JP2000086777A - Flame retardant decorative film and laminate using the same - Google Patents

Abstract

(57) [Problem] To provide a decorative film which is easily imparted with a design property and can be in-mold molded, and has a concealing property and flame retardancy, and using the film as a surface coating layer, Provided is a laminate formed by injection molding or the like. SOLUTION: A flame-retardant decorative film comprising at least four components of a filler, a concealing agent, a flame retardant, and a rubber-modified thermoplastic resin, and one or more inner layers (A) and at least one of the inner layers (A) Surface coating layer (B) covering the outermost layer surface
Wherein the surface coating layer (B) is formed of the flame-retardant decorative film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is useful and difficult as a film for interior and exterior materials which can be given a design property by printing or the like on the surface or can be attached to the surface of a substrate and molded together with the substrate. The present invention relates to a flame-retardant decorative film having excellent flammability, and a laminate having the film disposed on the surface.

[0002]

2. Description of the Related Art In recent years, there has been a diversification of consumer needs regarding the design and habitability of plastic molded products used in household appliances, automotive interior goods, kitchenware, cosmetic containers, toys and the like. Accordingly, there is a strong tendency that a surface finish having a high design property is desired. For this reason, in the case of a cash card, for example, screen printing is performed after punching a vinyl chloride sheet, but in this case, the number of steps is large, and the processing time and cost are large.

Further, in the case of IC cards which have begun to spread in recent years, a complicated processing method is required to embed an IC chip in the card, so that the cost becomes large and expensive, and the IC card is used for some special applications. We use only a small amount. Inexpensive manufacturing methods are being studied in various fields with the aim of widespread use. One of the most promising manufacturing methods is the in-mold molding method.

The in-mold molding method is an integral molding method in which a printed decorative film, an IC chip, and accessory parts are set in a mold, and then an injection molding resin is injected. At that time, a vinyl chloride film is generally used as a printed decorative film in the past, but the vinyl chloride film is inferior in durability and, in recent years, has been used to reduce the use due to environmental problems. Due to the fact that it is a chlorine-containing resin, its use is contrary to the public. In addition, when a polybutyl terephthalate film or a polycarbonate film is used, there is a problem that the film is not concealable and if a concealing agent is added, the film becomes brittle and the film becomes difficult to form. Further, even when a polyethylene terephthalate film is used, sinking occurs in the chip portion in the card when integrally molded, and there is no hiding property, and when a hiding agent is added, the film becomes brittle and it becomes difficult to form a film. When a rubber-modified thermoplastic film is used, it is difficult to use because there are problems such as low designability, lack of concealment, and generation of sink marks due to gloss.

On the other hand, IC cards tend to be required to have flame retardancy, and there has been a demand for the development of a material that satisfies these characteristics in a well-balanced manner.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and is a film which can be easily provided with a design property, can be molded in-mold, and has a concealing property and flame retardancy. An object of the present invention is to provide a decorative film and a laminate formed by injection molding or the like using the film as a surface coating layer.

[0007]

SUMMARY OF THE INVENTION The present invention provides a flame-retardant decorative film comprising at least four components of a filler, a concealing agent, a flame retardant, and a rubber-modified thermoplastic resin, and a laminate using the same. It is.

Hereinafter, the present invention will be described specifically. The rubber-modified thermoplastic resin used for the flame-retardant decorative film of the present invention comprises (a) a rubber component, (b) an aromatic vinyl monomer and / or an alkyl (meth) acrylate,
(C) vinyl cyanide monomers (b) and (c)
It is constituted by graft-polymerizing a vinyl monomer composed of the components.

(A) The rubber component is not particularly limited as long as it does not limit the function of the present invention, but a diene rubber or an olefin copolymer rubber is preferably used.

The diene rubber includes, for example, polybutadiene rubber, polyisoprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, polychloroprene rubber, butyl rubber, and the like, with polybutadiene rubber being preferred.

Examples of the olefin-based copolymer rubber include ethylene-α-olefin-based copolymer rubber, acrylic rubber, chlorinated polyethylene, ethylene-vinyl acetate copolymer rubber, and the like. -Α-olefin copolymer rubber is preferred.

The ethylene-α-olefin copolymer rubber includes, for example, an ethylene-α-olefin binary copolymer, an ethylene-α-olefin-nonconjugated diene terpolymer and the like. α-olefins include propylene, butene-1, pentene-1, 3-methylpentene
Α-olefins having about 3 to 8 carbon atoms, such as 1, hexene-1, heptene-1 and octene-1 are included. Preferred as α-olefins are α-olefins having about 3 to 6 carbon atoms, particularly propylene.

As the non-conjugated diene component, for example,
Chain non-conjugated dienes such as 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene; cyclo Cyclic non-conjugated dienes such as hexadiene, dicyclopentadiene and methyltetrahydroindene; 5-vinylnorbornene, 5-ethylidene-2
-Norbornene, 5-methylene-2-norbornene, 5
Alkenyl norbornenes such as -isopropylidene-2-norbornene and the like are used.

Preferred ethylene-α-olefin copolymer rubbers include, for example, ethylene-propylene copolymer rubber [for example, JSR-E manufactured by Nippon Synthetic Rubber Co., Ltd.]
PM (trade name) etc .; ethylene-propylene-ethylidene norbornene copolymer rubber, ethylene-propylene-
Ethylene-propylene-non-conjugated diene copolymer rubber such as dicyclopentadiene copolymer rubber and ethylene-propylene-1,4-hexadiene copolymer rubber [for example, JSR-EPDM (product of Nippon Synthetic Rubber Co., Ltd.) Name) etc.]
But ethylene-propylene copolymer rubber is particularly preferable.

