JP6977835B1 - Decorative film and decorative molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative film exhibiting excellent adhesion to an adherend containing a polypropylene resin, excellent in blocking resistance to a mold, and exhibiting excellent concealing property. Provided. A decorative film 30 having a base material 10 having a decorative layer, an adhesive layer 12 containing a coloring pigment, and a polypropylene layer 14 in this order, and an adherend (50) containing a polypropylene resin for decoration. Decorative film; decorative molded body 100. [Selection diagram] Fig. 1

Description

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

Conventionally, when protecting or decorating the surface of automobile interior / exterior parts, home appliance parts, building material parts, etc., after processing the molded body by injection molding or vacuum forming, the surface of the molded body The paint was applied to the vacuum by spray 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 product, 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. Also 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 a pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer has a silicone-based pressure-sensitive adhesive layer and an acrylic-based pressure-sensitive adhesive layer. The laminate for use is disclosed. Further, Patent Document 2 discloses a vacuum forming sheet having an adhesive layer on the lower surface of the surface film. Here, as the adhesive layer, a thermoplastic saturated copolymerized polyester resin mixed with 1.5 to 2.5 equivalents of polyisocyanate and cured is used.

Patent Document 3 discloses a decorative film used in the injection molding simultaneous transfer decoration method. Here, a three-dimensional molded decorative film for simultaneous transfer of injection molding, in which a release layer, a protective layer, a coloring layer, and an adhesive layer are laminated in this order on a substrate, is disclosed and used as an adhesive layer. Examples of the resin to be used include resins such as acrylic resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, styrene-acrylic copolymer resin, polyester resin, and polyamide resin. There is.

Japanese Unexamined Patent Publication No. 2017-154410 Japanese Unexamined Patent Publication No. 2010-120209 Japanese Unexamined Patent Publication No. 2011-088420

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 a polypropylene resin material is used for the adherend, if a conventional adhesive sheet for decorative molding (decorative film) is used, there is a problem that the adhesiveness of the decorative film to the adherend is not sufficiently exhibited. was there.

Further, when manufacturing a decorative molded body, a method of laminating a decorative film and an adherend may be used by a film insert molding method or an in-mold molding method. In this case, the decorative film may be molded into a desired shape before the molten resin constituting the adherend is injected. However, in such a processing step, the decorative film may not be peeled off from the processing die, and it may be difficult to preprocess the decorative film into a desired shape. As described above, if a defect occurs in the preprocessing stage of the decorative film, the production efficiency of the decorative molded product may be significantly reduced, or an unintended defect may occur in the decorative film itself, which is a problem. Become.

On the other hand, recently, a polypropylene resin adherend using a reuse resin or a resin mixed with a filler or the like to have functionality may be used. When such a polypropylene resin adherend can be seen through, if a conventional decorative film is used, there is a problem that the decorativeness of the decorative film is impaired. No mention is made of concealment in Patent Documents 1 to 3.

The problem to be solved by the present invention is a decorative film that exhibits excellent adhesion to an adherend containing a polypropylene resin, has excellent blocking resistance to a mold, and has excellent hiding power. It is to provide a decorative film that demonstrates the above.

As a result of diligent studies to solve the above problems, the present inventor has made a decorative film by laminating a base material having a decorative layer, an adhesive layer containing a coloring pigment, and a polypropylene layer in this order. , It has been found that a decorative film exhibiting excellent adhesion to an adherend containing a polypropylene resin, excellent blocking resistance to a mold, and exhibiting excellent concealing property can be obtained.
Specifically, the present invention has the following configurations.

[1] A decorative film having a base material having a decorative layer, an adhesive layer containing a coloring pigment, and a polypropylene layer in this order.
A decorative film for decorating an adherend containing polypropylene resin.
[2] The adhesive layer is
A block copolymer containing a block composed of an isopentane-derived structure and a block composed of a styrene-based polymer, and a block copolymer.
The decorative film according to [1], which contains a terpene-based resin.
[3] The terpene resin is at least one selected from the group consisting of terpene resin, aromatic-modified terpene resin and terpene phenol resin.
The softening point of the terpene resin is 60 to 130 ° C.
The decorative film according to [2], wherein the terpene-based resin has a number average molecular weight of 300 to 1500.
[4] The decorative film according to [2] or [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 coloring pigment contains at least one selected from a metal oxide and carbon black.
[6] The decorative film according to any one of [1] to [5], wherein the thickness of the adhesive layer is 0.5 to 20 μm.
[7] The decorative film according to any one of [1] to [6], wherein the polypropylene layer has a thickness of 1 to 30 μm.
[8] The decorative film according to any one of [1] to [7], wherein the decorative film is for decorating an adherend by a film insert molding method or an in-mold molding method.
[9] A decorative molded product obtained by laminating the decorative film according to any one of [1] to [8] to an adherend containing a polypropylene resin.
[10] The decorative molded article according to [9], 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, has excellent blocking resistance to a mold, and exhibits excellent concealing properties. ..

