JPH0737116B2 - Metal thin film laminated polyvinyl chloride resin molded article excellent in designability and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a metal thin film laminated vinyl resin molded article having excellent designability and a method for producing the same, and particularly excellent in durability and antifouling property, and cosmetics. In addition to indoor applications such as boards, wallpapers, blinds, and label stickers, it can also be used for outdoor applications such as shade tents, truck hoods, advertising signs, etc. And a manufacturing method thereof.

[Conventional technology]

Currently, in the fields of clothing, packaging materials, and ornaments, a metal thin film laminate using a vacuum vapor deposition technique is often used in order to impart a high-class feeling and a strange feeling.

As these metal thin film laminates, a material in which a metal thin film is laminated on a material having a small amount of volatile components, for example, a resin such as polyester or polyethylene in a vacuum chamber is often used for the sake of workability.

However, it is difficult to give a fine uneven pattern to these resin materials, and for such applications, it is common to use a thermoplastic polyvinyl chloride resin that can easily give a uneven pattern. is there.

When a polyvinyl chloride resin is used as a base material to produce a metal thin film laminate having a concavo-convex pattern, a step of applying the concavo-convex pattern to the base material or the final product is required.

As one of the methods for providing the uneven pattern, there is a method of printing the ultraviolet curable resin on the substrate or the final product, but it is difficult to say because it is expensive. In general,
A simple method is to use a polyvinyl chloride resin as a base material and subject it to embossing using an engraving roll.

In order to obtain a metal thin film laminate having an uneven pattern, the embossing step needs to be performed before or after the metal thin film forming step.

For example, when embossing is performed after forming a metal thin film, a substrate made of polyvinyl chloride resin is subjected to an undercoating treatment, a metal thin film is formed on this substrate by vacuum vapor deposition, and then a topcoat layer is provided. A method of embossing the laminate is conceivable. However, when a concavo-convex pattern is formed on the outermost layer, stains are likely to adhere to the concavo-convex portion, and it is difficult to maintain a good metallic luster.
Further, heat and pressure during the final embossing process often cause cracks and the like in the metal thin film layer, resulting in loss of metallic luster and a satisfactory product cannot often be obtained.

On the other hand, as disclosed in JP-A-53-36559,
A method of performing embossing treatment before forming the metal thin film, that is, after performing an undercoat treatment on the polyvinyl chloride resin substrate,
There is a method in which the laminate is embossed, and then a metal thin film layer and a topcoat layer are sequentially formed. In this method, it is unavoidable that the substrate and the undercoat layer are affected by a considerable amount of heat when the topcoat layer is baked. Due to the influence of heat, the wrinkles of the base material applied beforehand may return, and a product that meets the purpose may not be obtained. In particular, when the topcoat layer is formed of a resin material that requires high-temperature baking, baking at a predetermined temperature causes a large amount of wrinkling of the base material, which causes the metallic lustered pattern to disappear. In addition, baking at low temperature impairs the original properties of the resin, and the desired topcoat layer performance, such as abrasion resistance, weather resistance, and adhesiveness, is markedly reduced.

Further, as a means for providing a top coat layer that does not require heat treatment, coating of an ultraviolet curable resin is considered, but the use of these resins results in high cost, and further shrinkage during curing causes peeling of the metal thin film layer. So it's not a good idea.

[Problems to be Solved by the Invention]

The present invention is (a) that there is no wrinkle return of the base material in the baking treatment of the top coat layer, and that (b) it has metallic luster and has a clear uneven pattern and is excellent in durability and antifouling property. It is intended to provide a metal thin film-laminated polyvinyl chloride resin molded article having excellent designability, which satisfies the above requirements, and a method for producing the same.

[Means and actions for solving the problem]

A metal thin film-laminated vinyl resin molded article excellent in designability according to the present invention is a molded article substrate made of a polyvinyl chloride resin material, and is laminated and bound on at least one surface of the substrate and is made of a synthetic resin material. An undercoat layer having a thickness of 5 to 50 mm, a metal thin film layer formed and laminated on the undercoat layer, and a synthetic resin material laminated and bonded on the metal thin film layer. And a top coat layer, which is formed on the laminate of the substrate and the undercoat layer, by imprinting applied from the undercoat layer surface, an uneven pattern common to both is formed, and the metal thin film layer is The surface of the undercoat layer having an uneven pattern is covered with a corresponding uneven pattern, and the topcoat layer is baked by far infrared heating and has a smooth outer surface. It is characterized by doing.

Further, the method of the present invention for producing a polyvinyl chloride resin molded product having a metal thin film excellent in the above-mentioned design is an undercoat agent made of a synthetic resin material on at least one surface of a molded product substrate made of a polyvinyl chloride resin material. Is applied and baked to form an undercoat layer having a thickness of 5 to 50 μm, and the laminate of the base and the undercoat layer is subjected to a marking treatment from the undercoat layer surface to obtain a common Forming a concavo-convex pattern, the surface soil having a concavo-convex pattern of the laminate of the substrate and the undercoat layer, coating this, to form a metal thin film layer having a corresponding concavo-convex pattern, on the metal thin film layer A top coat layer having a smooth outer surface is formed by applying a coating solution containing a transparent synthetic resin material and baking it by far-infrared heating.

The details of the present invention will be described below.

FIG. 1 is a partial cross-sectional explanatory view of an example of a metal thin film laminated polyvinyl chloride resin molded product of the present invention.