In the ethylene-α-olefin copolymer rubber, the ratio of ethylene to α-olefin is usually 90/10 to 20/80 (ethylene / α-
Olefin), preferably 90/10 to 30 /
70, more preferably 90/10 to 60 by weight.
/ 40, particularly preferably 90/10 to 65/3 by weight.
5

In the ethylene-α-olefin-non-conjugated diene copolymer rubber, the non-conjugated diene content is as follows:
Usually, it is preferably 5 to 40 in terms of iodine value.

The acrylic rubber includes a copolymer mainly composed of an alkyl acrylate such as ethyl acrylate and butyl acrylate. Examples of the copolymerizable monomer constituting the copolymer include a chlorine-containing acrylic monomer, acrylonitrile, a carboxyl group-containing (meth) acrylic monomer, and an epoxy group-containing (meth) acrylic monomer.

The rubber component can be used alone or in combination of two or more.

(B) As the aromatic vinyl monomer, for example, styrene, alkyl-substituted styrene (for example, o-
Methylstyrene, p-methylstyrene, m-methylstyrene, 4-dimethylstyrene, p-ethylstyrene, p
-T-butylstyrene, etc.), α-alkyl-substituted styrene (eg, α-methylstyrene, α-methyl-p-methylstyrene, etc.), halogenated styrene (eg, o-chlorostyrene, p-chlorostyrene, etc.), etc. Styrene monomers such as styrene, p-methylstyrene and α-methylstyrene are preferred, and styrene monomers are particularly preferred.
These aromatic vinyl monomers can be used alone or in combination of two or more.

In order to enhance the light resistance, an alkyl (meth) acrylate may be used instead of or together with the aromatic vinyl monomer.
Examples of the alkyl include methyl, ethyl, n-
Propyl, isopropyl, n-butyl, isobutyl, t
And lower alkyl groups having about 1 to 4 carbon atoms such as -butyl.

Specifically, examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate. As the acrylate, alkyl methacrylate is preferred, and methyl methacrylate is particularly preferred. By using such an alkyl (meth) acrylate, the transparency of the film is improved. These alkyl (meth) acrylates can also be used alone or in combination of two or more.

(C) As the vinyl cyanide monomer,
For example, acrylonitrile, methacrylonitrile and the like can be mentioned, and acrylonitrile is preferable. These vinyl cyanide monomers can be used alone or in combination of two or more.

As long as the properties of the rubber-modified thermoplastic resin are not impaired, maleimides such as N-phenylmaleimide and cyclohexylmaleimide; and unsaturated dicarboxylic anhydrides such as maleic anhydride and itaconic anhydride can be copolymerized. Other monomers may be used in combination.

For use in the flame-retardant decorative film of the present invention,
More specifically, the rubber-modified thermoplastic resin is, for example, a polymer obtained by graft-polymerizing an aromatic vinyl monomer and a vinyl cyanide monomer to a diene rubber [for example, a polymer obtained by graft-polymerizing styrene and acrylonitrile to a polybutadiene rubber] (ABS resin) etc.]
(Hereinafter referred to as ABS polymer)); ethylene-α
-A polymer obtained by graft-polymerizing an aromatic vinyl monomer and a vinyl cyanide monomer onto an olefin rubber [for example, a polymer (AES resin) obtained by graft-polymerizing styrene and acrylonitrile onto an ethylene-propylene copolymer rubber, etc.] , AES-based polymer); a polymer obtained by graft-polymerizing an aromatic vinyl monomer and a vinyl cyanide monomer onto an acrylic rubber [eg, a polymer (AAS resin) obtained by graft-polymerizing styrene and acrylonitrile onto an acrylic rubber]; Polymers obtained by graft-polymerizing aromatic vinyl monomers and vinyl cyanide monomers onto chlorinated polyethylene [eg, polymers obtained by graft-polymerizing styrene and acrylonitrile onto chlorinated polyethylene (ACS resin), etc. A polymer obtained by graft-polymerizing an aromatic vinyl monomer and a vinyl cyanide monomer onto an ethylene-vinyl acetate copolymer [eg, a polymer obtained by graft-polymerizing styrene and acrylonitrile onto an ethylene-vinyl acetate copolymer, and the like]; No.

Preferred rubber-modified thermoplastic resins include AB
S-based polymers and AES-based polymers are included.

The rubber-modified thermoplastic resin comprises (a) a rubber component, B) an aromatic vinyl monomer and / or an alkyl (meth) acrylate, and (c) a vinyl cyanide monomer, (b) and (c) components. Since the copolymer composed of a vinyl monomer composed of the above is modified, it has high elongation at break and high rigidity, and also has excellent impact resistance, chemical resistance, and the like.

In the rubber-modified thermoplastic resin used for the flame-retardant decorative film of the present invention, (a) a rubber component and (b)
The ratio of the aromatic vinyl monomer and / or the alkyl methacrylate, (c) the vinyl cyanide monomer to the vinyl monomer composition composed of the components (b) and (c) depends on the type of each component and the use of the film. Depending on the weight ratio, (a) / ｛(b) +
(C)｝ = 2/98 to 50/50, more preferably 5/95 to 45/55 by weight, and particularly preferably 10/90 to 40/60 by weight. A resin in which the ratio of the rubber component to the monomer composition is in the above range has excellent rigidity and tensile strength, and also has excellent impact resistance. If the rubber component exceeds 50% by weight, the film formability tends to decrease.

