JP6834314B2 - Decorative sheet, decorative resin molded product, and manufacturing method of decorative resin molded product - Google Patents

Description

The present invention relates to a decorative sheet, a decorative resin molded product, and a method for manufacturing a decorative resin molded product.

Conventionally, in order to give a metallic design to vehicle interior / exterior parts, building material interior materials, home appliance housings, etc., members having a resin surface coated with metal such as metal plating or metal coating have been used. However, when performing metal plating, metal coating, etc., it is necessary to take measures such as treatment of wastewater containing metal and measures against solvent vapor. Moreover, in general, the yield of these members is not good.

Therefore, in recent years, as these members, a decorative resin molded product in which a decorative sheet having a metallic tone is laminated on the surface of the resin molded product has been used (see, for example, Patent Document 1). In the production of decorative resin molded products, a molding method in which a decorative sheet to which a design has been given in advance is integrated with the resin by injection molding or the like is used.

In such a decorative sheet, a metal thin film layer is formed on the base material layer, and the metal thin film layer is generally used for the purpose of improving the scratch resistance of the decorative resin molded product. A surface protective layer is formed on top of it. Further, a primer layer and the like are provided in order to improve the adhesion of the base material layer, the metal thin film layer, the surface protection layer and the like.

As a typical example of a molding method for a decorative resin molded product using a decorative sheet, the decorative sheet inserted into the mold during injection molding is integrated with the molten resin injected into the cavity. Examples include the injection molding simultaneous decoration method. In the injection molding simultaneous decoration method, generally, after integrating the decoration sheet with the resin, a step of trimming an excess portion of the decoration sheet is performed. As a trimming method, for example, a method of striking beads on an extra portion of a decorative sheet is known.

On the other hand, the decorative sheet provided with the metal thin film layer has a problem that the metal thin film layer is easily oxidized and discolored when exposed to a high temperature environment or a moist heat environment. As a method for suppressing such discoloration, for example, Patent Document 2 proposes a method in which the metal thin film layer has an island-like structure and the adhesive layer adhering to the metal thin film layer is a non-vinyl chloride resin. ..

Japanese Unexamined Patent Publication No. 2011-167844 Japanese Unexamined Patent Publication No. 2007-136755

However, as a result of studies by the present inventors, the method of Patent Document 2 using a non-vinyl chloride resin for the adhesive layer is insufficient in the effect of suppressing discoloration of the metal thin film layer in a high temperature environment or a moist heat environment. Met.

Further, when the decorative sheet is highly flexible, although it is excellent in moldability, there is a problem that the trimming property after integrating the decorative sheet with the resin is lowered. In order to solve this problem, when a hard resin such as acrylic resin is used for the base material layer, the base material layer made of acrylic resin and the metal thin film layer are brought into close contact with each other by the adhesive layer of Patent Document 2. There was also the problem of not being able to do it.

Under such circumstances, the present invention provides a decorative sheet having excellent trimming property after molding, preferably suppressing discoloration in a high temperature environment or a moist heat environment, and further having excellent adhesion. The main purpose.

The present inventor has made diligent studies to solve the above problems. As a result, at least in the decorative sheet composed of a laminated body including a base material layer, an adhesive layer, a first primer layer, a metal thin film layer, a second primer layer, and a surface protection layer in this order. The base material layer is made of acrylic resin, the first primer layer is made of polyester resin, and the adhesive layer contains a cured product of a resin having a glass transition point of 65 ° C. to 140 ° C. It has been found that the trimming property after molding is excellent, discoloration in a high temperature environment or a moist heat environment is suitably suppressed, and further, the adhesion is excellent. The present invention is an invention completed by further studying based on these findings.

That is, the present invention provides the inventions of the following aspects.
Item 1. It is composed of a laminate having at least a base material layer, an adhesive layer, a first primer layer, a metal thin film layer, a second primer layer, and a surface protection layer in this order.
The base material layer is made of acrylic resin.
The first primer layer is made of a polyester resin.
The adhesive layer is a decorative sheet containing a cured resin having a glass transition point of 65 ° C. or higher and 140 ° C. or lower.
Item 2. Item 2. The decorative sheet according to Item 1, wherein the second primer layer is composed of at least one selected from the group consisting of polyester resin, polyurethane resin, acrylic resin, and polyolefin resin.
Item 3. Item 2. The decorative sheet according to Item 1 or 2, wherein the resin of the adhesive layer contains an acrylic resin.
Item 4. Item 2. The decorative sheet according to any one of Items 1 to 3, wherein the base material layer has a thickness of 50 μm or more and 250 μm or less.
Item 5. The metal thin film layer is composed of at least one metal selected from the group consisting of tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and alloys containing at least one of these. Item 4. The decorative sheet according to any one of Items 1 to 4.
Item 6. It is composed of a laminate having at least a molding resin layer, a base material layer, an adhesive layer, a first primer layer, a metal thin film layer, a second primer layer, and a surface protection layer in this order.
The base material layer is made of acrylic resin.
The first primer layer is made of a polyester resin.
The adhesive layer is a decorative resin molded product containing a cured product of a resin having a glass transition point of 65 ° C. or higher and 140 ° C. or lower.
Item 7. The step of heating the decorative sheet according to any one of Items 1 to 5 and
The process of integrating the heated decorative sheet and the molding resin,
The process of trimming unnecessary parts of the decorative sheet and
A method for manufacturing a decorative resin molded product.
Item 8. Item 8. The method for manufacturing a decorative resin molded product according to Item 7, wherein the trimming step is a trimming step in which beads are struck on an unnecessary portion of the decorative sheet.

According to the present invention, it is possible to provide a decorative sheet having excellent trimming property after molding, preferably suppressing discoloration in a high temperature environment or a moist heat environment, and having excellent adhesion. Further, according to the present invention, it is possible to provide a decorative resin molded product using the decorative sheet and a method for producing the same.

It is a schematic sectional view of an example of the decorative sheet which concerns on this invention. It is a schematic sectional view of an example of the decorative sheet which concerns on this invention. It is a schematic sectional view of an example of the decorative resin molded article which concerns on this invention.

