JP2002210907A - Decorating sheet and method for injection molding and in-mold decorating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To simply impart a specular metallic luster feeling to a surface of each of various type articles such as a resin molding or the like. SOLUTION: A decorating sheet S comprises a smooth and transparent base sheet 1 having a centerline mean roughness specified according to JIS B 0601 of each both front and rear surfaces of 1 μm or less, a lustrous ink layer 2 containing a lustrous pigment (a) made of flaky particles having a metallic luster in a binder resin and formed on a rear surface of the sheet 1, so that a surface of a flat plate of the particles is parallel to or substantially parallel to the rear surface of the base sheet near the base sheet. Further, a colored ink layer of the same hue or substantially the same hue as the lustrous ink layer may be provided on the rear surface side of the layer 2, or an adhesive layer 4 may be provided on the rearmost surface. This decorating sheet may be laminated on a material to be coated such as a resin composition or the like by injection molding and in-mold decorating or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decoration technique for easily giving a mirror-like metallic gloss to the surface of various articles such as resin molded articles.

[0002]

2. Description of the Related Art Conventionally, there have been the following methods for obtaining a resin molded product having a metallic luster as a glittering appearance. (1) A resin molded product is coated with a paint containing flaky particles of a metal such as aluminum. (2) Electroless plating is performed on the resin molded product. (3) A decorative sheet made of a metal-deposited resin sheet is laminated on the resin molded article by a simultaneous decoration method for injection molding (see Japanese Patent Application Laid-Open No. 10-180795). (4) Direct metal deposition on the resin molded product.

[0003]

However, in the above method (1), from the viewpoints of metallic luster and coating suitability,
Normally, the surface of the molded product is coated with a coating containing aluminum powder having an average particle diameter of 1 to 30 μm. However, since the orientation direction of the aluminum powder on the coating film surface cannot be regulated as shown in FIG. The surface becomes uneven and light is scattered, and it is not possible to obtain a mirror-like metallic luster such as vapor deposition or plating. The resulting metallic luster is limited to matte metallic luster. In the above method (2), although a mirror-like metallic luster can be obtained,
The plating process is disliked due to pollution problems, and also requires waste liquid treatment. In addition, since the metal film obtained by the electroless plating is thin and has no durability, a coating process is required after the electroless plating process. Therefore, the number of steps is increased and the production efficiency is higher than in the coating method (1). In the above method (3), even if a mirror-like metallic luster is obtained, the number of vapor deposition steps increases in the decorative sheet manufacturing stage, and when the decorative sheet is laminated on a molded product, the sheet stretches. There was a possibility that the deposited film was cracked in some parts to impair the appearance. In addition, the above (4)
According to the method described above, a mirror-finished metallic luster can be obtained, but batch processing is performed for one or a small number of molded articles, resulting in poor production efficiency, and also requires a painting step, resulting in poor production efficiency.

[0004] That is, an object of the present invention is to easily give a mirror-like metallic gloss to an adherend such as a molded product without causing the above-mentioned problems.

[0005]

Therefore, in order to solve the above-mentioned problems, the decorative sheet of the present invention has JISB
Forming a glittering ink layer containing a glittering pigment composed of scaly particles having a metallic luster in a binder resin on the back surface of a smooth and transparent substrate sheet having a center line average roughness of 0601 standard of 1 μm or less. The flat surface of the scaly particles is parallel or substantially parallel to the back surface of the base sheet at least at the interface between the back surface of the base sheet and the glittering ink layer.

[0006] With such a configuration, a decorative sheet that can easily impart a mirror-like metallic luster to an adherend such as a resin molded product. That is, a glitter ink layer is provided on the back surface of a transparent and smooth base material sheet on both sides, and the glitter pigment in the glitter ink layer is flake-like particles, and the flat surface thereof is parallel or substantially parallel to the back surface of the base material sheet. Since the layers are arranged in parallel, as a result, even if the layer is formed using a bright pigment having a coarse particle size, light scattering hardly occurs on the substrate sheet surface and the surface of the bright pigment itself. Therefore, the metallic luster is obtained as a mirror-finished metallic luster.

The decorative sheet of the present invention is different from the above-mentioned constitution in that a colored ink layer having the same hue or substantially the same hue as that of the glittering ink layer is further formed on the back side of the glittering ink layer. The configuration was adopted. With such a configuration, even if the decorative sheet is formed and stretched, and the glittering ink layer is stretched and thinned, the presence of the specific coloring ink layer on the back surface allows the color tone of the glittering ink layer to be reduced. It is possible to reduce the change and the lack of concealment of the color of the adherend on the base.