In the rubber-modified thermoplastic resin used for the flame-retardant decorative film of the present invention, (b) an aromatic vinyl monomer and / or an alkyl methacrylate;
(C) vinyl cyanide monomers (b) and (c)
In a vinyl monomer composition composed of components,
The ratio of the component (b) to the component (c) is preferably (b) / (c) = 90/10 to 50/50 by weight, more preferably 80/20 to 60/40 (by weight). .

The thermal deformation temperature HDT of the rubber-modified thermoplastic resin used for the flame-retardant decorative film of the present invention can be appropriately selected according to the use of the flame-retardant decorative film of the present invention, but is preferably 70 to 70. The temperature is preferably 150 ° C., more preferably 80 to 130 ° C. The HDT can be adjusted by the amount of the rubber component, the type of the vinyl monomer, the graft ratio, and the like.

The rubber-modified thermoplastic resin used for the flame-retardant decorative film of the present invention can be obtained by a conventional grafting method. Examples of such a grafting method include, for example,
A graft polymerization method for polymerizing a monomer composition composed of the components (b) and (c) in the presence of a rubber component, and a polymer or copolymer comprising at least one monomer among the copolymerization components. A graft blending method in which a polymer is produced separately and blended with the graft copolymer obtained as described above may be used. Preferably, a graft copolymer is used.

The polymerization can be carried out by a conventional polymerization method, for example, emulsion polymerization, solution polymerization, suspension polymerization and the like.

In the rubber-modified thermoplastic resin used for the flame-retardant decorative film of the present invention, the graft ratio can be appropriately selected according to the type of each component and desired characteristics, but is preferably 10 to 90%. And more preferably 35 to 7
5% is good, particularly preferably 40-70%.

The rubber-modified thermoplastic resin is usually
A particulate (a) rubber component is dispersed in a continuous phase of a copolymer composed of (b) an aromatic vinyl polymer and / or an alkyl (meth) acrylate and (c) a vinyl cyanide monomer. Often. The average particle diameter of the dispersed rubber component particles is preferably 0.05 to 2.0 μm.
m is good, more preferably 0.1 to 1.0 μm, and particularly preferably 0.2 to 0.6 μm.

The rubber-modified thermoplastic resin used for the flame-retardant decorative film of the present invention is in a range not impairing its properties.
Other resins, such as nylon 6, polybutylene terephthalate, polycarbonate, and the like, may be included, and such resins may be blended or alloyed with the rubber-modified thermoplastic resin [for example, Daicel Chemical Industries (Trade name) Novalloy A (ABS / nylon 6-alloy), B (ABS / polybutylene terephthalate alloy), S (ABS / polycarbonate-alloy)
Series etc.]. In such a case, the content of the other resin in the rubber-modified thermoplastic resin is preferably 30% by weight or less, more preferably 20% by weight or less.

The filler used in the flame-retardant decorative film of the present invention includes calcium carbonate, clay, talc, silica, wollastonite, zeolite, diatomaceous earth, and the like.
Silica sand, pumice powder, slate powder, alumina colloid liquid,
Alumina white, aluminum sulfate, barium sulfate,
Litobon, calcium sulfate, molybdenum disulfide, surface treatment filler, mica powder, graphite, glass fiber, glass sphere, volcanic glass hollow body, carbon fiber, carbon hollow sphere,
Anthracite powder, artificial cryolite, silica spherical particles, alumina fiber, recycled rubber, rubber powder, ebonite powder, shellac, wood powder, coconut husk powder, cork powder, cellulose powder (powder fibrous material), wood pulp, Paper and cloth,
Silicone resin fine powder, polyvinyl alcohol fiber, aramid fiber, high-strength polyarylate fiber, and the like can be used, but are not limited thereto, and preferably a particulate form is preferred. Particularly preferred as the filler used in the present invention are talc and silica.

In the flame-retardant decorative film of the present invention,
The amount of the filler added to the rubber-modified thermoplastic resin and the average particle size are within a range that does not hinder the function and moldability of the flame-retardant decorative film, and the necessary surface roughness such as the use of the flame-retardant decorative film is required. May be determined as appropriate, but preferably,
Surface roughness (measured according to IJS B0601) of 50
The surface roughness (measured in accordance with IJS B0601) is more preferably 5 μm or less.
m to 30 μm. When the surface roughness is less than 5 μm, the design property is low, and when the surface roughness exceeds 30 μm, the film formability and printability are likely to be reduced. Preferably, a filler is added in an amount of 3 to 30% by weight based on 100% by weight of the components constituting the flame-retardant decorative film of the present invention. More preferably, it is 8 to 25% by weight. If the amount of the filler exceeds 30% by weight, the film becomes brittle and the film is difficult to form. If the amount is less than 3% by weight, the surface roughness is small and the design is poor, and sink marks occur to deteriorate the formability. Become.

The average particle size of the filler is preferably 1 to 1.
It is preferably 20 microns, more preferably 3 to 12 microns. If the average particle size of the filler is more than 20 microns, pinholes are formed in the film, making the film difficult to form. If the average particle size is less than 1 micron, the surface roughness is small, so the design is poor, and the sink mark is reduced. It occurs and moldability deteriorates.

