JPS6040458B2 - Decorative film containing metal foil powder - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is useful in a wide range of decorative applications, particularly in marking applications, and provides an excellent metallic look and significantly improved long-term retention ability (weather resistance) of the metallic look. ),
The present invention relates to a decorative casting film containing metal foil powder that exhibits various properties such as excellent anti-discoloration properties against light and heat, gasoline resistance, surface smoothness, and stability.

More specifically, the present invention provides about 5 to about 25 weight percent of an ethylene-vinyl acetate copolymer based resin of about 75 to about 95 weight percent of a vinyl chloride-based resin and about 15 to about 6 weight percent of a vinyl acetate compound.
About 10 to 100 parts by weight of the mixed resin component containing
The present invention relates to a metal foil powder-containing economical film, characterized in that it contains about 6 parts by weight of metal foil powder dispersed throughout the film.

Conventionally, metal powders for metal preparation, such as aluminum powder, bronze powder, and aluminum vapor-deposited film powder, are added to vinyl chloride resin and molded into a film shape to provide a decorative film with a metal steel surface. However, it has been difficult to provide a product that exhibits a satisfactory metallic tone and can maintain this metallic tone for a long period of time.

At present, it is practically impossible to provide a product that can maintain a satisfactory metallic appearance for a long period of time, especially when used outdoors. The present inventors have conducted research to provide a decorative film that is inexpensive and easily available, made of vinyl chloride resin, and that can exhibit a fresh metallic feel and its long-term retention ability (weather resistance).

As a result, a mixed resin component containing a vinyl chloride resin and an ethylene-vinyl acetate copolymer resin in a specified amount range, and a decorative metal powder, especially metal foil powder, in a specified amount range proportion to the mixed resin component. A film that satisfies the above combinations exhibits the unique property of exhibiting a fresh metallic feel that could not be provided by the above-mentioned conventional attempts, and being able to maintain that metallic feel with significantly improved long-term retention ability (weather resistance). I discovered that. In addition to this unique property, it also has desirable properties such as excellent anti-discoloration properties against light and heat, gasoline resistance, surface smoothness, and mildness, which were previously not available. .

It was found that this was an excellent decorative film containing metal foil powder. However, when a metal powder is blended with a vinyl chloride resin to form a melt-extruded film, the desired metallic tone cannot be imparted. Furthermore, if aluminum powder is used to make a silver color appear, the product will be gray, and if bronze powder is used to make a gold color, it will be an ocher-colored product, making it impossible to produce the desired product. Considering the well-known fact that a mixed resin containing a vinyl resin and a substantial amount of ethylene-vinyl acetate copolymer resin causes a non-negligible deterioration in weather resistance.
The exhibiting of the above-mentioned unique properties discovered by the present inventors was a completely unexpected result. Therefore, an object of the present invention is to provide a decorative film containing metal foil powder that can have excellent improved properties. The above objects and many other objects and advantages of the present invention will become more apparent from the following description.

The resin components of the decorative film containing metal foil powder of the present invention include about 75 to about 95% by weight of a vinyl chloride resin and about 5% by weight of an ethylene-vinyl acetate copolymer resin with a total vinyl acetate content of about 15 to about 6%. A mixed resin component containing ~25% by weight.

Examples of the vinyl chloride resin include vinyl chloride homopolymers, vinyl chloride copolymers containing a copolymer component of about 1% by weight or less, and blends of vinyl chloride homopolymers and vinyl chloride copolymers. is available.

Examples of such copolymer components include ethylene, polymer. Pyrene, butene, acrylic ester, vinylidene chloride,
Examples include single-base bodies such as vinyl ester and vinyl ether. The ethylene-pinyl acetate copolymer resin has a vinyl acetate content of about 15 to about 6% by weight, preferably about 25 to about 6% by weight, particularly preferably about 35 to about 5% by weight. A vinyl acetate copolymer resin is used.

When the vinyl acetate content falls outside the above range,
The effect of improving weather resistance and heat discoloration resistance cannot be obtained, and if the amount is excessive, the compatibility with the vinyl chloride resin deteriorates, resulting in an increase in the blowing of stabilizers, lubricants, ultraviolet absorbers, etc. onto the surface: This causes a decrease in weather resistance and gasoline resistance. As the above-mentioned ethylene monovinyl acetate copolymer resin, those produced by high-pressure bulk polymerization, solution polymerization, emulsion polymerization, etc. can be used, and examples of these include Ebaflex manufactured by Mitsui Polychemical Co., Ltd. P-1907 (VAC, 19
(wt%), P-2505 (VAC, 25 wt%), P-
3307 (3% by weight), Soabrene BH (VAC, 55% by weight), CH (VAC, 6% by weight) manufactured by Nippon Gosei Chemical Industry ■
% by weight), 45 dishes of Bayer Bubbles, 45 Iso (
VAC, 45% by weight), Lutracene manufactured by Toyo Soda, Evatate manufactured by Sumitomo Chemical, Cucaroneva manufactured by Mitsubishi Yuka,
etc. can be exemplified.