[0008] Further, the decorative sheet of the present invention has a structure in which an adhesive layer is further provided on the rearmost surface in addition to any of the above structures. With such a configuration, the decorative sheet can be laminated with good adherence to the adherend made of various materials.

In addition, the injection molding simultaneous decoration method of the present invention comprises:
Any of the decorative sheets described above, with the glitter ink layer side facing the injection resin side with respect to the base sheet, and inserted between the male and female molds, then the molds are clamped. A method of injecting a resin in a fluid state into a cavity to be formed, solidifying the resin, opening the mold, and obtaining a decorative molded product in which the decorative sheet is laminated on the surface of a resin molded product. did.
By adopting such a decoration method, since the molding is performed using the decorative sheet of the present invention, the effect of the decorative sheet described above is obtained, and as a result, the resin molding process can be performed without further increase in the process. In addition, it is possible to easily impart a specular metallic luster to a molded article without having to perform waste liquid treatment.

[0010]

Embodiments of the present invention will be described below with reference to the drawings.

Decorative sheet: First, the decorative sheet will be described.

[Outline] One embodiment of the decorative sheet of the present invention is illustrated in the sectional view of FIG. The decorative sheet S in the same figure has a center line average roughness of 1 μm on both the front and back sides specified in JIS B0601.
m, a glittering ink layer 2 containing a glittering pigment a composed of scaly particles having metallic luster in a binder resin is formed on the back surface of a smooth and transparent base sheet 1 having a thickness of not more than m. The flat surface F (see FIG. 3) of the scaly particles serving as the glittering pigment is arranged parallel or substantially parallel to the back surface of the base sheet 1 on the back surface of the base sheet 1 and in the vicinity thereof. Further, the decorative sheet has a configuration in which an adhesive layer 4 is further provided on the rearmost surface on the rear side of the glittering ink layer 2. With this configuration, as conceptually shown in FIG. 1, a part of the light reflected by the glittering ink layer, that is, a part of the incident light L _IN to the base sheet 1, is first applied to the base sheet surface. Is reflected light L _RF1 which is specularly reflected by
Of the scaly particles of the glittering pigment a near the base sheet 1 in the glitter ink layer 2 (and the flat face F is at least near the base sheet 1). In this case, the glitter pigment a is oriented so as to be parallel or substantially parallel to the base sheet 1, and as a whole approximates a substantially perfect mirror surface.) Then, the light again passes through the smooth front and back surfaces of the base sheet 1 and _exits from the decorative sheet as reflected light _LRF2 , so that there are few elements in which light is scattered in multiple directions, and a beautiful mirror-like metallic luster is obtained. Will be done.

FIG. 2 is a cross-sectional view illustrating another embodiment of the decorative sheet of the present invention. In the decorative sheet S shown in FIG. 2, both the front and back surfaces have a center line average defined by JIS B0601. On the back surface of a smooth and transparent base sheet 1 having a roughness of 1 μm or less, a glittering ink layer 2 containing a glittering pigment a composed of scaly particles having a metallic luster in a binder resin is the same as in FIG. A colored ink layer 3 having the same hue or substantially the same hue as that of the glittering ink layer is formed on the backside of the glittering ink layer in the same manner, and further has an adhesive layer 4 on the rearmost surface. It is a decorative sheet of a structure.

[Base Sheet] The base sheet 1 has a center line average roughness of 5 μm on both front and back surfaces specified in JIS B0601.
Hereinafter, it is more preferably 1 μm or less, and still more preferably 0.1 μm or less. In addition, transparent means colorless and transparent or colored and transparent. Further, the transparency is defined as a transparency within a range that does not impair the metallic luster appearance of the glittering ink layer on the back surface.
As such a base sheet, a thermoplastic resin sheet is preferably used as it preferably has moldability.

As the thermoplastic resin, the smoothness,
There is no particular limitation on the transparency and the moldability as long as the moldability is further satisfied. For example, homopolymers of (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, or these (meth) acrylates Acrylic resin such as a copolymer of each other or a (meth) acrylate and another monomer such as styrene, ethylene, etc. [The (meth) acrylate means an acrylate or a methacrylate. ], Polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, ethylene-isophthalate-terephthalate copolymer, polyester-based thermoplastic elastomer (high crystalline high melting point aromatic polyester in the hard segment,
The soft segment is a block polymer or the like using an amorphous polyether having a glass transition temperature of −70 ° C. or lower, and the highly crystalline, high melting point aromatic polyester is, for example, polybutylene terephthalate, Polytetramethylene glycol or the like is used as the amorphous polyether. Polyester resins such as completely amorphous polyesters (typically, ethylene glycol-1,4-cyclohexanedimethanol-terephthalic acid copolymer), vinyl chloride resins, and vinyl chloride-vinyl acetate copolymers. Polymers, vinyl resins such as ethylene-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, polyethylene, polypropylene, polymethylpentene, polybutene, ionomer, ethylene-propylene copolymer, olefin-based thermoplastic elastomer, etc. Fluorine resin such as polyolefin resin, polyvinyl fluoride, polyvinylidene fluoride, ethylene-tetrafluoroethylene copolymer, styrene resin such as polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, polycarbonate Sulfonates, nylon (polyamide), thermoplastic urethane resins, polyimides, polyphenylene sulfide, a resin such as polyether ether ketone. The thickness of the base sheet is usually about 50 to 500 μm.