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. FIG. 3 is an evaluation pattern used for the concealment evaluation.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be based on typical embodiments and specific examples, but the present invention is not limited to such embodiments. In the present 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 decorative film of the present invention relates to a decorative film having a base material having a decorative layer, an adhesive layer containing a coloring pigment, and a polypropylene layer in this order. The decorative film of the present invention is for decorating an adherend containing polypropylene 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. Therefore, the decorative film of the present invention is preferably used for bonding to an adherend containing polypropylene resin as a main component.
Further, since the decorative film of the present invention has the above-mentioned structure, it is excellent in blocking resistance to the mold. That is, the decorative film of the present invention is excellent in peelability from the mold. Therefore, when the decorative film is processed into a mold, the decorative film can be easily peeled off from the processing mold, and the subsequent bonding process with the adherend can be smoothly performed. Further, since the decorative film can be easily peeled off from the processing die, it is possible to suppress the occurrence of defects in the decorative film, so that the design of the decorative molded product is not impaired.
Further, since the decorative film of the present invention has the above-mentioned structure, it exhibits excellent concealing property. Therefore, it is preferably used as a decorative film with a concealing function for bonding to a resin adherend mixed with a filler or the like.

Conventionally, a polycarbonate resin or an ABS resin has been used as an adherend of a decorative molded product. Therefore, the specific structure of the decorative film for decorating the adherend containing polypropylene resin as a main component has not been sufficiently studied. Further, when the adherend is decorated to produce a decorative molded body, a film insert molding method or an in-mold molding method may be used, but the processability and processing efficiency of the decorative film at that time may be used. There was still a problem with this. Therefore, the present inventor repeatedly drastically reviewed and examined the layer structure of the decorative film, laminated a polypropylene layer on the outermost layer of the decorative film, and contained a base material having a decorative layer and a colored pigment. A decorative film having an adhesive layer and a polypropylene layer in this order has been produced. As a result, it is a decorative film that exhibits excellent adhesion to an adherend containing polypropylene resin as a main component, and when the decorative film is processed into a mold, the decorative film is used as a processing mold. We succeeded in obtaining a decorative film that can be easily peeled off from.
Further, among the decorative films, the adhesive layer arranged on the adherend side of the decorative layer contains a coloring pigment to sufficiently conceal the color, pattern, foreign matter, etc. of the adherend, and the adherend. We succeeded in suppressing the loss of decorativeness due to the fact that the film can be seen through.

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 includes a base material 10 having a decorative layer, an adhesive layer 12 containing a coloring pigment, and a polypropylene layer 14 in this order. In the decorative film 30, another layer may be provided between the layers, but in the present embodiment, the base material 10 having the decorative layer and the adhesive layer 12 are laminated so as to be in direct contact with each other. It is preferable that the adhesive layer 12 and the polypropylene layer 14 are also laminated so as to be in direct contact with each other. In particular, it is preferable that the adhesive layer 12 and the polypropylene layer 14 are laminated so as to be in direct contact with each other.

In FIG. 1, the base material 10 having a decorative layer is drawn as a single layer for convenience, but the base material 10 having a decorative layer may be a single layer composed of a decorative layer, and at least with the base material. It may have a multi-layer structure including a decorative layer. Above all, the base material 10 having a decorative layer preferably has a multilayer structure including the base material and the decorative layer. When the base material 10 having the decorative layer includes the base material and the decorative layer, the decorative layer in the base material 10 having the decorative layer may be provided so as to be in contact with the adhesive layer 12. In this case, the base material in the base material 10 having the decorative layer is arranged on the outermost layer of the decorative film. Further, a layer such as an easy-adhesion layer for enhancing adhesion may be provided between the decorative layer and the adhesive layer 12.
Further, when the decorative film of the present invention is used for film insert molding, a hard coat layer or antireflection layer is provided on the outermost surface layer (opposite surface in contact with the adhesive layer 12) of the base material 10 having the decorative layer, in addition to the decorative layer. A functional layer such as a layer may be provided.
On the other hand, when the decorative film of the present invention is used for in-mold molding, the decorative layer of the base material 10 having the decorative layer is always provided on the surface in contact with the adhesive layer 12, and the base material and the decorative layer are formed after molding. By using a base material having a mold release property so that the film can be easily peeled off, or by providing a mold release layer between the base material and the decorative layer, the base material (release layer) and the decorative layer come into contact with each other. It is preferable that it is configured as such.