The average degree of polymerization of the pinyl chloride resin in the mixed resin component as exemplified above used in the present invention can be selected as appropriate. The average degree of polymerization of the resin can also be selected as appropriate, for example from about 1000 to about 600.
An average degree of polymerization such as 0 can be exemplified.

The mixing ratio of the above-mentioned vinyl chloride resin and ethylene-vinyl acetate copolymer resin in the mixed resin component used in the present invention is about 75 to about 95% by weight of the vinyl chloride resin and about 95% by weight of the ethylene-vinyl acetate copolymer resin. 5 to about 25% by weight.

Preferably, the former is about 85 to about 95% by weight and the latter about 5 to about 95% by weight.
It is 15% by weight. If the amount of the ethylene-vinyl acetate copolymer resin used is too small and deviates from the above mixing ratio, the desired improvement in weather resistance and heat discoloration resistance will not be achieved. On the other hand, if the amount used is too excessive, the compatibility with the pinyl chloride resin will deteriorate, the film resistance (metallic appearance retention time) will decrease, and it will cause bubbling on the film surface. Since it causes such inconveniences, it is used only for children. The above mixed resin components used in the decorative film containing metal foil powder of the present invention include stabilizers, antioxidants, lubricants, plasticizers, pigments,
It may contain additives such as dyes.

The amounts of these additives to be used can be selected as appropriate, but based on 10 parts by weight of the mixed resin component, about 0.5 to about 1 part by weight of the stabilizer, about 0.01 to about 2 parts by weight of the antioxidant. agent, about 0.2
~ about 1 part by weight of a thickening agent, about 1 to about 5 parts by weight of a plasticizer,
about 0.05 to 5 parts by weight of ultraviolet absorber, about 0.01 to 1
Examples include the amount of colorants such as pigments and dyes in parts by weight. Specific examples of these additives include, for example, calcium zinc stabilizer (manufactured by Katsuta Kako ■, CZ-1
9J), tin-based stabilizer (manufactured by Katsuta Kako ■, 181FSJ),
Barium zinc stabilizer (manufactured by Katsuta Kako ■, BZ51J),
Stabilizers such as lead stearate stabilizers (manufactured by Kosei ■, P6-St); for example, monophenolic antioxidants (manufactured by Yoshitomi Pharmaceutical ■, Yoshinox BHT), amino antioxidants (manufactured by Yoshitomi Pharmaceutical ■, Yoshinox EQ), polyphenol antioxidant (Ciba Gaigi, Irganox 1010)
Antioxidants such as: hydrocarbon-based lubricants (manufactured by Allied Chemical Co., Ltd., Ac-Ki), fatty acid-based lubricants (manufactured by Oilken Fine Chemicals, F-13), fatty acid ester-based lubricants (manufactured by Hoechst Japan Co., Ltd., Hoechst Female Lubricant such as alcohol 86) manufactured by Kao Soap; for example, phthalic acid plasticizer (DOP manufactured by Sanken Kako), epoxy plasticizer (manufactured by Adeka Argus ■, Adeka Cider ○-13ho)
, adipic acid ester plasticizer (manufactured by Sekisui Chemical Co., Ltd., D
OA), polyester plasticizers (manufactured by Rohm and Haas, Paraflex G25); for example, penzotriazole-based UV absorbers (manufactured by Ciba Gaigi, Tinuvin P), hydroxybenzophenone-based UV absorbers (American Cyanamid). For example, ultraviolet absorbers such as Cyasorp UV-9) manufactured by Co., Ltd. The decorative film containing metal foil powder of the present invention contains metal foil powder in an amount of about 10 to about 6 parts by weight, preferably about 30 to about 5 parts by weight, based on 10 parts by weight of the mixed resin component as described above. The mixed resin components are dispersed throughout the film, preferably the cast film.

The metal foil powder used in the present invention has a foil powder shape under a microscope.
For example, those having a foil powder shape such as scales, fragments thereof, mixtures or aggregates thereof are used.