1. 1. Decorative sheet The decorative sheet of the present invention is composed of a laminate having a base material layer, an adhesive layer, a first primer layer, a metal thin film layer, a second primer layer, and a surface protective layer in this order. The base material layer is made of acrylic resin, the first primer layer is made of polyester resin, and the adhesive layer contains a cured product of a resin having a glass transition point of 65 ° C. to 140 ° C. It is characterized by that. In the decorative sheet of the present invention, the base material layer is made of acrylic resin, and the adhesive layer provided between the metal thin film layer and the surface protective layer cures the resin having the specific glass transition point. In addition, since a first primer layer made of polyester resin is provided between the adhesive layer and the metal thin film layer, it has excellent trimming property after molding and is in a high temperature environment. Discoloration in a moist heat environment is preferably suppressed, and an effect of excellent adhesion can be exhibited.

Hereinafter, the decorative sheet of the present invention will be described in detail. In addition, in this specification, the numerical range indicated by "~" means "greater than or equal to" and "less than or equal to", except for the parts specified as "greater than or equal to" and "less than or equal to". For example, the notation of 2 to 15 mm means 2 mm or more and 15 mm or less. Further, in the present specification, "(meth) acrylate" means "acrylate or methacrylate", and other similar substances have the same meaning.

Laminated structure of decorative sheet As shown in FIG. 1, the decorative sheet of the present invention has at least a base material layer 1, an adhesive layer 2, a first primer layer 3, a metal thin film layer 4, and a first. It has a laminated structure having the primer layer 5 of 2 and the surface protection layer 6 in this order.

Further, as shown in FIG. 2, in the decorative sheet of the present invention, a colored layer 7 may be provided on the back surface side of the base material layer 1 (the side opposite to the surface protective layer 6), if necessary. Good. From the viewpoint of enhancing the adhesion between the decorative sheet and the injection resin (molded resin layer 11), a second adhesive layer 8 may be provided on the back surface side of the base material layer 1, if necessary. A third primer layer 9 may be provided, if necessary, for the purpose of enhancing the adhesion between the surface protective layer 6 and the layer located below the surface protective layer 6. Further, a color clear layer 10 may be provided between the metal thin film layer 4 and the surface protective layer 6 as necessary for the purpose of further imparting gloss to the metallic tone of the metal thin film layer 4. Good.

As the laminated structure of the decorative sheet of the present invention, a laminated structure in which a base material layer / an adhesive layer / a first primer layer / a metal thin film layer / a second primer layer / a surface protection layer are laminated in this order; Laminated structure in which layers / colored layer / base material layer / adhesive layer / first primer layer / metal thin film layer / second primer layer / surface protection layer are laminated in this order; second adhesive layer / colored layer / group Examples thereof include a laminated structure in which a material layer / adhesive layer / first primer layer / metal thin film layer / second primer layer / color clear layer / third primer layer / surface protection layer are laminated in this order.

In FIG. 1, as one aspect of the laminated structure of the decorative sheet of the present invention, a base material layer / adhesive layer / first primer layer / metal thin film layer / second primer layer / surface protection layer are laminated in this order. A schematic cross-sectional view of an example of a decorative sheet is shown. FIG. 2 shows, as one aspect of the laminated structure of the decorative sheet of the present invention, a second adhesive layer / colored layer / base material layer / adhesive layer / first primer layer / metal thin film layer / second primer layer / A schematic cross-sectional view of an example of a decorative sheet in which a color clear layer / a third primer layer / a surface protective layer is laminated in this order is shown.

Composition of each layer forming the decorative sheet [Base material layer 1]
The base material layer 1 serves as a support in the decorative sheet of the present invention. In the present invention, the base material layer 1 is made of an acrylic resin. Therefore, the decorative sheet of the present invention is excellent in trimming property after molding (particularly, trimming property using beads). The base material layer 1 may be formed of a single layer sheet or a multi-layer sheet.

As the acrylic resin, an acrylic resin having a (meth) acrylic acid monomer as a constituent unit and an acrylic resin having a (meth) acrylic acid ester monomer as a constituent unit are preferable. In addition, these acrylic resins may be homopolymers of one kind of monomer, block copolymers of two or more kinds of monomers, or random copolymers. In the present invention, "(meth) acrylic" is a general term for "acrylic" and "methacrylic", and other similar substances with (meth) have the same meaning.

The base material layer 1 may be subjected to physical or chemical surface treatment such as an oxidation method or an unevenness method on one side or both sides, if necessary, in order to improve the adhesion to the adjacent layer. .. Examples of the oxidation method performed as the surface treatment of the base material layer 1 include a corona discharge treatment, a plasma treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, and an ozone ultraviolet treatment method. Further, examples of the unevenness method performed as the surface treatment of the base material layer 1 include a sandblast method and a solvent treatment method. These surface treatments are appropriately selected according to the type of resin component constituting the base material layer 1, but from the viewpoint of effect and operability, a corona discharge treatment method is preferable.

Further, the base material layer 1 may be colored by blending a colorant or the like, painted to adjust the color, or formed a pattern to impart designability.

The thickness of the base material layer 1 is not particularly limited and is appropriately set according to the intended use of the decorative sheet, etc., but from the viewpoint of exhibiting excellent trimming properties, it is preferably about 50 to 250 μm, more preferably 60. It is about 230 μm, more preferably about 70 to 220 μm.

[Adhesive layer 2]
The adhesive layer 2 is a layer provided between the base material layer 1 and the first primer layer 3 described later in order to improve the adhesion between the base material layer 1 and the metal thin film layer 4 described later.

In the present invention, the adhesive layer 2 contains a cured product of a resin having a glass transition point of 65 ° C. to 140 ° C. As a result, excellent adhesion between the base material layer 1 made of the acrylic resin and the layer located above the adhesive layer 2 is exhibited. More specifically, the decorative sheet of the present invention not only exhibits excellent initial adhesion, but also has excellent adhesion even after being placed in a moist heat environment or a high temperature environment. Demonstrate.