The decorative film of the present invention is preferably used for decorating an adherend by a film insert molding method or an in-mold molding method. In the film insert molding method and the in-mold molding method, the decorative film is processed into a three-dimensional shape in advance, placed in the cavity of the mold, and the molten resin constituting the adherend is injected into the mold. A decorative molded body in which a decorative film and an adherend are integrated can be obtained.

(Adhesive layer)
The decorative film has an adhesive layer. In the present invention, a base material having a decorative layer and a polypropylene layer are laminated on both sides of the adhesive layer, and the adhesive layer is not exposed in the decorative film.

-Coloring pigment-
The adhesive layer contains a colored pigment.
The coloring pigment is more preferably at least one kind selected from a black pigment and a white pigment, and it is more preferable to use both in combination. By using a black pigment and a white pigment together as the coloring pigment, it is possible to more effectively enhance the concealing property of the decorative film (the degree to which the adherend cannot be seen through when the decorative molded body is used). .. The coloring pigment may contain other coloring pigments in addition to the black pigment and the white pigment.
Further, the coloring pigment is more preferably at least one kind selected from a metal oxide and carbon black, and it is more preferable to use both in combination. By using a metal oxide and carbon black in combination as the coloring pigment, the concealing property of the decorative film can be more effectively enhanced without impairing the decorative property. The coloring pigment may contain other coloring pigments in addition to the metal oxide and carbon black.

Metal oxides include copper oxide, iron tetraoxide, manganese dioxide, titanium oxide, lead oxide, zinc oxide, zirconium oxide, barium titanate, potassium titanate, iron titanate, copper-chromium oxide, copper-manganese. Examples thereof include oxides, copper-iron-manganese oxides, copper-chromium-manganese oxides or copper-iron-chromine oxides, titanium black and the like. Among them, the metal oxide is more preferably a metal oxide whose metal type is selected from titanium, lead, zinc, copper, iron and manganese, and particularly preferably a white metal oxide, and titanium oxide. Is more particularly preferable. By selecting the above type as the coloring pigment, the coloring stability becomes good, and the hiding power of the decorative film can be more effectively enhanced.

The primary average particle size of the coloring pigment is preferably 0.01 μm or more. Further, the primary average particle size of the coloring pigment is preferably less than 5 μm, more preferably less than 3 μm, further preferably less than 1 μm, and particularly preferably less than 0.5 μm. By setting the primary average particle size of the coloring pigment within the above range, the concealing property of the decorative film can be more effectively enhanced without impairing the adhesiveness.

When a white pigment (particularly a metal oxide such as titanium oxide) is used as the coloring pigment, the content of the coloring pigment is 1 part by mass with respect to 100 parts by mass of a block copolymer containing a block composed of an isopentan-derived structure. The above is preferable, it is more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more. When a white pigment is used as the coloring pigment, the content of the coloring pigment is preferably 30 parts by mass or less with respect to 100 parts by mass of the block copolymer containing the block composed of the isopentane-derived structure. It is more preferably parts by mass or less, and particularly preferably 15 parts by mass or less. By setting the content of the white pigment within the above range, the concealing property of the decorative film can be more effectively enhanced without impairing the adhesiveness.
When a black pigment (particularly carbon black) is used as the coloring pigment, the content of the coloring pigment is 0.1 part by mass or more with respect to 100 parts by mass of the block copolymer containing the block composed of the isopentane-derived structure. It is preferable, it is more preferably 1 part by mass or more, and further preferably 2 parts by mass or more. When a black pigment is used as the coloring pigment, the content of the coloring pigment is preferably 20 parts by mass or less with respect to 100 parts by mass of the block copolymer containing the block composed of the isopentane-derived structure. It is more preferably parts by mass or less, and particularly preferably 5 parts by mass or less. By setting the content of the black pigment within the above range, the concealing property of the decorative film can be more effectively enhanced without impairing the adhesiveness.
When the white pigment and the black pigment are used in combination as the coloring pigment, the preferable range of the content of the coloring pigment is the same as the preferable range when the white pigment or the black pigment is used alone.