Such metal foil powder has an average microscopic foil thickness of about 0.1 μm to about 5 μm, preferably about 0.2 μm to about 3 μm, and an average microscopic foil size of about 2 μm to about 70 μm, It is preferable to use metal foil powder having a particle size of preferably about 5 to about 40 mm, and preferably about 8 to about 30 mm. Here, the microscopic average foil powder thickness and microscopic average foil powder size are as follows. Metal foil powder IQ was mixed with EPN812 (epoxy resin), 80 parts by weight (Shell Chemical Co., Ltd.); EPN815 (
Eboxy resin), 20 parts by weight (manufactured by Shell Chemical Co., Ltd.): DD
SA (dodecylsuccinic acid: curing agent), 14 parts by weight (Sanyo Chemical); DMP-30 (Tori 2,4,6 dimethylaminomethylphenol: curing accelerator), 5 parts by weight (Nippon IG-yaku); The mixture was added to 25 cc of an epoxy embedding liquid adjusted to a ratio of 25 ml, and heated and cured for 6000 x 7 hours.

After that, it is cut with a razor blade to a size of about 5 pieces in length, 5 pieces in width, and 1 piece in thickness, and gold is vacuum-deposited on the entire surface to be used as a measurement sample.
Next, the layer surface of the sample was observed using a scanning electron microscope at 40 mm, and a photograph of 10 layers x 10 layers was taken. At this time, the 10 ribs in the photo become 25 Buddhas. Select 30 foil powder images centered on the center of the photo, and measure the major axis of each according to the JIS standard.
The total value was divided by 30 and the microscopic average foil powder size (r) was determined using a grade 1 caliper. In addition, the foil powder was cut perpendicularly to the layer surface of the measurement sample with a razor blade so that the cut surface was exposed, the cut surface was vacuum-deposited with gold, and the cut surface of the foil powder was examined using a scanning electron microscope ( The thickness of the 10 foil powders from the top of the photograph was measured in the same way as above, and the total value was gradually calculated by 10 to determine the microscopic average foil powder thickness. ).

An example of metal foil powder used is an average foil powder thickness of approximately 0.1
Examples include metal foil powder having a size of ~0.8r, a major axis of about 0.5 to about 80, a major axis/average foil powder thickness of about 1 to about 300, and a major axis/breadth of about 1 to about 6. . The metal foil powder used in the present invention preferably has a foil powder shape under a microscope, accounting for at least about 50% of the total metal powder,
More preferably, about 70% or more, particularly about 80% or more of the powder is in the form of foil powder. Although there are no particular restrictions on the method for producing such metal powder in the form of foil powder, it is preferable to use a mechanical crushing means that can easily crush the metal powder into the shape of foil powder, such as a stamp mill method. Such metal foil powder can be used after being divided into rings, if desired. As for the type of metal, the ratio of copper and zinc is 2:1 to 6 for golden color.
:1 bronze alloy, and silver tone can be exemplified by aluminum.

Such metal foil powders are available on the market, and can be used by blending multiple types as desired, with or without selective treatment. Examples of such commercially available products include bronze foil powder manufactured by Nippon Metal Powder Industries, Ltd.
Bronze pastes TP and ATH manufactured by Fukuda Metal Foil & Powder Kogyo ■, bronze pastes HRD and HRS manufactured by Fukuda Metal Foil & Powder Kogyo ■, and bronze resists CT and AT manufactured by Eckal Co., Ltd.
In addition, examples of aluminum foil powder include aluminum foil powder LG12, LP12, LL12, Maru 12, Shin 12 manufactured by Nihon Kinzoku Kogyo Co., Ltd., and aluminum foil powder AA39AA manufactured by Fukuda Metal Foil Powder Kogyo ■.
15AA12, aluminum paste 0 manufactured by Toyo Aluminum Industry ■
100M, 0200M, SAP600 series (61 sails, 62 dishes, etc.) SA manufactured by Showa Aluminum Powder Kogyo ■
Examples include the Ploo series (110, 120, 130, etc.). In the present invention, the metal foil powder used is one whose surface has been subjected to chromic acid treatment, silicon treatment, rust preventive treatment, antioxidant treatment, fatty acid treatment, resin treatment, etc. for the purpose of improving dispersibility. It's not something that gets in the way.

In the decorative film containing metal foil powder of the present invention, the metal foil powder as described above can be used in an amount of about 10 to about 6 parts by weight based on the mixed resin component 10 parts by weight.

Preferably, about 30 parts by weight of mixed resin component 10
It can be utilized in up to about 5 parts by weight. If the blending amount is too small outside the above range, the ratio will be insufficient and it will be difficult to obtain the desired metallic surface appearance, and if it is too large, the surface smoothness will deteriorate. , used within the scope of the above chapter. The thickness of the decorative film containing metal foil powder of the present invention is appropriately selected depending on the purpose of use, but the thickness is about 20 µm to about 1 µm.
20mm, preferably about 30mm to 60mm.