From the viewpoint of further improving the adhesion between the base material layer 1 and the metal thin film layer 4 described later, the glass transition point is preferably 80 to 140 ° C., more preferably 90 to 140 ° C. In the present invention, the glass transition point (Tg) is a value obtained by differential scanning calorimetry (DSC) based on JIS K7121-1987.

The resin forming the adhesive layer 2 is not particularly limited as long as it can improve the adhesion between the base material layer 1 and the metal thin film layer 4, and examples thereof include thermoplastic resins. The thermoplastic resin is not particularly limited, but for example, acrylic resin; polypropylene resin such as polypropylene and polyethylene; polycarbonate resin; ABS resin; polyester resin such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN); polyvinyl chloride. , Polyvinyl chloride resin such as chlorinated polyethylene, polyvinylidene chloride, ethylene-vinyl chloride copolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate- (meth) acrylic copolymer, polyvinyl chloride , Chlorine-based resins such as chlorinated polypropylene and the like. As the resin forming the adhesive layer 2, an acrylic resin or a chlorine-based resin is preferably used from the viewpoint of enhancing the adhesion between the base material layer 1 and the metal thin film layer 4. Examples of the chlorine-based resin include vinyl chloride resin and vinyl chloride-vinyl acetate copolymer from the viewpoint of enhancing the adhesion between the base material layer 1 and the metal thin film layer 4, and more preferably vinyl chloride. − Vinyl acetate copolymers can be mentioned. As the resin forming the adhesive layer 2, one type may be used alone, or two or more types may be mixed and used.

When, for example, a mixed resin of an acrylic resin and a chlorine-based resin is used as the resin forming the adhesive layer 2, the adhesive layer 2 is used from the viewpoint of improving the adhesion between the base material layer 1 and the first primer layer 3. The mass ratio of the acrylic resin to the chlorine-based resin in the resin to be formed is preferably about 20/80 to 80/20, and more preferably about 30/70 to 70/30.

When the adhesive layer 2 contains an acrylic resin, the content of the acrylic resin contained in the adhesive layer 2 is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more. The adhesive layer 2 may be substantially composed of only acrylic resin.

The thickness of the adhesive layer 2 is not particularly limited, but from the viewpoint of improving the adhesion between the base material layer 1 and the metal thin film layer 4, the thickness is about 0.6 to 3.5 μm, preferably about 1 to 2 μm. Can be done.

The method of forming the adhesive layer 2 is not particularly limited. The adhesive layer 2 can be formed, for example, by applying the above resin on the surface of a layer adjacent to the adhesive layer 2, and for example, a dry laminating method or the like can be used.

[First primer layer 3]
The first primer layer 3 enhances the adhesion between the base material layer 1 (adhesive layer 2) and the metal thin film layer 4, and discolors the metal thin film layer 4 when exposed to a high temperature environment and a moist heat environment. It is a layer provided between the adhesive layer 2 and the metal thin film layer 4 in order to suppress it. The first primer layer 3 is made of a polyester resin. In the decorative sheet of the present invention, since the first primer layer 3 is provided between the adhesive layer 2 and the metal thin film layer 4, the metal due to the components (for example, chlorine component) that can be contained in the adhesive layer 2 is provided. Discoloration of the thin film layer 4 can be effectively suppressed.

It is preferable to use a polyester polyol as the polyester resin constituting the first primer layer 3. Examples of the polyester polyol include condensed polyester diol obtained by reacting a low molecular weight diol with a dicarboxylic acid, polylactone diol obtained by ring-opening polymerization of lactone, polycarbonate diol and the like. Examples of the dicarboxylic acid include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid and fumaric acid, and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid. Further, as the lactone, for example, ε-caprolactone or the like is used. Specific examples of the polyester polyol include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, polyethylene butylene adipate, polybutylene hexabutylene adipate, polydiethylene adipate, poly (polytetramethylene ether) adipate, and polyethylene alloy. Examples thereof include zate, polyethylene sebacate, polybutylene zate, polybutylene sebacate, and polyhexamethylene carbonate diol. One type of polyester polyol may be used alone, or two or more types may be used in combination.

Further, the polyester resin constituting the first primer layer 3 may be a cured product of the polyester polyol and the curing agent. Examples of the curing agent include isocyanate compounds, and examples of isocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, and the like. 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, polymethylenepolyphenylene polyisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-Diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropanediisocyanate, m-phenylenediocyanate, p-phenylenediocyanate, naphthylene Aromatic isocyanates such as -1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate; 1,4-diisocyanatobutane, 1,5-diisocyanate Natopentane, 1,6-diisocyanatohexane (1,6-hexamethylenediisocyanate, HDI), 1,6-diisocyanato-2,2,4-trimethylhexane, methyl 2,6-diisocyanatohexanoate (lysine) Diisocyanates) and other aliphatic isocyanates; examples thereof include isophorone diisocyanates, hydrogenated xylylene diisocyanates, and alicyclic diisocyanates such as hydrogenated diphenylmethane diisocyanates. Among these, aliphatic isocyanates and aromatic isocyanates are preferable from the viewpoint of effectively suppressing discoloration of the metal thin film layer 4. One type of isocyanate compound may be used alone, or two or more types may be used in combination.

When the above-mentioned curing agent is used for the first primer layer 3, the content of the curing agent is not particularly limited, but it enhances the adhesion of the decorative sheet and effectively discolors the metal thin film layer 4. From the viewpoint of suppressing, the amount is preferably about 1 to 15 parts by mass, and more preferably about 3 to 10 parts by mass with respect to 100 parts by mass of the resin other than the curing agent such as polyester polyol.

Such a cured product forming the first primer layer 3 may be either a one-component curing type or a two-component curing type, and is preferably a two-component curing type.

The thickness of the first primer layer 3 is not particularly limited, but is preferably about 0.5 to 3 μm from the viewpoint of improving the adhesion of the decorative sheet and effectively suppressing discoloration of the metal thin film layer 4. , More preferably about 1 to 2 μm.