The colored pigment is preferably mixed with a block copolymer containing a block composed of an isopentane-derived structure and a terpene-based resin in the state of the colored pigment composition dispersed in the dispersed resin. Examples of the dispersed resin include polyester resin, urethane resin, acrylic resin, polyether resin, phenol resin, rosin resin and the like. The preferable range of the content of the coloring pigment with respect to the block copolymer containing the block composed of the isopentane-derived structure is the preferable range of the value converted into the content of only the coloring pigment excluding the dispersion resin from the coloring pigment composition. be.

-Resin-
In the present embodiment, the adhesive layer preferably further contains a resin.
The adhesive layer preferably contains a block copolymer and a terpene-based resin as the resin. Here, the block copolymer includes a block composed of an isopentane-derived structure and a block composed of a styrene-based polymer. 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 base material having the decorative layer can be enhanced. can.

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 adhesive layer can more effectively increase the interlayer strength between the base material having the decorative layer and the polypropylene layer.

-Block copolymer-
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 obtained by polymerizing the isopentane-derived structure having the above structure. The isopentane-derived structure is preferably a propylene / ethylene copolymer.

The block made of a styrene-based polymer is preferably a block made of a styrene polymer or an 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, as well as 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. The block copolymer contained in the adhesive layer may contain a block composed of an ethylene-derived structure, which facilitates the combined use of metal oxide and carbon black without impairing the adhesiveness to the polypropylene resin, and has a concealing property. It is preferable from the viewpoint of enhancing.

In the block copolymer contained in the adhesive layer, when the block composed of isopentan-derived structure is I and the block composed of styrene polymer is S, the block copolymer is a diblock having an IS structure. It may be a copolymer, or it may be an IS-I structure or a triblock copolymer having an SI-S structure. Further, it may be a block copolymer having a repeating structure of each block such as -IS-IS- 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 its polymer chain, and for example, a block copolymer having a substituent having an unsaturated bond may be used as the substituent.

The above-mentioned block copolymer 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.

-Terpene resin-
The adhesive layer preferably contains a terpene resin. The terpene resin contained in the adhesive layer is preferably at least one selected from the group consisting of terpene resin, aromatic-modified terpene resin and terpene phenol resin. 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. By setting the softening point of the terpene resin within the above range, the decorative film can exhibit excellent adhesion to the adherend containing the polypropylene resin. Further, by setting the softening point of the terpene resin within the above range, it is possible to improve the interlayer adhesion between the adhesive layer and the decorative layer. 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 further preferably 1300 or less. By setting the number average molecular weight of the terpene-based resin within the above range, the decorative film can exhibit excellent adhesion to an adherend containing a polypropylene resin. Further, by setting the number average molecular weight of the terpene resin within the above range, it is possible to improve the interlayer adhesion between the adhesive layer and the decorative layer. 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. may be used. can.

-Additives-
The adhesive layer may contain additives in addition to the above-mentioned colored pigments, block copolymers and terpene-based resins. 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-based resin include petroleum-based resins such as styrene-based resin, rosin-based resin, C5-based resin, C9-based resin, and C5 / C9-based 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-drawing initiator include benzophenone compounds such as methyl benzoylate and 4-methylbenzophenone.

-Thickness of adhesive layer-
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 40 μm or less, preferably 20 μm or less, more preferably 15 μm or less, and even more preferably 10 μm or less. In the present invention, even if the thickness of the adhesive layer is reduced as in the above-mentioned preferable range, the hiding property can be sufficiently exhibited by controlling the content of the coloring pigment in the preferable range.

(Base material with a decorative layer)
The decorative film has a base material having a decorative layer. Here, the base material having a decorative layer preferably includes a film-shaped base material and a decorative layer.

The decorative layer constituting the base material having the decorative layer may be a layer provided on the outermost surface (opposite side of the side in contact with the adhesive layer) of the decorative film, or a layer provided on the side in contact with the adhesive layer. However, it is preferable that the layer is provided on the surface on the side in contact with the adhesive layer. In particular, when the decorative film is used for in-mold molding, the decorative layer needs to be provided on the surface on the side in contact with the adhesive layer. On the other hand, when the decorative film is used for film insert molding, it is preferable that the decorative layer is provided on the outermost surface of the decorative film (the opposite surface on the side where the adhesive layer is in contact), and in this case, the decorative layer is further formed on the outermost surface layer. May be provided with a functional layer such as a hard coat layer or an antireflection layer.