The decorative film containing metal foil powder of the present invention is particularly useful as a marking film such as, for example, labels, stickers, wheels, containers, vehicle decorations, or indicating strap stickers. ,
In a wide range of fields of use, such as advertising stickers used to display figures, letters, etc. on advertisements and information boards, signs, product marks, and other display stickers, the stone-like metal and Significantly improved long-term retention ability (
It is useful as a decorative film that exhibits various properties such as excellent anti-discoloration properties against light and heat, gasoline resistance, surface smoothness, and overall durability. The decorative film containing metal foil powder of the present invention can be in various forms when used.

For example, the film of the present invention can be in the form of any multilayer structure that allows the layers of the film of the present invention to be seen through during its use. For example, it can be provided with a suitable top coat layer or overlay layer. For example, the film layer of the present invention is formed on a stretched overlay layer film by a casting film forming method such as a caster method or a coater method, which is known per se, to form an overlay layer. The present invention can be used in the form of a film. In this case, the film for the overlay layer may be a film that has been subjected to, for example, a discharge method, an oxidation method, a chemical etching method, or any other known surface activity improvement method in order to improve the bonding strength with the film layer of the present invention. . Furthermore, a top coat layer may be provided on the film layer of the present invention, with or without an adhesive layer, using any top coating method known per se.

The resin material for the top coat layer or overlay layer can be selected as appropriate, such as polyethylene terephthalate and other aliphatic or aromatic polyester resins,
Vinyl fluoride type, vinylidene fluoride type, tetrafluoroethylene/ethylene type and other fluorine type polymerized or copolymerized resins, olefin type polymerized or copolymerized resins,
Examples include aliphatic or aromatic polyamide resins, acrylic resins, urethane resins, vinyl resins, and appropriate blend resins thereof.

Furthermore, the decorative film of the present invention may contain various coloring agents in addition to the metal foil powder, and the top coat layer or overlay layer as described above may also contain a layer that can be seen through the film layer of the present invention. May contain type and star colorants. By using such a coloring agent, it is possible to manifest a desired color tone such as a golden metallic tone or a modulated color such as red, blue, yellow, green, brown, or black. or. The decorative film of the present invention can also be used in the form of a known laminate film with a release paper that is peeled off from a release paper before use.

The decorative film containing metal foil powder of the present invention contains about 10 to about 6 parts by weight of the metal foil powder as described above, per 10 parts by weight of the specific mixed resin component as described above, dispersed throughout the film. Preferably, a cast film is used, and a solvent solution containing the mixed resin component and the metal foil powder is formed by a method known per se, for example, a cast film forming means such as a cast method or a coater method. It is preferably used in the form of an unstretched film. Stretching significantly reduces surface gloss and causes dimensional changes during use, making it undesirable for use. Examples of the solvent to be used include tetrahydrofuran, methyl ethyl ketone, methylene chloride, dimethylformamide, and alcohol. Below, along with comparative examples, the decorative film of the present invention and manufacturing examples thereof will be shown.

Examples 1 to 19 and Comparative Examples 1 to 9 In addition to the compositions shown in Table 1, the plasticizer dioctyl phthalate ( 5 parts by weight of calcium zinc stabilizer (manufactured by Katsuta Kako, trade name CZ-190)
), 1 part by weight of Nagunkari Axop (manufactured by Hoechst), and 1 part by weight of ultraviolet absorber Tinuvin P (manufactured by Ciba-Geigi).
By weight, further blend together and add tetrahydrofuran so that the resin concentration of the mixed resin component is 2% by weight,
A resin solution composition was obtained by dissolving Touzuka in a closed container at 100oC for 2 hours.

Next, the resin solution composition was cooled and degassed, and then casted onto a stainless steel slope using casters.
It was dried with hot air for 1 minute and peeled off to obtain a dried film with a thickness of 50 mm.

Details of the composition components shown in Table 1 are as follows.

1 Vinyl chloride resin: Vinyl chloride homopolymer (average degree of polymerization 1100), manufactured by Ryoichi, trade name SG-11〇〇2
VCP: Copolymer resin of vinyl chloride and propylene with a propylene content of 6% by weight (average degree of polymerization 750), manufactured by Toagosei Kagaku ■, product name Nipolit FB-7303 EVA: vinyl acetate content (w%), product name Manufacturer are shown in the table below.