In the base sheet made of a resin sheet, a coloring agent, a lubricant, a lubricant, a lubricant, an antioxidant, an ultraviolet absorber, and the like may be used as long as the transparency and smoothness are not impaired. Light stabilizer, plasticizer, antistatic agent, fungicide, antibacterial,
An additive such as a flame retardant may be added.

The colorant is an additive for coloring the base sheet. As the coloring agent, for example, titanium white,
Zinc flower, red pattern, vermilion, ultramarine, cobalt blue, titanium yellow,
Inorganic pigments such as graphite, carbon black, and iron black; organic pigments (or dyes) such as isoindolinone yellow, benzidine yellow, quinacridone red, permanent red 4R, phthalocyanine blue, indaslen blue RS, and aniline black; Known coloring agents can be used. In addition, as long as it does not interfere with the design of the mirror surface metallic luster by the lower glittering ink layer, metal powder such as aluminum and brass, flake foil, titanium dioxide-coated mica, basic lead carbonate, etc. A pearlescent (pearl) pigment or the like composed of scale foil pieces may be used.

The above lubricant is an additive for improving abrasion resistance and the like. Examples of the lubricant include silica, alumina, and aluminosilicate.
Particles of about 0 μm are added in an amount of about 5 to 30% by mass. The above-mentioned lubricant is also an additive for improving abrasion resistance and the like. Examples of the lubricant include waxes such as wood wax, montan wax, paraffin wax, and silicone resin.
About 5% by weight is added.

In particular, in applications where weather (light) resistance is required, organic ultraviolet absorbers such as benzotriazole, benzophenone, and salicylate esters, and particles having a particle size of 0.
It is preferable to add a light stabilizer such as an inorganic ultraviolet absorber such as zinc oxide, cerium oxide or titanium oxide having a particle size of 2 μm or less, a radical scavenger such as a hindered amine radical scavenger or a piperidine radical scavenger. The amount of addition
Usually, both are each in the range of 0.1 to 5% by mass.

For applications requiring flame retardancy, a flame retardant such as aluminum hydroxide, magnesium hydroxide, antimony trioxide or molybdenum oxide may be added. The addition amount is usually about 5 to 30% by weight.

The resin sheet used as the base sheet can be obtained by forming a film by a known film forming method such as a calendar method, an inflation method, a T-die extrusion method, and a casting method.

Further, if the base sheet is a sheet having an active hydrogen-containing group such as a hydroxyl group, a carboxyl group, or an amino group on the surface, an adjacent layer provided in contact with the base sheet, for example, a glitter When the ink layer, the primer layer, and the like contain a two-component curable urethane resin, the adhesion between the adjacent layers and the base sheet can be improved. In order to have an active hydrogen-containing group on the surface of the base material sheet, specifically, a known surface treatment such as a corona discharge treatment, a plasma treatment, and an ozone treatment may be performed.

[Glitter ink layer] The glitter ink layer 2
This is a layer formed using a glitter ink containing a glitter pigment a composed of scale particles having metallic luster in a binder resin. The glitter pigment preferably has an average particle size of 1
５０50 μm is used. If the average particle size is larger than this, layer formation by printing or coating becomes difficult. Conversely, if the average particle size is smaller than this, sufficient mirror surface metallic luster cannot be obtained. As one of the conditions for exhibiting a sufficient specular metallic luster, it is preferable that the glitter pigment particles use scale-like particles made of a substance having a high reflectivity and a metallic luster. In the case of such scaly particles, the particle size is
It is defined as the diagonal length of the scaly particles on the flat surface F or the diameter of the circumscribed sphere. In addition, the thickness t of the flaky particles is 0.
It is about 1 to 1 μm. FIG. 3 is a perspective view illustrating the flat surface F and the thickness t in a certain shape of the brilliant pigment a which is a scaly particle. As the material of the glitter pigment, metals such as aluminum, nickel, copper, gold, silver, tin, and brass, titanium dioxide-coated mica, and basic lead carbonate are used.