The decorative layer is preferably a print layer. The printing layer is formed by printing on one surface side of the film-shaped substrate 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. Further, although a transparent film is usually used as the film-like base material, a colorant such as carbon (graphite) may be blended in order to impart designability, or a colored layer may be used.

The base material having a decorative layer may further have a surface protective layer and 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 base material having a 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 print layer to prevent scratches.

The surface protective layer may further contain fine particles. Examples of the fine particles include inorganic fine particles, and a metal oxide 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-wearing agent, and an anti-blocking agent, if necessary. You may.

The base material having a decorative layer may further include a protective film and a separator layer when 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. For example, the separator layer preferably has 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 body.

Examples of the configuration of the base material having the decorative layer include the following layer configurations. In addition, in order to bond each layer, a pressure-sensitive adhesive layer or an easy-adhesive layer may be provided between the layers, if necessary.
(1) Configuration in which the base material layer, print layer, and print protection layer are provided in this order (2) Configuration in which the surface protection layer, print layer, and base material layer are provided in this order (3) Base material layer, printing Configuration in which layers are provided in this order (4) Configuration in which functional layers, substrate layers, and printing layers are provided in this order (generally, this configuration is used for film insert molding and not for in-mold molding. )
(5) A structure in which a base material layer, a release layer, a print protection layer, and a print layer are provided in this order (generally, this structure is used for in-mold molding and not for film insert molding).
(6) A structure in which a protective film is further provided on the outermost surface of the above-mentioned configurations (1) to (5) (7) An adhesive layer and a separator are further provided on the outermost surface of the above-mentioned configurations (1) to (5). Configuration with layers

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, silicone-based pressure-sensitive adhesives, and the like. The pressure-sensitive adhesive may be solvent-based, solvent-free, emulsion-based, or water-based.

(Polypropylene layer)
The decorative film has a polypropylene layer. The thickness of the polypropylene layer is preferably 1 μm or more, more preferably 2 μm or more, and further preferably 3 μm or more. The thickness of the polypropylene layer is preferably 30 μm or less, more preferably 25 μm or less, further preferably 20 μm or less, further preferably 15 μm or less, and particularly preferably 10 μm or less. preferable.

(Manufacturing method of decorative film)
In the method for producing a decorative film of the present invention, an adhesive composition containing a colored pigment is applied onto a substrate having a decorative layer, and the adhesive layer is dried or cured to form an adhesive layer containing the colored pigment. It is preferable to include a step of forming and a step of forming a polypropylene layer on the adhesive layer or laminating a polypropylene film. Alternatively, the method for producing a decorative film of the present invention comprises a step of applying an adhesive composition containing a coloring pigment on a polypropylene layer and drying or curing the adhesive layer to form an adhesive layer containing the coloring pigment. , The step of adhering a base material having a decorative layer on the adhesive layer may be included.

-Preparation of adhesive composition-
The adhesive composition can be prepared by an existing method.
For example, the resin and the coloring pigment may be dissolved in a solvent to prepare an adhesive composition. Further, the resin and the coloring pigment may be heated and kneaded to prepare an adhesive composition.

-Coating the adhesive composition-
The adhesive composition can be applied by existing methods. When the 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 adhesive composition 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.

When forming a polypropylene layer on an adhesive layer formed on a base material having a decorative layer, a method of laminating a polypropylene film on the adhesive layer and crimping it can be adopted. As a bonding method, an existing bonding machine can be used. For example, the adhesive layer and the polypropylene layer may be bonded by a combination of roll-to-roll, sheet-to-roll, roll-to-sheet, sheet-to-sheet, etc., and at this time, they may be bonded while being pressed by a nip roll or a roller. preferable. Further, even when the adhesive layer is formed on the polypropylene layer, the base material having the decorative layer can be bonded by the same method.

When the polypropylene layer is formed on the adhesive layer formed on the base material having the decorative layer, the polypropylene layer is formed on the adhesive layer by melt extrusion using a T-die by the extrusion laminating method. It may be formed.

<Decorative molded body>
The decorative molded body of the present invention is formed by laminating the decorative film of the present invention 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 polypropylene layer, and at least the surface of the adherend is at least. A part is covered with a decorative film (or a decorative layer).
In addition, in the decorative molded body of the present invention obtained by in-mold molding, there is also an embodiment in which the base material is peeled off from the base material having the decorative layer of the decorative film of the present invention and only the decorative layer remains. included.