The first primer layer 3 is formed by using the primer composition containing the above polyester resin. Specifically, the first primer layer 3 uses a primer composition, a gravure coat, a gravure reverse coat, a gravure offset coat, a spinner coat, a roll coat, a reverse roll coat, a kiss coat, a wheeler coat, a dip coat, and silk. It is formed by a normal coating method such as a solid coat, a wire bar coat, a flow coat, a comma coat, a flow coat, a brush coat, a spray coat, or a transfer coating method using a screen. Here, the transfer coating method is a method in which a coating film of the first primer layer 3 is formed on a thin sheet (film base material), and then the surface of the target layer in the decorative sheet is coated.

[Metal thin film layer 4]
The metal thin film layer 4 is provided between the base material layer 1 (first primer layer 3) and the surface protective layer 6, and is a layer that imparts a metallic design similar to that of the metal surface to the decorative sheet.

The metal forming the metal thin film layer 4 is not particularly limited as long as it is a metal that can give a metallic design to the decorative sheet, but for example, tin, indium, chromium, aluminum, nickel, copper, silver, gold, and platinum. , Zinc, and alloys containing at least one of these. Among these, tin, indium, and chrome are preferably mentioned from the viewpoint of being rich in extensibility. Since the metal thin film layer 4 is formed of a metal having high extensibility, it has an advantage that cracks are less likely to occur when the decorative sheet is three-dimensionally molded. The metal thin film layer 4 may be formed of one kind of metal or may be formed of two or more kinds of metals.

The method for forming the metal thin film layer 4 is not particularly limited, but from the viewpoint of imparting a high-quality metallic design to the decorative sheet, for example, vapor deposition such as a vacuum vapor deposition method using the above metal is used. The method, the sputtering method, the ion plating method and the like are preferable. In particular, the vacuum vapor deposition method is preferable in that it is low in cost and causes less damage to the deposited material. The vaporization conditions may be appropriately set according to the melting temperature or evaporation temperature of the metal to be used. In addition to the above-mentioned forming method, a method of applying a paste containing the above-mentioned metal, a plating method using the above-mentioned metal, or the like can also be used.

The thickness of the metal thin film layer 4 is not particularly limited, but the optical density (OD value) is preferably about 0.6 to 1.8, more preferably from the viewpoint of enhancing the design and moldability of the decorative sheet. Is about 0.8 to 1.4.

[Second primer layer 5]
The second primer layer 5 is a layer provided directly above the metal thin film layer 4 for the purpose of improving the adhesion between the metal thin film layer 4 and the layer provided on the metal thin film layer 4.

Examples of the resin forming the second primer layer 5 include a thermosetting resin and a thermoplastic resin, and preferably a polyester resin, a polyurethane resin, an acrylic resin, a polyolefin resin and the like. Examples of the resin contained in the second primer layer 5 include polyester resin and acrylic resin from the viewpoint of imparting high moldability to the decorative sheet and suppressing discoloration during heat molding.

The polyester resin, polyurethane resin, acrylic resin, and polyolefin resin are not particularly limited, but the discoloration of the metal thin film layer 4 is further further improved while improving the adhesion between the metal thin film layer 4 and the layer provided on the metal thin film layer 4. From the viewpoint of effective suppression, for example, polyester polyol which is a polyester resin; urethane polyol which is a polyurethane resin, polyester urethane polyol, acrylic urethane polyol, etc .; acrylic polyol which is an acrylic resin; polyethylene polyol which is a polyolefin resin, Examples thereof include polyolefin polyols such as polypropylene polyols, polybutadiene polyols, and polyisoprene polyols.

Examples of the polyester polyol include the same polyester polyols as those exemplified in the above-mentioned first primer layer 3.

The acrylic polyol is not particularly limited as long as it is an acrylic resin having a plurality of hydroxyl groups, and for example, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, -n-propyl (meth) acrylic acid, (meth) acrylic. One of (meth) acrylic acid alkyl ester monomers such as isopropyl acid acid, -n-butyl (meth) acrylic acid, isobutyl (meth) acrylic acid, octyl (meth) acrylic acid, ethylhexyl (meth) acrylic acid, etc. It has two or more types and hydroxyl groups in molecules such as -2-hydroxyethyl (meth) acrylate, -2-hydroxypropyl (meth) acrylate, and -2-hydroxy-3-phenoxypropyl (meth) acrylate (). Meta) A copolymer obtained by copolymerizing one or more kinds of acrylic acid ester monomers and, if necessary, a styrene monomer or the like, and having a plurality of hydroxyl groups can be mentioned. ..

Further, in the second primer layer 5, the polyester resin and the acrylic resin may be a polyester polyol or a cured product of an acrylic polyol and a curing agent, respectively. Examples of the curing agent include isocyanate compounds, and examples of the isocyanate compound include the same as those exemplified in the above-mentioned first primer layer 3.

When the above-mentioned curing agent is used for the second primer layer 5, the content of the curing agent is not particularly limited, but it enhances the adhesion of the decorative sheet and effectively discolors the metal thin film layer 4. From the viewpoint of suppressing, preferably about 1 to 15 parts by mass, more preferably about 3 to 10 parts by mass with respect to 100 parts by mass of the resin other than the curing agent.

Such a cured product forming the second primer layer 5 may be either a one-component curing type or a two-component curing type, and is preferably a two-component curing type.

The thickness of the second primer layer 5 is not particularly limited, but from the viewpoint of enhancing the three-dimensional moldability of the decorative sheet, it is preferably about 0.5 to 3 μm, more preferably about 1 to 2 μm.

The second primer layer 5 is formed by using the primer composition containing the above resin. Specifically, it can be formed by the same method as that of the first primer layer 3.

[Surface protection layer 6]
The surface protective layer 6 is a layer provided on the outermost surface of the decorative sheet for the purpose of improving scratch resistance, weather resistance, and the like of the decorative sheet. The material forming the surface protective layer 6 is not particularly limited, but a resin is usually used, and an ionizing radiation curable resin is preferably used. Hereinafter, the ionizing radiation curable resin used for forming the surface protective layer 6 will be described in detail.