As the binder resin for the glitter ink layer, a resin having high transparency is used. For example, chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyester resins, urethane resins, acrylic resins, vinyl acetate resins, A vinyl chloride-vinyl acetate copolymer, a cellulose resin or the like is used alone or in combination of two or more.

As the binder resin for the glitter ink layer, when the base sheet has a structure having an active hydrogen-containing group on its surface and when the glitter ink layer is in contact with the base sheet, it is preferably 2 It is preferable to use a liquid-curable urethane resin from the viewpoint of improving the adhesion between the base sheet and the glittering ink layer. In this way, even if a polyolefin resin having generally poor adhesion is used as the resin component of the base sheet, the adhesion between the base sheet and the glittering ink layer is improved, and the interior of the decorative sheet is improved. Can improve the interlayer adhesion. This is because a glitter ink layer is formed on the base sheet adjacent to the base sheet, and when the two-part curable urethane resin of the glitter ink layer is cured, the isocyanate component is applied to the surface of the base sheet. The binder resin of the glittering ink layer and the resin of the base sheet are molecularly bonded to each other by chemically reacting with the active hydrogen-containing group of This is because they can be brought into close contact. As a result, when the decorative sheet is laminated on an adherend such as a resin molded product to form a decorative molded product, poor adhesion such as peeling of the glittering ink layer due to poor interlayer adhesion of the decorative sheet itself. The occurrence can be prevented.

The two-component curable urethane resin has a polyol as a main component and an isocyanate as a crosslinking agent (curing agent).
Urethane resin. The polyol is a compound having two or more hydroxyl groups in the molecule, for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol and the like. As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in a molecule is used. For example, 2,4-tolylene diisocyanate, xylene diisocyanate,
Aromatic isocyanates such as naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, or 1,6-hexamethylene diisocyanate;
2,4-trimethylhexamethylene diisocyanate,
Aliphatic (or alicyclic) isocyanates such as isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are used. Alternatively, adducts or multimers of the above various isocyanates, for example, adducts of tolylene diisocyanate, trimers of tolylene diisocyanate (trime)
r) and the like are also used.

In order to ensure that the isocyanate reacts with the active hydrogen-containing groups on the surface of the base sheet, the number of isocyanate groups in the isocyanate is adjusted to the number of hydroxyl groups of the polyol to be reacted therewith. It is preferable to mix them more than the number. Specifically, [the number of isocyanate groups / the number of hydroxyl groups] is about 1.05 to 1.4.

The brilliant ink layer is formed on the entire surface or partially in a desired pattern by using the brilliant ink as described above by a conventionally known printing method such as gravure printing, silk screen printing, offset printing or the like. I do. In addition, when it forms on the whole surface, it can also be formed using conventionally well-known coating methods, such as a gravure coat and a roll coat. In addition,
As shown in FIGS. 1 and 2, on the back surface of the base sheet and in the vicinity thereof, the flat surface F of the flaky particles serving as the brilliant pigment is arranged in parallel or substantially parallel to the back surface of the base sheet. It is preferable to adopt the following methods (1) to (3). (1) As a forming method, a coating or printing method is used in which a shear stress is applied to a coating film during formation of gravure rotary printing, gravure coating, roll coating, or the like. (2) As the glittering ink, a solvent-diluted ink or a curable type having curing shrinkage is used, and the coating film has shrinkage during drying and curing. (3) Combination of (1) and (2).

When the glitter ink layer is partially formed in a pattern, the pattern of the glitter ink layer is optional.
For example, wood grain patterns, stone patterns, sand patterns, cloth patterns, leather patterns, tiled patterns, brickwork patterns, geometric figures, letters, symbols, or a combination of two or more kinds of solid surfaces Pattern is used.

It is essential that the glitter ink layer contain a glitter pigment.
The layer colored by the colorant may be formed by adding the colorant as described in the base sheet.

[Picture ink layer] Incidentally, if necessary,
A pattern ink layer that does not contain a glitter pigment but does contain a coloring agent may be provided between the base sheet and the glitter ink layer (not shown). The picture ink layer is a layer formed using a coloring ink containing a coloring agent in a binder resin.
As the binder resin, the resins described above for the glittering ink layer can be used. The same applies to the preferred embodiment of the two-component curable urethane resin. Further, as the coloring agent, the coloring agent as described in the base sheet can be used. Therefore, further description is omitted here.

The pattern ink layer is formed by applying the above-described colored ink to a known printing method such as gravure printing, letterpress printing, offset printing, silk screen printing, transfer printing from a transfer sheet, ink jet printing, or a hand-painted method. It is formed over the entire surface or partially in a desired pattern by a known forming method. When forming over the entire surface,
It can also be formed using a conventionally known coating method such as gravure coating or roll coating.