As the concealing agent used in the flame-retardant decorative film of the present invention, conventionally known concealing agents can be used, and examples thereof include the following, but are not limited thereto. White pigments (titanium oxide, zinc white, lead white, lithopone, barite, precipitated barium sulfate, calcium carbonate, gypsum, precipitated silica), black pigments (carbon black, lamp black, titanium black, synthetic iron black), gray pigment (Zinc powder, Lead oxide, Slate powder), Red pigment (Cadmium red, Cadmium mercury red, Silver vermilion, Bengala,
Molybdenum red, lead red, Komyo red), brown pigment (amber,
Iron oxide tea), yellow pigments (cadmium yellow, zinc yellow, ocher,
Oka, yellow iron oxide, synthetic ocher, graphite, titanium yellow),
Inorganic pigments such as green pigments (chromium oxide green, cobalt green, chrome green), blue pigments (ultra blue, navy blue, iron blue, cobalt blue), metal powder pigments, etc .; azo pigments (permanent red 4)
R, Para Red, First Yellow G, First Yellow 10G, Disazo Yellow G, Disazo Yellow GR, Disazo Orange, Pyrazolone Orange,
Brilliant Carmin 3B, Brilliant Carmin 6B, Brilliant Scarlet G, Brilliant Carmin
Bordeaux 10B, Bordeaux 5B, Permanent Red F5R, Permanent Carmin FB, Risor Red R, Risor Red B, Rake Red C, Rake Red D, Brilliant Fast Scarlet,
Pyrazolone red, bon maroon light, bon
Maroon media, fire red), nitroso pigment (naphthol green B), nitro pigment (naphthol yellow S), basic dye lake (rhodamine B lake, rhodamine 6G lake), mordant dye lake, vat dye Pigments, phthalocyanine pigments (phthalocyanine
Organic pigments such as blue, phthalocyanine green, fast sky blue, aniline black) and dioxazine pigments (dioxazine violet); organic fluorescent pigments; pearl foil;

The concealing agent used in the flame-retardant decorative film of the present invention preferably includes inorganic pigments such as titanium oxide and carbon black having a high concealing property. As the base, white titanium oxide is used because white is highly versatile.

In the flame-retardant decorative film of the present invention,
The amount of the concealing agent added to the rubber-modified thermoplastic resin and the average particle size are within a range that does not hinder the action and moldability of the flame-retardant decorative film, and provide the necessary concealing properties such as the use of the flame-retardant decorative film. The total light transmittance (measured in accordance with JIS K7105) is preferably determined at the time of forming the flame-retardant decorative film in combination with the filler.
Is preferably 20% or less, more preferably the total light transmittance (measured according to JIS K7105) is 15% or less, particularly preferably the total light transmittance (JIS). (Measured according to K7105)
Is preferably 7% or less. If the total light transmittance exceeds 20%, the IC chips and attached parts in the molded product can be seen through, which is not preferable.

Within the above range of the total light transmittance (measured according to JIS K7105), the average particle size of the concealing agent used in the present invention is preferably 20 μm or less, more preferably 5 μm or less. When the average particle size of the concealing agent exceeds 20 μm, pinholes are generated in the film, and it becomes difficult to form the film.

The flame retardant used in the flame-retardant decorative film of the present invention may be either a halogen-based flame retardant or a non-halogen-based flame retardant, which hinders the action and moldability of the flame-retardant decorative film. You can set it within the range that does not exist.

Examples of the halogen-based flame retardants include tetrabromobisphenol A, carbonate oligomers of brominated bisphenol A, brominated bisphenol A type epoxy resins, decabromodiphenyl ether, bis ( Tribromophenoxy) ethane, perchloropentanecyclodecane, tris (tribromoneopentyl) phosphate and the like. These may be used alone or in combination of two or more.

When a halogen-based flame retardant is used as the flame retardant, the mechanical strength of the film is reduced if the compounded amount of the flame retardant is large, so that the compounded amount is preferably as small as possible.

Examples of the non-halogen flame retardant include phosphorus flame retardants such as aromatic phosphate flame retardants. These may be used alone or in combination of two or more.

It is preferable that the flame retardant is combined with a flame retardant auxiliary. As the flame-retardant auxiliary, it is preferable to use a metal oxide such as antimony trioxide, particularly antimony trioxide for a halogen-based flame retardant, and to use a non-halogen-based flame retardant such as tetrafluoroethylene. It is preferable to use a fluorine-based monomer or polymer, or a copolymer containing the monomer.

The antimony trioxide has an average particle size (particle size distribution is measured by a centrifugal sedimentation type particle size distribution analyzer [SA-CP3: manufactured by Shimadzu Corporation] to which a liquid layer sedimentation type light transmission method is applied). The particle size of 50% by weight was defined as the average particle size.)
It is preferably at least 3 μm, more preferably from 3 to
The thickness is preferably 9 μm, particularly preferably 4 to 7 μm. If the average particle size is less than 3 μm, the light resistance of the film tends to decrease, and if it exceeds 9 μm, the mechanical strength such as tensile strength and impact strength of the film tends to decrease.

The above-mentioned antimony trioxide can be produced by a commonly used method, for example, a method of producing naturally occurring ore or valentine ore by boiling an antimony chloride sodium hydrochloride solution of a hydrolysis product of antimony chloride. Alternatively, it can be produced by a method of air oxidation of metal antimony.