(Ionizing radiation curable resin)
The ionizing radiation curable resin used for forming the surface protective layer 6 is a resin that is crosslinked and cured by irradiation with ionizing radiation, and specifically, a polymerizable unsaturated bond or an epoxy group in the molecule. Examples thereof include those obtained by appropriately mixing at least one of a prepolymer, an oligomer, a monomer, and the like having the above. Here, ionizing radiation means electromagnetic waves or charged particle beams that have energy quanta capable of polymerizing or cross-linking molecules, and usually ultraviolet rays (UV) or electron beams (EB) are used, but in addition, X It also includes electromagnetic waves such as rays and γ-rays, and charged particle beams such as α-rays and ion rays. Among the ionizing radiation curable resins, the electron beam curable resin is suitable for forming the surface protective layer 6 because it can be solvent-free, does not require a photopolymerization initiator, and has stable curing characteristics. Used for.

As the above-mentioned monomer used as the ionizing radiation curable resin, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable. The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more (bifunctional or higher), preferably three or more (trifunctional or higher) polymerizable unsaturated bonds in the molecule. Specific examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (). Meta) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate of hydroxypivalate, dicyclopentanyldi (meth) acrylate, caprolactone-modified dicyclopentenyldi (meth) Meta) acrylate, ethylene oxide-modified di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethyl propantri (meth) acrylate, ethylene oxide-modified trimethyl propanthry (meth) acrylate , Dipentaerythritol tri (meth) acrylate, propionic acid-modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide-modified trimethylol propantri (meth) acrylate, tris (acryloxyethyl) isocyanurate , Propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate and the like. These monomers may be used alone or in combination of two or more.

Further, as the above-mentioned oligomer used as an ionizing radiation curable resin, a (meth) acrylate oligomer having a radically polymerizable unsaturated group in the molecule is preferable, and among them, two or more polymerizable unsaturated bonds in the molecule. A polyfunctional (meth) acrylate oligomer having (bifunctional or higher) is preferable. Examples of the polyfunctional (meth) acrylate oligomer include polycarbonate (meth) acrylate, acrylic silicone (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. , Polybutadiene (meth) acrylate, silicone (meth) acrylate, oligomers having a cationically polymerizable functional group in the molecule (for example, novolac type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc.) and the like. .. Here, the polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth) acrylate group in the terminal or side chain, and for example, a polycarbonate polyol (meth) is used. It can be obtained by esterification with acrylic acid. The polycarbonate (meth) acrylate may be, for example, urethane (meth) acrylate having a polycarbonate skeleton. The urethane (meth) acrylate having a polycarbonate skeleton can be obtained, for example, by reacting a polycarbonate polyol, a polyisocyanate compound, and a hydroxy (meth) acrylate. Acrylic silicone (meth) acrylate can be obtained by radical copolymerizing a silicone macromonomer with a (meth) acrylate monomer. Urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by reacting a polyether polyol or a polyester polyol with a polyisocyanate compound with (meth) acrylic acid. Epoxy (meth) acrylate can be obtained, for example, by reacting (meth) acrylic acid with the oxylan ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin to esterify it. Further, a carboxyl-modified epoxy (meth) acrylate in which this epoxy (meth) acrylate is partially modified with a dibasic carboxylic acid anhydride can also be used. Polyester (meth) acrylate can be obtained, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, or to a polyvalent carboxylic acid. It can be obtained by esterifying the hydroxyl group at the end of the oligomer obtained by adding an alkylene oxide with (meth) acrylic acid. The polyether (meth) acrylate can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid. Polybutadiene (meth) acrylate can be obtained by adding (meth) acrylic acid to the side chain of the polybutadiene oligomer. Silicone (meth) acrylate can be obtained by adding (meth) acrylic acid to the terminal or side chain of silicone having a polysiloxane bond in the main chain. These oligomers may be used alone or in combination of two or more.

Among the above-mentioned ionizing radiation curable resins, it is preferable to use polycarbonate (meth) acrylate from the viewpoint of obtaining excellent three-dimensional moldability. Further, from the viewpoint of achieving both three-dimensional moldability and scratch resistance, it is more preferable to use a combination of polycarbonate (meth) acrylate and urethane (meth) acrylate.

(Other additive ingredients)
Various additives can be added to the surface protective layer 6 according to the desired physical properties to be provided in the surface protective layer 6. Examples of this additive include weather resistance improvers such as ultraviolet absorbers and light stabilizers, abrasion resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesive improvers, and leveling agents. Examples thereof include a thixophilic imparting agent, a coupling agent, a plasticizer, an antifoaming agent, a filler, a solvent, and a coloring agent. These additives can be appropriately selected and used from those commonly used. Further, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can also be used.

(Thickness of surface protective layer 6)
The thickness of the surface protective layer 6 after curing is not particularly limited, and examples thereof include 1 to 100 μm, preferably 1 to 50 μm, and more preferably 1 to 30 μm. When the thickness in such a range is satisfied, sufficient physical properties such as scratch resistance and weather resistance can be obtained as a surface protective layer, and when the surface protective layer 6 is formed by using an ionizing radiation curable resin, the surface protective layer 6 is formed. Since it is possible to uniformly irradiate ionizing radiation, it is possible to cure uniformly, which is economically advantageous.

(Formation of surface protective layer 6 when ionizing radiation curable resin is used)
The surface protective layer 6 is formed, for example, by preparing an ionizing radiation curable resin composition containing an ionizing radiation curable resin, applying the composition, and cross-linking and curing the composition. The viscosity of the ionizing radiation curable resin composition may be any viscosity that can form an uncured resin layer on the surface of the layer adjacent to the surface protective layer 6 by the coating method described later.

In the present invention, the prepared coating liquid is gravure-coated, bar-coated, and rolled on a metal thin film layer 4, a third primer layer 9 to be described later, which is provided as needed, so as to have the above-mentioned thickness. It is applied by a known method such as coating, reverse roll coating, comma coating, preferably gravure coating to form an uncured resin layer.