When the pattern ink layer is partially formed in a pattern, the pattern is arbitrary. For example, a wood grain pattern, a stone grain pattern, a grain grain pattern, a cloth grain pattern, a leather pattern, a tiled pattern, a brick A product pattern, a geometric figure, a character, a symbol, or a pattern obtained by combining one or two or more kinds of solid areas or the like are used. When the pattern ink layer is formed on the entire surface, the color of the pattern ink layer is, of course, transparent so that the glittering ink layer below the pattern ink layer can be seen. In addition, the transparent coloring includes translucent.

[Colored Ink Layer] The colored ink layer 3 has the same hue or substantially the same color as that of the glittering ink layer on the back side of the glittering ink layer 2 (the side opposite to the substrate sheet with respect to the glittering ink layer). This is a layer formed as a colored layer having the same hue. Specifically, (1) a red or reddish-brown colored ink layer is formed on the back surface of a glitter ink layer containing a glitter pigment composed of copper particles, or (2) a glitter pigment composed of brass or gold particles. A yellow or yellow-brown colored ink layer is formed on the back surface of the glitter ink layer containing (3) or a gray ink is formed on the back surface of the glitter ink layer containing the glitter pigment composed of silver or aluminum particles. Or a colored ink layer. By providing such a colored ink layer, it is preferable to prevent the color of the stretched portion of the decorative sheet at the time of molding from being lightened. More preferably, the color ink layer has the same or substantially the same brightness and saturation as the glitter ink layer.

Such a colored ink layer is formed using a colored ink containing a colorant in a binder resin.
As the binder resin, a resin as described in the glossy ink layer can be used. Further, as the coloring agent, the coloring agent as described in the base sheet can be used. Therefore, further description is omitted here. The colored ink layer is formed on the entire surface or partially in a desired pattern by using a conventionally known printing method such as gravure printing, silk screen printing, offset printing, or the like. In addition, when forming on the entire surface, a gravure coat,
It can also be formed using a conventionally known coating method such as roll coating.

[Adhesive Layer] The back side of the decorative sheet may be optionally subjected to corona discharge treatment, plasma treatment, primer coating, etc., in order to improve the adhesion to the adherend such as a resin molded product. Alternatively, the adhesive layer 4 may be provided after or without the easy adhesion treatment (see FIG. 1). As the adhesive layer 4, for example, a known resin such as a thermoplastic resin or a thermosetting resin is used as a heat-sensitive adhesive depending on an adherend material, a lamination method, or the like. In the thermoplastic resin, for example, acrylic resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, polyamide resin,
One type or a mixture of two or more types such as a rubber-based resin is used. As the thermosetting resin, a urethane resin, an epoxy resin, or the like is used. The adhesive layer is formed by using a known printing or coating method such as gravure printing or roll coating. The thickness of the adhesive layer is not particularly limited, but is usually about 1 to 100 μm.

[Laminating method of decorative sheet on adherend]
As a method of laminating the decorative sheet of the present invention to an adherend,
Basically, there is no particular limitation, and various conventionally known lamination methods may be employed according to the application. For example, for example, (1) simultaneous injection molding decoration method, (2) vacuum forming and laminating method [Japanese Patent Publication No. Sho 5
6-45768 (overlay method), Japanese Patent Publication No. 60
-58014 (vacuum press method) etc.], (3)
A laminating method using an elastic roller (including a lapping method (see Japanese Patent Publication No. 61-5895 and Japanese Patent Publication No. 56-23377)) and the like can be mentioned. (1)
Is a preferred method as the lamination method of the present invention, and will be described in detail below.

The injection-mold decorating method: injection-mold decorating method of the present invention, by using the decorative sheet of the present invention described above, by a so-called injection-mold decorating method, decorated on the surface of the resin molded product This is a method in which a sheet is formed and laminated to obtain a decorative molded article which is decorated with a mirror-like metallic glossy design using the decorative sheet.

As described in Japanese Patent Publication No. 50-19132 and Japanese Patent Publication No. 43-27488, the simultaneous decorating method by injection molding involves inserting a decorative sheet between the male and female molds, The molds are clamped, the resin in the fluid state is injected into the cavity formed by the molds and solidified, and a decorative sheet is laminated on the surface at the same time as the molding of the resin molded product to obtain a decorative molded product. Is the way.