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 base material (or a decorative layer in the case of in-mold molding) 10 having a decorative layer, an adhesive layer 12, and a polypropylene layer 14, and is a polypropylene layer. 14 is directly attached to the adherend 50. In FIG. 2, the polypropylene layer 14 is drawn as a layer in order to explain the configuration of the decorative molded body 100 in an easy-to-understand manner. However, in the actually obtained decorative molded body, the polypropylene layer 14 is used. The adherend 50 is integrated, and the boundary thereof may not be known.

The adherend contains polypropylene resin. Here, it is preferable that 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 polypropylene resin content in the adherend may be 100% by mass, and the adherend may be made of polypropylene resin.
The present invention is preferably used when the polypropylene resin content in the adherend is less than 100% by mass and a polypropylene resin containing an additive such as a polypropylene resin which is a reuse resin or a filler is used. In the present invention, the content of the polypropylene resin in the adherend is preferably 99% by mass or less, more preferably 95% by mass or less, and particularly preferably 90% by mass or less.

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 members 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 a decorative molded product preferably includes a step of attaching the decorative film of the present invention to an adherend. Examples of the method for producing a decorative molded product include hot press molding, in-mold molding, film insert molding, molding under vacuum conditions or reduced pressure conditions, and the like. Above all, the method for producing the decorative molded body is preferably a film insert molding method or an in-mold molding method, and the above-mentioned decorative film is suitable for decorative molding in the film insert molding method or the in-mold molding method. It is a decorative film.

When in-mold molding is adopted as a method for manufacturing a decorative molded body, a decorative film is fixed in a mold of an injection molding machine, and a resin composition containing a polypropylene resin constituting an adherend in the mold. An article is injected to solidify the resin composition, and then only the substrate having the decorative layer is removed to obtain a decorative molded product. When a film insert molding method is adopted as a method for manufacturing a decorative molded body, a resin composition in which the decorative film is fixed in a molding mold of an injection molding machine and a polypropylene resin is contained in the molding mold. Is injected and the resin composition is solidified to obtain a decorative molded product.

Hereinafter, 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 limiting by the specific examples shown below.
Examples 1, 2, 7 to 9 are reference examples.

<Preparation of adhesive composition>
Adhesive composition (A-1)
100 parts by mass of a block copolymer (Septon 1020 manufactured by Kuraray Co., Ltd .; a resin represented by the following structural formula) containing a block composed of a structure derived from isopentan, a terpene resin (YShara Chemical Co., Ltd., YS resin PX 1150, softening point 115). 60 parts by mass (° C, number average molecular weight 1000), 0.6 parts by mass of antioxidant (BASF, IRGANOX1010), 20 parts by mass of titanium oxide pigment composition (Toyo Color, Multilac S-161 White) as a coloring pigment. Parts (10 parts by mass in terms of titanium oxide) were dissolved in toluene so that the solid content concentration became 30% by mass to obtain an adhesive composition (A-1).

Adhesive composition (A-2)
A block copolymer containing a block composed of another isopentane-derived structure instead of Septon 1020, which is a block copolymer containing a block composed of an isopentan-derived structure (Claret Co., Ltd., Septon 2002; represented by the following structural formula). (Resin) is used, and the carbon black pigment composition (multi-rack A 903 manufactured by Toyo Color Co., Ltd.) is adhered except that 30 parts by mass (3 parts by mass in terms of carbon black) is used instead of the titanium oxide pigment composition. An adhesive composition (A-2) having a solid content concentration of 30% by mass was obtained in the same manner as in the method for producing the agent composition (A-1).

Adhesive composition (A-3)
A block copolymer containing a block composed of another isopentane-derived structure instead of Septon 1020, which is a block copolymer containing a block composed of an isopentan-derived structure (Claret, Septon 4033; represented by the following structural formula). In addition to 20 parts by mass (10 parts by mass in terms of titanium oxide) of a titanium oxide pigment composition (manufactured by Toyo Color Co., Ltd., Multilac S-161 White) as a coloring pigment, a carbon black pigment composition is further used. (Multi-rack A 903 manufactured by Toyo Color Co., Ltd.) The solid content concentration is 30% by mass in the same manner as in the method for producing the adhesive composition (A-1) except that 30 parts by mass (3 parts by mass in terms of carbon black) is used. The adhesive composition (A-3) of the above was obtained.

Adhesive composition (A-4)
Other than changing to another terpene resin (Yasuhara Chemical Co., Ltd., YS resin PX 800, softening point 80 ° C., number average molecular weight 700) instead of the terpene resin YS resin PX 1150, and changing the addition amount to 100 parts by mass. Obtained an adhesive composition (A-4) 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 (A-5)
Adhesive composition (A-3) except that the terpene resin YS resin PX 1150 was replaced with an 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 production method of.