4 ABS; acrylonitrile. Butane diene. Styrene copolymer resin, manufactured by Ube Sicon ■, trade name: Blendex 2015 MBS; Methyl methacrylate. butadiene. Styrene copolymer resin, manufactured by Kanefuchi Chemical Industry ■, trade name Kanease B-126 Fronze foil powder; manufactured by Nippon Metal Powder Industry ■, trade name Gold Paste-TP, average foil powder thickness 0
．． 5 Buddhas, average foil powder size 15 Buddhas, major axis 0.5-60mm,
Long axis/average foil powder thickness 1-120 Long axis/breadth 1-47 Aluminum foil powder; manufactured by Showa Aluminum Industry ■, product name SapliD,
Average foil powder thickness 0.3 mm, average foil powder size 13 peaks, major axis 0
．． 5 to 65 peaks, major axis/average foil powder size 1 to pine 〇 major axis/minor axis 1 to 3 Thus obtained Examples 1 to 19 and Comparative Examples 1 to 9
Table 1 shows the results of measuring the weather resistance, heat discoloration resistance, gasoline resistance, and film appearance (metallicity, blow-out, mildness) of the film.

The above performance measurements were performed using the following test method.

1 Weather Resistance 1-1 Preparation of Test Piece 140 For the above-mentioned film with a thickness of about 50 mm obtained by drying with hot air for 15 minutes and peeling, the side of the film that was hit by the hot air was Acrylic adhesive (Nissei ■
Co., Ltd., trade name PE-121) was applied in an amount of 30 g/
A test piece was prepared by laminating aluminum base material (1 piece thick, 15 ribs x 30 pieces).

1-2 Black panel temperature 63±3℃ with weather resistance test piece set
, a spray cycle of 18 minutes/180 minutes, and a sunshine weather meter (manufactured by Suga Test Instruments) under the conditions of JIS.
According to AI415 "Accelerated Exposure Test Method for Plastic Building Materials", the irradiation time until the film of the test piece reaches a certain color change is measured.

Discoloration was measured by measuring the color difference between the standard original film and the film of the above test piece using a color difference meter (manufactured by Tokyo Denshoku Co., Ltd., type TC-5 mark) in accordance with JIS Z8729rUVW System Object Color Display Method. The color difference value ΔE (UVW) is determined, and the irradiation time until the color difference value reaches evaluation grade 4 shown in Table 2 is measured to evaluate weather resistance. Table 2 2 Heat Resistance Test specimens were prepared in exactly the same manner as in Section 1-1 above, except that the base material was changed to a stainless steel plate (1 piece thick, 3 pieces x 5 watts). and 100q of discussion soap pieces.
After heating for one hour even in the open state of C, the color difference value (△E
) and convert it into an evaluation grade according to the third evaluation.

Table 3 3 Gasoline resistance A test piece whose base material was a stainless steel plate prepared by the method described in item 2 above was immersed in leaded gasoline for 25,002 hours.
Observe the change in the film surface and convert it into an evaluation grade according to Table 4 for evaluation.

Table 4: Film Appearance 4-1 Metallicity 14 0. Using a film obtained by drying with hot air for 15 minutes, a gloss meter (manufactured by Tokyo Denshoku Co., Ltd., Type TG) was measured at an incident angle of 60 degrees.
- Gloss (%) measurement according to P) and visual observation are combined to
Evaluate by converting into evaluation grade according to the table.

Table 5 4-2 The presence or absence of bleed-out is determined by rubbing the mainly calcium-zinc stabilizer, lubricant, and ultraviolet absorber that migrate to the surface of the blown film with a finger.

4-3 Draw a straight line with a thickness of 3 ribs on a high-quality paper with black marker ink at 1-inch intervals as a mount, place a film on top of it, visually check the straight line, and rate it according to the following evaluation. was evaluated.

A: I can't see straight lines at all. B: Straight lines are faintly visible. C: Straight lines are clearly visible. Table 1 Table 1 (continued)

Claims (1)

[Scope of Claims] 1. A mixed resin containing about 75 to about 95% by weight of a vinyl chloride resin and about 5 to about 25% by weight of an ethylene-vinyl acetate copolymer resin with a vinyl acetate content of about 15 to about 60% by weight. A decorative film containing metal foil powder, characterized in that about 10 to about 60 parts by weight of metal foil powder is dispersed throughout the film based on 100 parts by weight of the components. 2 The average thickness of the metal foil powder obtained by microscopy is approximately 0.1μ.
2. The decorative film of claim 1, wherein the decorative film has a microscopic average foil powder size of about 2 to about 70 microns. 3. The decorative film according to claim 1, wherein the film is an unstretched film.