The injection molding simultaneous decorating method of the present invention can take various forms in the conventionally known injection molding simultaneous decorating method, except that the above-described decorative sheet of the present invention is used as the decorative sheet to be used. Things. For example, basically, in a mode in which the decorative sheet is preformed or not,
Either is acceptable. Further, the decorative sheet may or may not be preheated. Note that the decorative sheet is usually preheated at the time of preforming. However, in order to maximize the effect of the decorative sheet of the present invention, it is preferable that the decorative sheet is formed anyway.

Of course, when the decorative sheet has a large drawing, it is preferable to perform preforming. On the other hand, when the decorative sheet is not narrowed down, the decorative sheet may be formed by the resin pressure of the resin in the flowing state to be injected. At this time, if the drawing is shallow, the decorative sheet may be formed only by the resin pressure of the resin in the flowing state to be filled in the mold at the same time as the resin injection without preforming. Further, even when the decorative sheet is formed by resin pressure, the decorative sheet may utilize the heat of the injection resin without preheating. In addition, the pre-molding of the decorative sheet is usually performed by using the injection mold also as the vacuum mold, but before supplying the decorative sheet between the molds, the decorative mold is decorated with another vacuum mold outside the mold. Preforming such as vacuum forming of a sheet (offline preforming) may be used. However, the preforming is preferably performed by using both the injection molding die and the vacuum molding die in that the decorative sheet can be efficiently and accurately laminated. However, in the case where the preformed decorative sheets are collectively manufactured in another place in advance, the preforming is preferably in the form of off-line preforming. In the description of the present invention, vacuum forming includes vacuum pressure forming.

The injection molding simultaneous decorating method of the present invention will be described with reference to a conceptual diagram of FIG. In addition, the form described here is a form in which the decorative sheet is heated and softened between the molds, preliminarily molded by vacuum molding with an injection mold, and then resin is injected by clamping before the mold is clamped. .
This form is more preferable when the decorative sheet is deeply drawn out of the various combinations of the preforming and preheating of the decorative sheet described above. It should be noted that the decorative sheet used in the simultaneous injection molding decorative method of the present invention may be either a single sheet or a continuous strip.

First, as shown in FIG. 4A, the injection mold includes a mold Ma having a runner (runner) and a gate (gate) communicating with the injection nozzle, and a suction hole 4 formed in the cavity surface.
A pair of molds Mb having the number 1 and also serving as a sheet preform is used. These molds are made of metal such as iron or ceramics. Both molds Ma and Mb in the mold open state
The decorative sheet S is supplied in between, and the decorative sheet S is fixed to the mold Mb by pressing it with a sheet clamp 42 having a frame shape in plan view. At this time, it is a matter of course that the glittering ink layer side (relative to the base sheet) of the decorative sheet faces the injection resin side on the right side of the drawing. Next, the decorative sheet is appropriately heated and softened by a heater (not shown) inserted between both molds. The heating is, for example, non-contact radiation heating, but may be conduction heating by contact. Then, the decorative sheet is sucked through the suction hole and vacuum formed, and the decorative sheet is preformed along the cavity surface of the mold Mb. Next, the heater is retracted from between the two dies, and FIG.
As shown in (B), both molds are clamped, and a cavity formed by both molds is filled with a resin in a flowing state such as a heated and molten state. After the resin is solidified by cooling or the like, the mold is opened and the molded product is taken out. Then, if the unnecessary portion of the decorative sheet is trimmed appropriately, the decorative sheet is laminated on the resin molded product to obtain a decorative molded product having a configuration.

[Injection Resin] In the simultaneous decorating method for injection molding of the present invention, the resin to be injection-molded is not particularly limited and may be a known resin. What is necessary is just to select according to the required physical properties of a product, cost, etc. If it is a thermoplastic resin, it may be an ABS (acrylonitrile-butadiene-styrene copolymer) resin, a styrene resin, an acrylic resin, a vinyl chloride resin, a polycarbonate resin, a polyolefin resin, or the like. In the case of a curable resin, it is a two-liquid curable resin, for example, an uncured resin liquid such as a urethane resin, an unsaturated polyester resin, or an epoxy resin. The thermoplastic resin is melted by heating and injected in a fluid state, and the curable resin (the uncured product) is injected in a flowing state at room temperature or appropriately heated. Note that, as the injection resin, a resin colored by adding a coloring agent may be used as appropriate depending on the application. As the colorant, a known colorant as described in the base sheet may be used. In addition, the injection resin contains, as necessary, various known additives such as silica, alumina, talc, calcium carbonate, inorganic powders such as aluminum hydroxide, fillers such as glass fibers, stabilizers, and lubricants. .