The uncured resin layer thus formed is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer to form the surface protective layer 6. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage thereof can be appropriately selected depending on the resin to be used and the thickness of the layer, but usually an acceleration voltage of about 70 to 300 kV can be mentioned.

In electron beam irradiation, the higher the acceleration voltage, the higher the transmission capacity. Therefore, when a resin that is easily deteriorated by electron beam irradiation is used under the surface protection layer 6, the electron beam transmission depth and surface protection are used. The acceleration voltage is selected so that the thicknesses of the layers 6 are substantially equal. As a result, it is possible to suppress the irradiation of the layer located below the surface protective layer 6 with the extra electron beam, and it is possible to minimize the deterioration of each layer due to the excess electron beam.

The irradiation dose is preferably an amount at which the crosslink density of the surface protective layer 6 is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).

Further, the electron beam source is not particularly limited, and for example, various electron beam accelerators such as cockloft Walton type, bandegraft type, resonance transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type can be used. Can be used.

When ultraviolet rays are used as ionizing radiation, light rays containing ultraviolet rays having a wavelength of 190 to 380 nm may be emitted. The ultraviolet source is not particularly limited, and examples thereof include a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, and a carbon arc lamp.

By adding various additives to the surface protective layer 6 thus formed, a hard coating function, an antifogging coating function, an antifouling coating function, an antiglare coating function, an antireflection coating function, and an ultraviolet shielding coating function, A process for imparting a function such as an infrared shielding coating function may be performed.

[Colored layer 7]
The coloring layer 7 is provided on the back surface side of the base material layer 1 as needed for the purpose of coloring the back surface side of the decorative sheet.

The colored layer 7 can be made of a resin containing a pigment or a dye. Examples of the resin include acrylic resin, polyurethane resin, acrylic-urethane copolymer resin, polyester resin and the like.

The thickness of the colored layer 7 is not particularly limited, and may be about 0.1 to 30 μm.

[Second adhesive layer 8]
The second adhesive layer 8 is a layer provided on the back surface side of the base material layer 1 as needed for the purpose of improving the adhesiveness and adhesion between the decorative sheet and the molding resin. The resin forming the second adhesive layer 8 is not particularly limited as long as it can improve the adhesiveness and adhesion between the decorative sheet and the molding resin, and is, for example, a thermoplastic resin or thermosetting. A sex resin is used. Examples of the thermoplastic resin include acrylic resin, acrylic modified polyolefin resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, polyamide resin, rubber resin and the like. .. One type of thermoplastic resin may be used alone, or two or more types may be used in combination. Examples of the thermosetting resin include urethane resin and epoxy resin. One type of thermosetting resin may be used alone, or two or more types may be used in combination.

The thickness of the second adhesive layer 8 is not particularly limited, and examples thereof include about 0.1 to 30 μm, preferably about 0.5 to 20 μm, and more preferably about 1 to 8 μm.

[Third primer layer 9]
The third primer layer 9 is a layer provided directly under the surface protective layer 6 as necessary for the purpose of enhancing the adhesion between the surface protective layer 6 and the layer located below the surface protective layer 6. The material forming the third primer layer 9 is not particularly limited as long as it can improve the adhesion between these layers, and is, for example, an acrylic resin, a polyurethane resin, an acrylic-urethane copolymer resin, or a polyester. Examples include resins such as resins.

The thickness of the third primer layer 9 is not particularly limited, but is usually about 0.5 to 2.5 μm, preferably about 1 to 2 μm. A colorant can be mixed with the third primer layer 9 to adjust the color and improve the design, and further, a pattern can be formed from a design point of view.

The method for forming the third primer layer 9 is not particularly limited, and examples thereof include a method of applying the above resin on the surface of a layer adjacent to the third primer layer 9. Further, the above resin is applied onto a separately prepared mold release sheet, and a layer to be located directly under the third primer layer 9 in the decorative sheet is further formed on the resin. A method of forming by peeling off the release sheet can also be mentioned.

[Color clear layer 7]
The color clear layer 7 is a layer provided on the metal thin film layer 4 as needed for the purpose of further imparting luster to the metallic tone of the metal thin film layer 4. The material for forming the color clear layer 7 is not particularly limited, and examples thereof include a transparent resin colored with a colorant or the like. The colorant is not particularly limited, and examples thereof include a color pigment and a dye. The transparent resin is not particularly limited, and examples thereof include acrylic resin, polyurethane resin, acrylic-urethane copolymer resin, and polyester resin.

The thickness of the color clear layer 7 is not particularly limited, but is usually about 0.5 to 4 μm, preferably about 1 to 3 μm. The method for forming the color clear layer 7 is not particularly limited, and examples thereof include a method of applying the above resin on the surface of a layer adjacent to the color clear layer 7.

2. 2. Decorative resin molded product The decorative resin molded product of the present invention is formed by integrating the decorative sheet of the present invention and the molding resin. That is, the decorative resin molded product of the present invention has at least the molding resin layer 11, the base material layer 1, the adhesive layer 2, the first primer layer 3, the metal thin film layer 4, and the second primer layer. The base material layer 1 is made of acrylic resin, the first primer layer 3 is made of polyester resin, and the adhesive layer 2 is composed of a laminate including 5 and a surface protective layer 6 in this order. Is characterized by containing a cured product of a resin having a glass transition point of 65 ° C. to 140 ° C. In the decorative resin molded product of the present invention, if necessary, at least one layer such as the above-mentioned colored layer 7, the second adhesive layer 8, the third primer layer 9, and the color clear layer 10 is further added to the decorative sheet. It may be provided.

The decorative resin molded product of the present invention is produced by, for example, various injection molding methods such as an insert molding method, an injection molding simultaneous decoration method, a blow molding method, and a gas injection molding method using the decorative sheet of the present invention. To. Among these injection molding methods, an insert molding method and an injection molding simultaneous decoration method are preferably mentioned, and the injection molding simultaneous decoration method is particularly suitable. The decorative resin molded product of the present invention is prepared by a decoration method such as a vacuum pressure bonding method in which the decorative sheet of the present invention is attached onto a three-dimensional resin molded body (molded resin layer) prepared in advance. Can also be produced.