In the flame-retardant decorative film of the present invention,
A method for blending the respective raw materials can be a conventionally known method, and is not particularly limited. For example, the raw materials can be produced by heating and melting and mixing the respective components. Usually, the heat melting and mixing are usually performed under normal pressure, but may be performed under increased pressure or reduced pressure. The apparatus for heat melting and mixing is not particularly limited as long as heating and mixing are possible, and a commonly used tank with a stirrer, an intecip mixer, a Banbury mixer, a super mixer, a Henschel mixer, or the like can be used. . Alternatively, the components may be heated and melted and mixed by an extruder equipped with a screw, extruded from a mold and cooled to form a desired shape such as a pellet, and then molded.

The flame-retardant decorative film of the present invention contains other components such as a plasticizer, a light stabilizer, a heat stabilizer, and an ultraviolet absorber as needed, as long as the function of the present invention is not impaired. May be.

The method for forming the flame-retardant decorative film of the present invention may be a conventionally known method, and is not particularly limited. For example, a film can be formed by subjecting it to an extrusion molding method such as an inflation method or a T-die method. In addition,
When the resin composition is extruded from a T-die and cooled by a cooling roll to form a film, a film having desired surface smoothness and uniformity may be obtained by adjusting the temperature of the cooling roll.

The thickness of the flame-retardant decorative film of the present invention is as follows:
It is not particularly limited, and may be appropriately determined as necessary, such as use, as long as it does not hinder the function and moldability of the flame-retardant decorative film. For example, when used as a surface coating layer of an IC card, it is preferably 20-350 microns is good. When the thickness of the film is less than 20 microns, the concealing property is reduced. When the thickness exceeds 350 microns, when a laminate such as an IC card is formed, the coating layer becomes thick and the card cannot maintain its strength.

The flame-retardant decorative film of the present invention may be subjected to decorative printing or the like on its surface or may be bonded to another resin layer, and the flame-retardant decorative film of the present invention may be used as a surface coating layer. The used laminate can be obtained. Therefore, the surface of the flame-retardant decorative film of the present invention may be subjected to conventionally known surface treatment, if necessary. For example, when bonding with other resin layers, corona discharge treatment, flame treatment,
Surface treatment such as ultrasonic treatment and plasma treatment may be performed.

Since the flame-retardant decorative film of the present invention has an appropriate surface roughness, it can be used alone after printing or the like, or it can be used as a surface coating layer or as a laminate. In particular, it comprises at least one inner layer (A) and a surface coating layer (B) covering at least one outermost layer surface of the inner layer (A), wherein the surface coating layer (B) is the flame retardant of the present invention. A laminate formed of a decorative film, such as an IC card, which is formed by disposing components such as an IC chip between the flame-retardant decorative films of the present invention and filling the voids with a resin or the like. Can be suitably used.

In the present invention, in the case of the above-mentioned laminate, the material (core resin or the like) forming the inner layer (A) is not particularly limited as long as physical properties such as card strength are satisfied. Examples include resin compositions such as polyester, polyamide, polyolefin, polystyrene, polycarbonate, and acrylic resin. Preferably, the above resin can be bonded or laminated by heat or pressure using in-mold molding or the like without using an adhesive with the surface coating layer (B) (the flame-retardant decorative film of the present invention). Preferable examples include a rubber-modified thermoplastic resin, polybutylene terephthalate, an AS resin, an acrylic resin, and polycarbonate. More preferably, a material constituting the surface coating layer (B), that is, a rubber-modified thermoplastic resin, particularly an ABS resin or an AS resin, having properties similar to those of the flame-retardant decorative film of the present invention is preferred.

Further, the above-mentioned resin composition constituting the inner layer (A) preferably contains a flame retardant. As the flame retardant, the halogen-based flame retardant or the non-halogen-based flame retardant used for the surface coating layer (B) (the flame-retardant decorative film of the present invention) can be used. It is also preferable to use a flame retardant auxiliary in the same manner as the surface coating layer (B) (the flame retardant decorative film of the present invention).

In the laminate of the present invention, as a method of laminating the surface coating layer (B) (the flame-retardant decorative film of the present invention) without using an adhesive, for example, heat bonding using in-mold molding or the like is used. No. In particular, in the formation of a laminated body in which components are built like an IC card, an in-mold molding method is preferable. The in-mold molding method used for forming the laminate of the present invention may be a general method. That is, FIG.
As shown in (a), using a mold 1 having a cavity and a mold 2 having an injection port, a flame-retardant decorative film of the present invention is brought into close contact with the cavity surface of the mold 1 and a resin layer ( This is a method in which a molded article and a flame-retardant decorative film are integrated at the same time as the injection of the molten resin composition for forming the inner layer (A)) to produce a decorative molded article in one step. FIG. 1 (b) shows the formation of a laminated body incorporating components such as an IC card.
As shown in the figure, the flame-retardant decorative film of the present invention is also mounted on the mold 2 side, and a component such as an IC chip is placed on the inner surface when forming one of the laminates of the flame-retardant decorative film. A resin composition to be filled (core resin layer = inner layer (A)) is injected between two flame-retardant decorative films, and at the same time, a molded product and a flame-retardant decorative film are integrated to form a multilayer. It shall be a thin molded product. When the shape of the cavity is designed according to the shape of the laminate, a product of the laminate is obtained by this manufacturing method. Otherwise, a punching step is required after molding. The injection molding method is not particularly limited, but when molding a thin-walled molded product having a thickness of 1 mm or less such as a card, an injection compression molding method, an injection press molding method, or the like is preferably used. Hereinafter, the effects will be described with reference to examples and comparative examples, but the technical scope of the present invention is not limited thereto.