[Decorative molded article] The decorative molded article obtained as described above is obtained by forming the above-described decorative sheet of the present invention on a resin molded article, and forming a glitter ink layer on the base sheet. A molded product having a configuration in which the components are laminated in a direction facing the resin molded product side is obtained. What is necessary is just to shape | mold to a desired various shape as a shape of a molded article. In addition, the obtained decorative molded product is an interior or exterior member of an automobile, a housing (cabinet) of a home appliance,
It can be used as various members such as containers and daily necessities.

[0046]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples.

Example 1 A decorative sheet S having the structure shown in FIG. 1 was produced as follows. As the base sheet 1, a thickness 1 obtained by adding 0.2% by mass of an aliphatic alcohol-based lubricant and 0.5% by mass of a benzotriazole-based ultraviolet absorber to a methyl methacrylate-butyl methacrylate copolymer.
A 25 μm colorless and transparent acrylic resin sheet was prepared.
Also, JIS B on both sides of this acrylic resin sheet
The center line average roughness of 0601 standard was 0.1 μm.

On the back side of the base sheet, a 6: 4 mass ratio mixed resin of an acrylic resin and a vinyl chloride-vinyl acetate copolymer was used as a binder resin, and the average particle size was 15 μm.
A glittering ink layer having a thickness of 4 μm by printing a glittering ink containing a glittering pigment a composed of aluminum flaky particles of 60% by mass with respect to the resin content by two-color overprinting of gravure printing. 2 was formed. Further, an adhesive ink using a 6: 4 mass ratio mixed resin of an acrylic resin and a vinyl chloride-vinyl acetate copolymer is printed on the entire surface of the glitter ink layer by gravure printing to obtain a thickness. The decorative sheet S having the configuration as shown in FIG. 1 was obtained by forming the 6 μm adhesive layer 4.

The decorative sheet is laminated on the surface of the resin molded article simultaneously with the molding of the resin molded article by the simultaneous injection molding and decorating method of the present invention as shown in the conceptual diagram of FIG. A decorative molded product P of the present invention having a configuration was obtained. In addition,
As a molded product to be decorated, a width of 40 mm and a length of 40 mm
The vehicle interior panel had a thickness of 0 mm and a thickness of 3 mm. And the injection molding simultaneous decorating method, the female mold of injection molding was used as a vacuum mold, and after inserting the decorative sheet between the male and female molds, the sheet was heated to a sheet temperature of 110 ° C. with an infrared radiation heating type heater and softened. Then, vacuum suction from the groove-shaped suction holes provided in the female mold, the decorative sheet (relative to the base sheet) so that the glitter ink layer and the adhesive layer face the male mold side, Preformed along the shape of the female cavity.

Thereafter, the injection resin temperature is 240 ° C., the mold temperature is 7
Under the condition of 0 ° C., brown heat-resistant ABS resin (heat-resistant temperature 95
° C) was injected from a male gate, and the decorative sheet and the resin molded product were integrated to form a decorative molded product.

The decorative molded article thus obtained has a silver-colored surface, and the glittering ink layer can be seen through a smooth surface (front and back surfaces of the base sheet). In the vicinity of the interface with the substrate, as shown in FIG. 1, the glittering pigment a is arranged so that its flat surface is parallel to the back surface of the base material sheet. A molded product having a mirror-like metallic luster similar to that of the metal was obtained.
However, as shown in FIG. 5 (A), the corners of the decorative molded product P are turned to a thin film by extending the glittering ink layer 2, and the color of the underlying resin molded product 5 is seen through to brown. It looked like it, and therefore the mirror gloss was also slightly reduced.

Example 2 In Example 1, a colored ink layer 3 was formed between the glitter ink layer 2 and the adhesive layer 4 in the following manner. Otherwise, in the same manner as in Example 1, a decorative sheet (see FIG. 2) and a decorative molded product were obtained.

The coloring ink used for the coloring ink layer was a mixture of an acrylic resin and a vinyl chloride-vinyl acetate copolymer in a ratio of 6: 4 by mass, and the coloring agent was gray (Munsell containing carbon black and titanium white). Lightness V in color system
= 4). The colored ink layer was formed to a thickness of 4 μm by two-color gravure printing.

The obtained decorative molded product had a silver color on the surface and had a mirror-like metallic luster similar to the plating. At the corners of the decorative molded product (see FIG. 5 (B)), the change in color tone and the decrease in specular metallic luster were inconspicuous to the naked eye.