Examples of the method for producing the decorative resin molded product of the present invention include a step of heating the decorative sheet of the present invention, a step of integrating the heated decorative sheet and the molded resin, and an unnecessary portion of the decorative sheet. There is a method including a step of trimming. As described above, this trimming step can preferably be performed by striking beads on an unnecessary portion of the decorative sheet.

More specifically, for example, in the injection molding simultaneous decoration method, the decoration sheet of the present invention is placed in a female mold that also serves as a vacuum molding mold provided with suction holes for injection molding, and premolding is performed with this female mold. After performing (in-line premolding), the injection molding mold is molded, the fluid resin is injection-filled in the mold, solidified, and the present invention is added to the outer surface of the resin molded product at the same time as the injection molding. A decorative resin molded product is manufactured by integrating the decorative sheet and further striking an unnecessary portion of the decorative sheet to trim it.

A more specific manufacturing method by the injection molding simultaneous decoration method is as follows.
After installing the decorative sheet of the present invention so that the surface of the base material layer of the decorative sheet faces the molding surface of the movable mold having a molding surface having a predetermined shape, the decorative sheet is heated. A pre-molding step of pre-molding a decorative sheet by softening and vacuum-sucking from the movable mold side to bring the softened decorative sheet into close contact with the molding surface of the movable mold.
After the movable mold having the decorative sheet adhered along the molding surface and the fixed mold are molded, the fluid resin is injected, filled and solidified into the cavity formed by both molds. As a result, a resin molded body is formed, and an integration step of laminating and integrating the resin molded body and the decorative sheet, and resin molding in which all layers of the decorative sheet are laminated by separating the movable mold from the fixed mold. Extraction process for taking out the body A process for trimming by striking beads on unnecessary parts of the decorative sheet existing in the removed resin molded body.

In the pre-molding process of the injection molding simultaneous decoration method, the heating temperature of the decoration sheet is not particularly limited, and may be appropriately selected depending on the type of resin constituting the decoration sheet, the thickness of the decoration sheet, and the like. When a polyester resin film or an acrylic resin film is used as the base material layer, the temperature can usually be about 70 to 130 ° C. Further, in the injection molding step, the temperature of the resin in the fluid state is not particularly limited, but can be usually about 180 to 320 ° C., preferably about 220 to 280 ° C.

In the decorative resin molded product of the present invention, the molding resin layer may be formed by selecting a resin according to the intended use. The resin forming the molding resin layer may be a thermoplastic resin or a thermosetting resin.

Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene, ABS resin, styrene resin, polycarbonate resin, acrylic resin, vinyl chloride resin and the like. These thermoplastic resins may be used alone or in combination of two or more.

Further, examples of the thermosetting resin include urethane resin and epoxy resin. These thermosetting resins may be used alone or in combination of two or more.

The decorative resin molded product of the present invention is preferably suppressed from discoloration in a high temperature environment or a moist heat environment, and has excellent adhesion. Therefore, for example, an interior material or an exterior material of a vehicle such as an automobile; Joinery such as window frames and door frames; interior materials for buildings such as walls, floors and ceilings; housings for home appliances such as television receivers and air conditioners; containers and the like.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

<Examples 1 to 5 and Comparative Examples 1 to 5>
(Making a decorative sheet)
A polyethylene terephthalate (PET) film having a thickness of 75 μm was used as the base sheet for transfer. Using a bar coater, an electron beam curable resin composition (urethane acrylate / acrylic resin = 30/70) was applied to the release surface of this PET film so that the thickness after curing was 9 μm. The uncured resin layer was irradiated with an electron beam having an acceleration voltage of 165 kV and an irradiation dose of 50 kGy (5Mrad) to cure the electron beam curable resin composition to form a surface protective layer. Next, a second primer layer composed of an acrylic polyol and an isocyanate (curing agent) was formed on the surface protective layer by gravure printing (solid plate) (thickness 1.2 μm). Next, tin (Sn) was deposited on the second primer layer by a vacuum deposition method (optical density OD1.1). Next, from above the tin vapor deposition surface, a first primer layer (thickness 1.2 μm) composed of resin A or resin B described later, and an adhesive layer (thickness) formed by adhesives A to F described later. 1.2 μm) was continuously formed by gravure printing (solid plate). Separately, an acrylic film (base material layer) with a thickness of 125 μm is prepared, and a colored layer (black ink, thickness 1.2 μm) and an adhesive (acrylic resin / vinyl chloride-vinyl acetate copolymer = 1) are prepared on the surface of the acrylic film. The second adhesive layer (thickness 1.5 μm) formed by / 1) was formed by gravure printing (solid plate). Next, the surface of the other side of the acrylic film and the adhesive layer formed on the transfer substrate sheet described above are adhered to each other, and while pressurizing with a 100 ton press machine, the temperature is 120 ° C. for 10 minutes. By placing and peeling off the transfer base sheet, the second adhesive layer / colored layer / base material layer / adhesive layer / first primer layer / metal thin film layer / second primer layer / surface protection layer are sequentially arranged. Each laminated decorative sheet was obtained. As shown in Table 1, in Comparative Example 3, the adhesive layer was not provided. Further, in Comparative Example 4, the first primer layer was not provided.

(First primer layer)
Resin A: Polyester resin, Tg 70 ° C
Resin B: Acrylic polyol, Tg 50 ° C
Hardener: Xylylene diisocyanate (added so that NCO equivalent and OH equivalent are the same amount)

(Adhesive layer)
Adhesive A: Acrylic resin, Tg 105 ° C, OH value 0
Adhesive B: Acrylic resin, Tg 129 ° C, OH value 0
Adhesive C: Acrylic resin / vinyl chloride-vinyl acetate copolymer = 1/1, acrylic resin Tg 105 ° C, OH value 0, vinyl chloride-vinyl acetate copolymer Tg 70 ° C
Adhesive D: Acrylic polyol, Tg 90 ° C., OH value 81, acid value 6.0
Adhesive E: Acrylic resin, Tg 80 ° C, OH value 0, acid value 18.5
Adhesive F: Acrylic resin, Tg 60 ° C, OH value 0, acid value 228
The hydroxyl value (OH value) of the acrylic resin and the acrylic polyol is a value measured in accordance with the provisions of JIS K0070: 1992.