Test Examples (I) Raw Materials Used (1) Main Component (Flame Retardant Decorative Film = Surface Coating Layer (B)) Rubber Modified Thermoplastic Resin (abbreviated as ABS1 hereinafter) (2) Hiding Agent (Flame retardant Decorative film = surface coating layer (B)) Titanium oxide (rutile type, R-11P) Sakai Chemical Industry Co., Ltd.
(3) filler (flame-retardant decorative film = surface coating layer (B)) talc (PS talc, Takehara Chemical Co., Ltd.): average particle size 11
(Micron) (4) Flame retardant (flame retardant decorative film = surface coating layer (B)) Decabromodiphenyl ether (5) Flame retardant auxiliary (flame retardant decorative film = surface coating layer (B)) Antimony trioxide (6) Stabilizer (flame retardant decorative film = surface coating layer (B)) Zinc oxide (7) Filled resin (IC card core resin layer = inner layer (A)) Rubber-modified thermoplastic resin (SER-90 Daicel) Manufactured by Chemical Industry Co., Ltd .: Abbreviated as ABS2 in the table.) Polyester (2016 Polyplastics Co., Ltd.)
Production: Abbreviated as PBT1 in the table. ) Rubber-modified thermoplastic resin (Sebian-V500, manufactured by Daicel Chemical Industries, Ltd .; abbreviated as ABS3 in the table) Polyester (200FP Polyplastics Co., Ltd.)
Made: Abbreviated as PBT2 in the table. )

(II) Test Method (1) Film Formability The films of Examples 1 to 5 and Comparative Examples 1 to 5 were visually inspected for the possibility of film forming based on the following criteria. : Good: Somewhat bad ×: Bad

(2) Total light transmittance For the films of Examples 1 to 5 and Comparative Examples 1 to 5,
The total light transmittance was measured using a haze meter (Model 206 manufactured by Toyo Seiki Co., Ltd.) in accordance with SK7105 to evaluate the concealing property. (unit:%)

(3) Surface Roughness For the films of Examples 1 to 5 and Comparative Examples 1 to 5,
According to SB0601, the surface roughness was measured using a surface roughness meter (Surfcom 103B manufactured by Toyo Seiki Co., Ltd.) (unit: μm).

(4) Printability on Surface The films of Examples 1 to 5 and Comparative Examples 1 to 5 were screen-printed on the surface, and the possibility of forming a printed image was visually confirmed based on the following criteria. : Good: Somewhat bad ×: Bad

(5) In-Mold Formability ICs of Examples 6 to 11, Reference Examples 1 and 2, and Comparative Examples 6 to 10
The card was visually checked for sink marks during in-mold molding based on the following criteria. : Good: Somewhat bad ×: Bad

(6) Adhesion to core resin layer during in-mold molding ICs of Examples 6 to 11, Reference Examples 1 and 2, and Comparative Examples 6 to 10
Regarding the card, the adhesiveness between the surface covering layer (B) and the inner layer (A) was measured using a sample width of 15 mm,
Peeling was performed at a speed of mm / min and confirmed.

(7) Flame Resistance ICs of Examples 6 to 11, Reference Examples 1 and 2, and Comparative Examples 6 to 10
About the card, Underwriters Laboratory (USA) UL standard UL94 (September 1985)
A combustion test was carried out in accordance with the third edition on March 3) and evaluated based on the following criteria. High flame retardancy V-0 → V-1 → V-2 → H
B Low flame retardancy (V-0 has no dropping, V-2 has dropping)

(III) Test Results Table 1 shows the test results (1) to (4) for each film.
Table 2 shows the test results (5) to (7) for the IC card.

[0067]

[Table 1]

[0068]

[Table 2]

Table 1 shows that when the amount of the concealing agent is small, the concealing property is reduced, and when the amount of the filler is small, the printability is reduced. Also, from Table 2, it can be seen that when the amount of the filler added is small, in-mold moldability such as generation of sink occurs. Further, it can be seen that when both the inner layer (A) and the surface coating layer (B) contain a flame retardant, the flame resistance is excellent. Therefore, the results in Tables 1 and 2 show that the flame retardant decorative film of the present invention is excellent overall.

[0070]

EXAMPLES Example AS resin: styrene / acrylonitrile = 74/2
6 (weight ratio) manufactured by suspension polymerization. ABS resin: styrene / acrylonitrile / butadiene = 45/15/40 (weight ratio). Manufactured by emulsion polymerization. Were mixed at a weight ratio of 40/60 to obtain a rubber-modified thermoplastic resin having a rubber component content of 40% by weight and a graft ratio of 55 mol%. (ABS1) Next, 4 kg of titanium oxide (rutile type, average particle size 0.2 micron: R-11P, manufactured by Sakai Chemical Industry Co., Ltd.) as a concealing agent was added to 7 kg of the obtained rubber-modified thermoplastic resin, and talc was used as a filler. (Average particle size 11 microns: PS talc
4 kg of decabromodiphenyl ether as a flame retardant, 1 kg of antimony trioxide as a flame retardant, and 100 g of zinc oxide as a stabilizer,
After kneading with a single-screw extruder, the mixture was formed into pellets using a pelletizer, and the resulting mixture was 190 to 260 with a T-die extruder.
A film was formed at 100 ° C. to obtain a flame-retardant decorative film having a thickness of 100 μm.