Comparative Example 1 In Example 1, the same brilliant pigment a as that used in Example 1 for the brilliant ink layer was added to the acrylic resin sheet used as the base material sheet in an amount of 60% by mass. This was used as a glittering base sheet 11.
Instead, the formation of the glittering ink layer was omitted, and the adhesive layer 4 was formed to produce a decorative sheet 10 as shown in the sectional view of FIG. Then, a decorative molded product was produced in the same manner as in Example 1. The obtained decorative molded product had a silver color on the surface, but remained matte-like metallic luster. As conceptually shown in FIG. 6, the incident light L _IN to the substrate sheet is a result of reflected as substrate diffusion in multiple directions in the sheet surface (turbulent) reflected reflected light L _RF1a. On the other hand, no change in color tone or change in metallic gloss at the corners of the decorative molded product was visually observed. The decorative sheet has a center line average roughness of 7 μm on its surface.
Met.

Comparative Example 2 In Example 1, an acrylic resin sheet having the same center line average roughness of 6 μm, which had the same resin composition but had matte embossing on both front and back surfaces, was used as the base sheet. Except for this, a decorative sheet and a decorative molded product were obtained in the same manner as in Example 1. The obtained decorative molded product had a silver color on the surface, but remained matte-like metallic luster. Further, the change in color tone and metallic luster at the corners of the decorative molded product was visually noticeable.

[0057]

(1) According to the decorative sheet of the present invention, an adherend such as a resin molded product can be easily provided with a mirror-like metallic luster. Moreover, since the plating process is not used, there is no problem of pollution in the plating process and no problem of waste liquid treatment.
Production efficiency does not decrease due to an increase in the post-coating process. Further, in the portion where the decorative sheet is extended, the appearance is not deteriorated due to cracks such as a vapor deposition film. (2) Further, if the decorative sheet has a configuration in which a specific colored ink layer is provided on the back side of the glitter ink layer, the decorative sheet is formed and stretched, and the glitter ink layer is stretched and thinned. However, due to the presence of the colored ink layer on the back surface, it is possible to reduce a change in color tone of the glittering ink layer and a lack of concealment of the color of the underlying adherend. (3) Further, if a decorative sheet having an adhesive layer on the outermost surface is used, it can be laminated with good adherence to an adherend made of various materials. (4) According to the simultaneous injection molding and decorating method of the present invention,
The effect of the decorative sheet of the present invention can be obtained, and a mirror-finished metallic luster can be easily imparted to the resin molded product.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating one embodiment of a decorative sheet of the present invention.

FIG. 2 is a cross-sectional view illustrating another embodiment of the decorative sheet of the present invention.

FIG. 3 is a perspective view for explaining the definition of a flat surface and a diameter of a glittering pigment which is a scaly particle.

FIG. 4 is a conceptual diagram illustrating the simultaneous injection molding decorating method of the present invention in one embodiment.

FIG. 5 is a sectional view conceptually illustrating a corner portion of the decorative molded product.

FIG. 6 is a cross-sectional view illustrating one form of a conventional decorative sheet.

[Explanation of symbols]

REFERENCE SIGNS LIST 1 base sheet 2 brilliant ink layer 3 colored ink layer 4 adhesive layer 5 resin molded article 10 conventional decorative sheet 11 brilliant base sheet 41 suction hole 42 sheet clamp a brilliant pigment F Scale-like particles Flat surface of bright pigment L _IN incident light L _RF reflected light Ma Injection mold (male type) Mb Injection mold (female type) P Decorative molded product S Decorative sheet t Thickness of luminous pigment which is scale-like particles

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4F100 AB10H AH03H AK01B AK01C AK15 AK22 AK25 AL01 AR00D BA03 BA04 BA07 BA10A BA10C BA10D CA07 CA13B DE02B DE02H EC182 EH362 GB90 HB31B HB31C JK15A JL10JNJAD11 JA07 JB19 JF05 JL02

Claims (4)

[Claims] 1. A brilliant composition comprising scaly particles having a metallic luster in a binder resin on the back surface of a smooth and transparent base sheet having a center line average roughness of 1 μm or less according to JIS B 0601 on both front and back surfaces. It is formed by forming a brilliant ink layer containing a pigment, and the flat surface of the scaly particles is parallel or at least parallel to the back surface of the base sheet at the interface between the back surface of the base sheet and the brilliant ink layer. A decorative sheet that is almost parallel. 2. The decorative sheet according to claim 1, further comprising a colored ink layer having the same hue or substantially the same hue as the glittering ink layer formed on the back side of the glittering ink layer. 3. The decorative sheet according to claim 1, further comprising an adhesive layer on the rearmost surface. 4. The decorative sheet according to any one of claims 1 to 3 is inserted between the male and female molds with the glitter ink layer facing the injection resin side with respect to the base sheet. After that, the molds are clamped, the resin in a fluid state is injected into the cavity formed by the molds, and after the resin is solidified, the mold is opened, and the decorative sheet is formed on the surface of the resin molded product. Injection molding simultaneous decoration method to obtain laminated decorative molded products.