(Manufacturing of decorative resin molded products)
Each of the decorative sheets obtained above was subjected to an injection molding simultaneous decoration method to prepare each decorative resin molded product. Specifically, the decorative sheet is placed in a mold, heated to 100 ° C. from the second adhesive layer side by an infrared heater in the mold, and preformed so as to follow the shape in the mold. I tightened it. Then, the injection resin (ABS resin) was injected into the mold, and the decorative sheet and the injection resin were integrated to obtain each decorative resin molded product.

(Evaluation of trimming property)
The decorative resin molded product obtained above was trimmed under the following conditions, and the trimming property was evaluated according to the following criteria. The results are shown in Table 1. In the trimming of the decorative resin molded product, beads were struck on the decorative resin molded product for about 2 minutes, and only the decorative sheet part was trimmed from the decorative resin molded product.
〇: No “burr” on the sheet was generated on the decorative resin molded product.
Δ: Sheet “burrs” were generated in the decorative resin molded product, but they were slight.
X: Sheet "burrs" occurred in the decorative resin molded product.

(Initial adhesion evaluation)
On the surface of each of the decorative resin molded products obtained above, 11 × 11 cuts having a width of 1 mm were made with a cutter knife to form a grid. Next, Nichiban cellophane tape (registered trademark) was firmly attached to the grid and peeled off while being pulled in the direction perpendicular to the surface of the decorative resin molded product, and the adhesion of the decorative sheet was evaluated according to the following criteria. The results are shown in Table 1.
◯: No peeling was observed.
Δ: Peeling was observed at the portion where the notch was made with a cutter knife.
X: Peeling was also seen in the part other than the part where the notch was made with the cutter knife (the grid part).

(Evaluation of moisture resistance)
Each of the decorative resin molded products obtained above was placed in a constant temperature and humidity chamber having a temperature of 50 ° C. and a humidity of 95%, allowed to stand for 500 hours, and the color difference before and after being placed in the constant temperature and humidity chamber was measured. The color difference was measured using a color difference meter (SPECTRO PHOTO METER CM-3700d manufactured by MINOLTA). In addition, the adhesion after standing in a constant temperature and humidity chamber for 500 hours was evaluated in the same manner as the above initial adhesion. The results are shown in Table 1.

(Heat resistance evaluation)
Each of the decorative resin molded products obtained above was placed in a constant temperature and humidity chamber having a temperature of 100 ° C. and a humidity of 65%, allowed to stand for 500 hours, and the color difference before and after being placed in the constant temperature and humidity chamber was measured. The color difference was measured using a color difference meter (SPECTRO PHOTO METER CM-3700d manufactured by MINOLTA). In addition, the adhesion after standing in a constant temperature and humidity chamber for 500 hours was evaluated in the same manner as the above initial adhesion. The results are shown in Table 1.

As is clear from the results shown in Table 1, a laminate having a base material layer, an adhesive layer, a first primer layer, a metal thin film layer, a second primer layer, and a surface protection layer in this order. The base material layer is made of acrylic resin, the first primer layer is made of polyester resin (resin A), and the adhesive layer is a resin having a glass transition point of 65 ° C to 140 ° C. The decorative sheets of Examples 1 to 5 containing the cured product of (adhesives A to E) are excellent in trimming property after molding, and discoloration in a high temperature environment or a moist heat environment is suitably suppressed. Furthermore, it was excellent in adhesion (initial adhesion, adhesion after exposure to a high temperature environment or a moist heat environment).

1 ... Base material layer 2 ... Adhesive layer 3 ... First primer layer 4 ... Metal thin film layer 5 ... Second primer layer 6 ... Surface protection layer 7 ... Colored layer 8 ... Second adhesive layer 9 ... Third primer Layer 10 ... Color clear layer 11 ... Molded resin layer

Claims (7)

It is composed of a laminate having at least a base material layer, an adhesive layer, a first primer layer, a metal thin film layer, a second primer layer, and a surface protection layer in this order.
The base material layer is made of acrylic resin.
The first primer layer is made of a polyester resin.
The adhesive layer is formed of a resin having a glass transition point of 65 ° C. or higher and 140 ° C. or lower.
A decorative sheet in which the resin of the adhesive layer contains an acrylic resin. The decorative sheet according to claim 1, wherein the second primer layer is composed of at least one selected from the group consisting of polyester resin, polyurethane resin, acrylic resin, and polyolefin resin. The decorative sheet according to claim 1 or 2 , wherein the thickness of the base material layer is 50 μm or more and 250 μm or less. The metal thin film layer is composed of at least one metal selected from the group consisting of tin, indium, chromium, aluminum, nickel, copper, silver, gold, platinum, zinc, and alloys containing at least one of these. The decorative sheet according to any one of claims 1 to 3. It is composed of a laminate having at least a molding resin layer, a base material layer, an adhesive layer, a first primer layer, a metal thin film layer, a second primer layer, and a surface protection layer in this order.
The base material layer is made of acrylic resin.
The first primer layer is made of a polyester resin.
The adhesive layer is formed of a resin having a glass transition point of 65 ° C. or higher and 140 ° C. or lower.
A decorative resin molded product in which the resin of the adhesive layer contains an acrylic resin. The step of heating the decorative sheet according to any one of claims 1 to 4,
The process of integrating the heated decorative sheet and the molding resin,
The process of trimming unnecessary parts of the decorative sheet and
A method for manufacturing a decorative resin molded product. The method for producing a decorative resin molded product according to claim 6 , wherein the trimming step is a trimming step in which beads are struck on an unnecessary portion of the decorative sheet.