Example 2 A film was formed in the same manner as in Example 1 to obtain a flame-retardant decorative film having a thickness of 50 μm.

Example 3 A film was formed in the same manner as in Example 1 to obtain a flame-retardant decorative film having a thickness of 300 μm.

Example 4 Titanium oxide (rutile type, average particle size: 0.2 μm) was added to 10 kg of the rubber-modified thermoplastic resin of Example 1 as a concealing agent.
1 kg of R-11P, manufactured by Sakai Chemical Industry Co., Ltd., 4 kg of talc (average particle size: 11 μm: PS Talc, manufactured by Takehara Chemical Co., Ltd.), 4 kg of decabromodiphenyl ether as a flame retardant, and 3 kg as a flame retardant aid 1 kg of antimony oxide and 100 g of zinc oxide as a stabilizer were blended, and a film was formed in the same manner as in Example 1 to obtain a flame-retardant decorative film having a thickness of 100 μm.

Example 5 Titanium oxide (rutile type, average particle size 0.2 μm) was added to 10 kg of the rubber-modified thermoplastic resin of Example 1 as a concealing agent.
R-11P Sakai Chemical Industry Co., Ltd., 4 kg, talc as filler (average particle size: 11 microns: PS Talc, manufactured by Takehara Chemical Co., Ltd.), 4 kg decabromodiphenyl ether as a flame retardant, and 3 kg as a flame retardant auxiliary 1 kg of antimony oxide and 100 g of zinc oxide as a stabilizer were blended, and a film was formed in the same manner as in Example 1 to obtain a flame-retardant decorative film having a thickness of 100 μm.

Example 6 Using a mold 1 having a cavity for in-mold molding and a mold 2 having an injection port, the shape of the cavity being designed according to the thickness of the IC card of 0.8 mm, The flame-retardant decorative film of Example 1 is adhered to the cavity surface of the mold 2 as the surface coating layer (B), and the surface of the flame-retardant decorative film on the mold 2 side that is not adhered to the mold. A rubber-modified thermoplastic resin (SER-90 manufactured by Daicel Chemical Industries, Ltd.) is used as a resin (inner layer (A)) to be filled between two flame-retardant decorative films. At the same time as the injection, the molded product and the flame retardant decorative film are integrated. After molding, it was punched into the shape of an IC card to obtain an IC card, which was used as Example 6.

Example 7 The flame-retardant decorative film of Example 1 was used as the surface coating layer (B), and polyester (2016 Polyplastics Co., Ltd.) was used as the filling resin (inner layer (A)). An IC card was obtained in the same manner as in Example 6 except for the above, and the result was referred to as Example 7.

Example 8 An IC card was obtained in the same manner as in Example 6, except that the flame-retardant decorative film of Example 2 was used as the surface coating layer (B).

Example 9 An IC card was obtained in the same manner as in Example 6, except that the flame-retardant decorative film of Example 3 was used as the surface coating layer (B).

Example 10 An IC card was obtained in the same manner as in Example 6, except that the flame-retardant decorative film of Example 4 was used as the surface coating layer (B).

Example 11 An IC card was obtained in the same manner as in Example 6, except that the flame-retardant decorative film of Example 5 was used as the surface coating layer (B).

Comparative Example 1 Titanium oxide (rutile type, average particle size 0.2 μm) was added as a concealing agent to 12 kg of the rubber-modified thermoplastic resin of Example 1.
R-11P 4 kg of Sakai Chemical Industry Co., Ltd.) and 4 kg of talc (PS talc Takehara Chemical Co., Ltd .: average particle size 11 μm) as a filler were blended, and a film was formed in the same manner as in Example 1. Then, a film having a thickness of 100 μm was obtained, and Comparative Example 1 was obtained.

Comparative Example 2 A film having a thickness of 100 μm was obtained by using the rubber-modified thermoplastic resin of Example 1 in the same manner as in Example 1 to obtain Comparative Example 2.

Comparative Example 3 16 kg of the rubber-modified thermoplastic resin of Example 1 was mixed with 4 kg of talc (average particle size: 11 μm: PS talc manufactured by Takehara Chemical Co., Ltd.) as a filler, and the same method as in Example 1 was used. And a film having a thickness of 100 microns was obtained as Comparative Example 3.

Comparative Example 4 Titanium oxide (rutile type, average particle size 0.2 μm) was added as a concealing agent to 16 kg of the rubber-modified thermoplastic resin of Example 1.
R-11P Sakai Chemical Industry Co., Ltd.)
A film was formed in the same manner as in Example 1 to a thickness of 10
A film of 0 micron was obtained to be Comparative Example 4.

Comparative Example 5 To 15 kg of the rubber-modified thermoplastic resin of Example 1, 4 kg of decabromodiphenyl ether as a flame retardant, 1 kg of antimony trioxide as a flame retardant aid, and 1 kg of zinc oxide as a stabilizer
Comparative Example 5 was prepared by mixing 100 g and forming a film in the same manner as in Example 1.
And

Comparative Example 6 An IC card was obtained in the same manner as in Example 6, except that the film of Comparative Example 1 was used as the surface coating layer (B).