Adhesive composition (A-6)
Preparation of adhesive composition (A-3) except that terpene phenol resin (YShara Chemical Co., Ltd., YS Polystar T80, softening point 80 ° C., number average molecular weight 500) was changed instead of the terpene resin YS resin PX 1150. An adhesive composition (A-6) having a solid content concentration of 30% by mass was obtained in the same manner as in the method.

Adhesive composition (B-1)
Adhesive composition except that a hydrogenated polybutadiene resin (manufactured by Kuraray Co., Ltd., Septon 8004) represented by the following structural formula, which does not have an isopentan-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)
The solid content is the same as the method for producing the adhesive composition (A-3) except that a styrene resin (manufactured by Mitsui Chemicals Co., Ltd., FTR8100, number average molecular weight 800) is used instead of the terpene resin YS resin PX 1150. An adhesive composition (B-2) having a concentration of 30% by mass was obtained.

Adhesive composition (B-3)
An adhesive composition (B-3) 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-1) except that the titanium oxide pigment composition as a coloring pigment was not added. rice field.

Adhesive composition (C-2)
As an acid component, terephthalic acid: isophthalic acid: adipic acid is blended so that the mass ratio is 30:30:40, and as a glycol component, 1,4-butanediol and 1,6-hexanediol have a mass ratio. 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 copolymerized polyester resin. The thermoplastic saturated copolymer 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, by adding 2 parts by mass of polyisocyanate (manufactured by Nippon Polyurethane Industry, "Coronate HX" (hexamethylene diisocyanate), solid content concentration 100% by mass) to the solution with respect to 100 parts by mass of the thermoplastic saturated copolymerized polyester resin. An adhesive composition (C-2) was obtained.

<Making decorative film>
(Example 1)
A decorative layer was provided by printing on an acrylic film (manufactured by Kuraray, Parapure HI grade 75 μm) used as a base material, and a base material having the decorative layer was prepared.
The adhesive composition (A-1) prepared above was applied to the decorative layer of the base material having the decorative layer prepared above using a knife coater so that the thickness of the adhesive layer after drying was 20 μm. After coating, it was dried at 100 ° C. for 3 minutes to volatilize and dry the solvent toluene. Next, a polypropylene film (EM-501 5 μm manufactured by Oji F-Tex Co., Ltd.) was bonded to the adhesive layer side with a hand roller to obtain a decorative film.

(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)
The thickness of the adhesive layer after drying was changed to 10 μm, and the polypropylene film was changed to a polypropylene film having a thickness of 20 μm (manufactured by Oji F-Tex Co., Ltd., SS-121, 20 μm). I got a film.

(Example 8)
The decorative film is the same as in Example 3 except that the thickness of the adhesive layer after drying is changed to 10 μm and the polypropylene film is a polypropylene film having a thickness of 12 μm (MAM-411, 12 μm manufactured by Oji F-Tex Co., Ltd.). Got

(Comparative Example 1)
A decorative film having no polypropylene layer was obtained in the same manner as in Example 1 except that the polypropylene film was not bonded.

(Example 9)
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).

(Example 10)
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 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 (C-1).

(Comparative Example 3)
A decorative film having an adhesive layer and a polypropylene 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>
(Making a decorative molded product)
Using the decorative films obtained in each Example and Comparative Example, a decorative molded body was produced by a film insert molding method. First, a decorative film was set inside a plate-shaped mold having a size of 100 mm × 100 mm × 2 mm so that the polypropylene layer was on the injection resin side. Subsequently, after heating the mold in which the decorative film is set to 60 ° C, polypropylene (manufactured by Mitsubishi Chemical Co., Ltd., Novatec ^TM PP) melted by heating to 200 ° C is poured into the mold, cooled to room temperature, and then decorated. A decorative molded body was obtained by taking out the molded body from the mold.

(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. did. Specifically, the adhesion test by the cross-cut method was performed as follows.
First, use a razor from the decorative film side to make a notch so that 100 squares of 1 mm x 1 mm cross cut can be made, and then press the cellophane tape (manufactured by Nichiban Co., Ltd., CT28) from above with your finger. After being brought into close contact with the decorative 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
In practice, the adhesion evaluation is preferably A or B, more preferably A.

