molding machine manufactured by Fuse Vacuum Co., Ltd.) so that the adhesive layer of the decorative film and the adhesive layer of the decorative film face each other. A decorative molded product was obtained by laminating a decorative film on the molded product at 140 ° C. using a TOM molding machine.
<Evaluation>
After curing the decorative molded product produced above for 24 hours in an environment of 23 ° C. and 50% relative humidity, the adhesion between the decorative film and the polypropylene resin adherend is evaluated in accordance with JIS K 5600-5-6. bottom. Specifically, the adhesion test by the cross-cut method was performed as follows.
First, use a razor to make a notch from the decorative film side so that 100 squares of 1 mm x 1 mm grid can be made, and then press the cellophane tape (manufactured by Nichiban Co., Ltd., CT28) from above with your finger to make the decorative film. After being brought into close contact with the film, it was peeled off. Of the 100 squares, 100/100 is the case where the decorative film is not peeled off in all the squares, 0/100 is the case where the decorative film is peeled off in all the squares, and the squares where the decorative film is not peeled off. Was counted, and the adhesion of the decorative film was evaluated according to the following evaluation criteria.
A: 80/100 to 100/100
B: 50/100 to 79/100
C: 0/100 to 49/100

The decorative film obtained in the examples showed good adhesion to the polypropylene resin adherend. On the other hand, in the decorative film obtained in the comparative example, the adhesion to the polypropylene resin adherend was inferior.

21 Decorative layer 11 Adhesive layer 30 Decorative film 50 Adhesive body 100 Decorative molded body

Claims (7)

A decorative film having a decorative layer and an adhesive layer.
The adhesive layer contains a block copolymer containing a block composed of an isopentane-derived structure and a terpene resin.
A decorative film for decorative molding under vacuum heating conditions or reduced pressure heating conditions. The block copolymer is
The decorative film according to claim 1, which is a block copolymer containing a block composed of an isopentane-derived structure and a block composed of a styrene-based polymer. The terpene resin is at least one selected from the group consisting of terpene resins, aromatic-modified terpene resins and terpene phenol resins.
The softening point of the terpene resin is 60 to 130 ° C.
The decorative film according to claim 1 or 2, wherein the terpene resin has a number average molecular weight of 300 to 1500. The decorative film according to any one of claims 1 to 3, wherein the content of the terpene resin is 40 to 200 parts by mass with respect to 100 parts by mass of the block copolymer. The decorative film according to any one of claims 1 to 4, wherein the thickness of the adhesive layer is 0.5 to 20 μm. A decorative molded product obtained by laminating the decorative film according to any one of claims 1 to 5 to an adherend containing a polypropylene resin. The decorative molded article according to claim 6, which is used for automobile members, electronic devices, or building materials.

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