Comparative Example 7 An IC card was obtained in the same manner as in Example 6, except that the film of Comparative Example 2 was used as the surface coating layer (B).

Comparative Example 8 An IC card was obtained in the same manner as in Example 6, except that the film of Comparative Example 3 was used as the surface coating layer (B).

Comparative Example 9 An IC card was obtained in the same manner as in Example 6, except that the film of Comparative Example 4 was used as the surface coating layer (B).

Comparative Example 10 An IC card was obtained in the same manner as in Example 6 except that the film of Comparative Example 5 was used as the surface coating layer (B).
And

Reference Example 1 The flame-retardant decorative film of Example 1 was used as the surface coating layer (B), and a rubber-modified thermoplastic resin (Sebian-V500 Daicel Chemical Industries, Ltd.) was used as the resin (inner layer (A)) to be filled. I) in the same manner as in Example 6 except that
C card was obtained, and it was set as Reference Example 1.

Reference Example 2 The flame-retardant decorative film of Example 1 was used as the surface coating layer (B), and polyester (200FP Polyplastics Co., Ltd.) was used as the resin (inner layer (A)) to be filled.
An IC card was obtained in the same manner as in Example 6 except for using, and Reference Example 2 was obtained.

[0093]

Since the flame-retardant decorative film of the present invention has the above-mentioned structure, it has good film moldability and in-mold moldability at the time of forming a laminate, and has an appropriate surface roughness. It is easy to provide design by printing or the like, and the concealing property is also good. Furthermore, the flame-retardant decorative film of the present invention has excellent flame resistance like the vinyl chloride resin, and can be replaced with a vinyl chloride resin. By using the flame-retardant decorative film of the present invention having the above-described effects, a high-quality laminate can be obtained by reducing the number of manufacturing steps, and this is particularly advantageous for cost reduction in IC card manufacturing.

[Brief description of the drawings]

FIGS. 1 (a) and 1 (b) are explanatory views showing how to manufacture a laminate using the flame-retardant decorative film of the present invention.

[Explanation of symbols]

 Reference Signs List 1 mold 2 mold 3 injection molding machine 4 flame-retardant decorative film 5 parts

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F071 AA02 AA10X AA12X AA14X AA22X AA33X AA34X AA77 AB17 AC03 AE07 AE17 AE22 AF27Y AF30Y AF47 AH14 BA01 BB05 BB06 BC01 BC16 4F100 AA08H AA29HABA AK05 AA29H AKA AK AK27A AK27C AK28A AK28C AK74A AK74C AL01A AL01C AL04A AL04C AL06A AL06B AL06C AN00A AN00C AT00B BA01 BA02 BA03 BA06 BA10A BA10C CA08A CA08B CA08C CA13A CA13C CA23A CA23C CA30A CA30BDD J07 GB01B07

Claims (15)

[Claims] 1. A flame-retardant decorative film comprising at least four components: a filler, a concealing agent, a flame retardant, and a rubber-modified thermoplastic resin. 2. A rubber-modified thermoplastic resin comprising (a) a rubber component, (b) an aromatic vinyl monomer and / or an alkyl (meth) acrylate, and (c) a vinyl cyanide monomer, (b) and (c). 2. The flame-retardant decorative film according to claim 1, which is a resin obtained by graft-polymerizing a vinyl monomer composed of component (1). 3. The rubber-modified thermoplastic resin is a resin obtained by graft-polymerizing a diene rubber or an olefin copolymer rubber with a vinyl monomer composed of a styrene monomer and acrylonitrile. Item 6. The flame-retardant decorative film according to Item 1. 4. The flame-retardant decorative film according to claim 1, wherein the rubber-modified thermoplastic resin is an ABS resin. 5. The flame retardant according to claim 1, wherein the flame retardant is a halogen-based flame retardant and contains antimony trioxide as a flame retardant auxiliary. Decorative film. 6. The flame-retardant decorative film according to claim 1, wherein the flame retardant is a non-halogen flame retardant. 7. The flame-retardant decorative film according to claim 1, wherein the total light transmittance (according to JIS K7105) is 20% or less. 8. The flame-retardant decorative film according to claim 1, which has a surface roughness (according to JIS B0601) of 5 to 30 μm. 9. An inner layer (A) comprising at least one layer, and a surface coating layer (B) for covering at least one outermost layer surface of the inner layer (A), wherein the surface coating layer (B) is provided. 8
A laminate comprising the flame-retardant decorative film according to any one of the above. 10. The laminate according to claim 9, wherein the inner layer (A) is mainly composed of a resin composition containing a flame retardant. 11. The flame retardant contained in the inner layer (A) is a halogen-based flame retardant, and the inner layer (A) contains antimony trioxide as a flame retardant aid. 11. The laminate according to 10. 12. The laminate according to claim 10, wherein the flame retardant contained in the inner layer (A) is a non-halogen flame retardant. 13. The laminate according to claim 9, wherein the inner layer (A) is mainly made of a rubber-modified thermoplastic resin containing a flame retardant. 14. The laminate according to claim 9, wherein the laminate is an IC card. 15. The method according to claim 9, wherein the material constituting the inner layer (A) is injected by an in-mold injection molding method, and the surface coating layer (B) is formed integrally. A laminate according to any one of the preceding claims.