<Blocking resistance evaluation>
Using the decorative films obtained in each Example and Comparative Example, the blocking resistance to the mold (adhesion to the mold) was evaluated. First, a decorative film was cut out to a size of 25 mm × 300 mm to prepare a film. This decorative film was pressure-bonded to a SUS304 steel sheet (surface finish BA) heated to 50 ° C. by a method according to JIS Z 0237 using a 2 kg roller. After 5 minutes from crimping, the adhesive strength was measured at a peeling speed of 300 mm / min and a peeling angle of 180 °, and evaluated according to the following criteria.
A: Adhesive strength is less than 0.05N / 25mm.
B: Adhesive strength is 0.05 N / 25 mm or more.
In practice, the adhesion evaluation is preferably A.

<Evaluation of concealment>
A film for evaluation of concealment was produced in the same manner as the decorative films of each Example and Comparative Example except that the decorative layer was not provided. Specifically, any one of the adhesive compositions (A-1) to (A-6), (B-1) to (B-3) or (C-2) is used with a knife coater. The surface of the acrylic film used as the base material is coated so that the thickness of the adhesive layer after drying is the same as that of each Example and Comparative Example, and then dried at 100 ° C. for 3 minutes to volatilize the solvent toluene. I let you. In this way, a film for hiding property evaluation having a base material, an adhesive layer and a polypropylene layer was obtained.
The printed surface of the art paper on which the evaluation pattern shown in FIG. 3 was printed was set so as to be in contact with the polypropylene layer of the film for hiding property evaluation, and heat-laminated using a heating roll at 150 ° C. to obtain an evaluation sample. rice field.
The obtained evaluation sample was evaluated according to the following evaluation criteria.
A: Halftone dots with a halftone dot ratio of 6.25% or more cannot be seen.
B: Halftone dots with a halftone dot ratio of 6.25% cannot be seen.
C: Halftone dots with a halftone dot ratio of 6.25% can be seen.
In practice, the adhesion evaluation is preferably A or B, more preferably A.

From Tables 1 and 2 above, the decorative film obtained in the examples showed good adhesion to the polypropylene resin adherend, good blocking resistance to the mold, and excellent hiding property. showed that.
On the other hand, the decorative film of Comparative Example 1 having no polypropylene layer was inferior in blocking resistance to the mold.
The decorative film of Comparative Example 2 in which the adhesive layer did not contain a coloring pigment was inferior in hiding power.
The decorative film of Comparative Example 3 in which the adhesive layer did not contain a coloring pigment and did not have a polypropylene layer was inferior in adhesion to a polypropylene resin adherend, blocking resistance to a mold, and concealing property. ..
The evaluation sample used in the concealment evaluation is black on a white background and the evaluation pattern shown in FIG. 3 is printed, but the evaluation sample on a white background is cyan, magenta or yellow and the evaluation pattern shown in FIG. 3 is printed. The results were similar to those in Tables 1 and 2.

10 Base material with decorative layer 12 Adhesive layer 14 Polypropylene layer 30 Decorative film 50 Adhesive body 100 Decorative molded body

Claims (10)

A decorative film having a base material having a decorative layer, an adhesive layer containing a coloring pigment, and a polypropylene layer in this order.
Ri der for adherends decorated comprising polypropylene resin,
The adhesive layer contains a block copolymer containing a block composed of an isopentan-derived structure, a block composed of an ethylene-derived structure, and a block composed of a styrene-based polymer.
The thickness of the polypropylene layer is Ru der below 10 [mu] m, the decorative film. The adhesive layer contains Te point pen-based resins, the decorative film of claim 1. The terpene-based resin is at least one selected from the group consisting of terpene resin, aromatic-modified terpene resin and terpene phenol resin.
The softening point of the terpene resin is 60 to 130 ° C.
The decorative film according to claim 2, wherein the terpene-based resin has a number average molecular weight of 300 to 1500. The decorative film according to claim 2 or 3, wherein the content of the terpene-based 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 coloring pigment contains at least one selected from a metal oxide and carbon black. The decorative film according to any one of claims 1 to 5, wherein the thickness of the adhesive layer is 0.5 to 20 μm. The decorative film according to any one of claims 1 to 6, wherein the polypropylene layer has a thickness of 1 to 10 μm. The decorative film according to any one of claims 1 to 7, wherein the decorative film is for decorating an adherend by a film insert molding method or an in-mold molding method. A decorative molded product obtained by laminating the decorative film according to any one of claims 1 to 8 to an adherend containing a polypropylene resin. The decorative molded article according to claim 9, which is used for automobile members, electronic devices, or building materials.

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