This molded article comprises a molded article substrate 1 made of a polyvinyl chloride resin material, an undercoat layer 2 formed thereon,
It comprises a metal thin film layer 3 formed thereon and a top coat layer 4 formed thereon.

The undercoat layer 2 is made of a synthetic resin material, and the laminate of the molded article substrate 1 and the undercoat layer 2 has an uneven pattern formed by stamping from the undercoat layer surface. Is common to both the substrate 1 and the undercoat layer. A metal thin film layer is formed on the uneven surface of the undercoat layer 2 to cover it. The metal thin film layer 3 naturally has an uneven pattern corresponding to the uneven pattern of the undercoat layer 2. The top coat layer 4 formed on the metal thin film layer 3 is made of a transparent synthetic resin material and baked by far infrared heating, and its outer surface is smooth.

The polyvinyl chloride resin material forming the molded article base is a soft polyvinyl chloride resin; a rigid polyvinyl chloride resin; vinyl chloride and olefins such as ethylene, propylene,
Or a copolymer resin with isobutylene, a copolymer resin with vinyl chloride and styrene; a copolymer resin with vinyl chloride and dienes such as butadiene or isoprene;
From a copolymer resin of vinyl chloride and acrylic acid, a halogenated olefin, or vinyl acetate; and a mixed resin of the above resin and a modifying resin, for example, rubber such as ABS, SBR, or NBR You can choose.

There are no particular restrictions on the type or amount of the plasticizer added to the polyvinyl chloride resin, and any of the generally available plasticizers may be included.

The polyvinyl chloride resin material used in the present invention,
Depending on the purpose, it may contain an appropriate amount of a stabilizer, a filler, a flameproofing agent, a flame retardant, an antioxidant, an ultraviolet absorber, a mildewproofing agent, a lubricant, a pigment and the like.

The molded article substrate used in the present invention is a polyvinyl chloride resin material prepared by any of an extrusion molding method, an injection molding method, a calender molding method, an inflation molding method, a compression molding method, a coating method, or a dipping method. It is obtained by molding into a desired shape and dimension by the molding method of. In addition, the molded article substrate may include an appropriate fiber material made of synthetic fibers, semi-synthetic fibers, natural fibers, or the like, which are incorporated for the purpose of improving physical strength.

The synthetic resin material forming the undercoat layer can be selected from, for example, epoxy resin, polyester resin, urethane resin, alkyd resin, vinyl chloride-vinyl acetate copolymer resin, acrylic resin and the like. The undercoat layer forming method is not particularly limited, and a general coating method such as gravure roll coating, reverse roll coating, air knife coating, rod coating, or spray coating can be used.

The undercoat layer is formed to a thickness of 5 to 50 μm. If this thickness is less than 5 μm, the gloss of the metal thin film may be impaired by the influence of additives such as a plasticizer that migrates from the polyvinyl chloride resin material forming the substrate.
If the thickness exceeds 50 μm, the characteristics of the substrate made of the polyvinyl chloride resin material such as flexibility will not be fully utilized. A concavo-convex pattern is imprinted on the laminate of the molded article substrate and the undercoat layer from the undercoat layer surface. As a method of engraving a concavo-convex pattern, a method of performing embossing using an engraving roll, or a sheet in which a solid pattern is printed using a hard resin on a hard film, for example, a UV-curable type on a polyester film having a thickness of 100 μm A polyester resin is printed in a three-dimensional pattern, and the cured sheet is subjected to heat lamination to a laminate of a molded article substrate and an undercoat layer, which is then cooled and the three-dimensional patterned sheet is peeled off to form a molded article substrate. A method of forming a concavo-convex pattern on the laminate with the undercoat layer can be used.

As described above, since the thickness of the undercoat layer is as thin as 5 to 50 μm, the uneven pattern due to the above-mentioned imprinting is
It is commonly formed on both the undercoat layer and the polyvinyl chloride substrate, so that they are firmly bound.

As a method for forming the metal thin film layer, known methods such as a vacuum vapor deposition method and a sputtering method can be used. As the metal material used in the present invention, it is preferable to select a metal having infrared reflectivity from the viewpoint of preventing induction heating of the polyvinyl chloride resin substrate by infrared rays and enhancing the heating effect of the top coat resin. Examples of such metal materials include metals such as Al, Ti, Ni, Cr, Cu, Ag, Au, Fe, Mn, Zn, and Sn, and ZnO, In ₂ O ₃ , SnO ₂ , and the like. Such metal oxides are also included. The metal thin film layer forming material is selected according to the intended use of the molded product and the required function. These metal thin film layers may be composed of a single layer or a laminate of a plurality of layers, or a laminate of a layer composed of these metal materials and another metal layer having no infrared reflectivity, For example, an interference film such as Al-MgFe-Al, Zn
Drude-mirror type stacks such as S-Ag-ZnS can be used.

The thickness of the metal thin film layer is preferably in the range of 100 to 3500Å. If the film thickness is less than 100Å, the infrared reflection efficiency will be reduced, which will induce the grain return phenomenon of the polyvinyl chloride resin substrate, and if it exceeds 3500Å, the metal thin film layer will be cracked and the appearance will be significantly impaired. Be seen.

The top coat layer is for the purpose of protecting the metal thin film layer and preventing stains on the product, and is generally formed of an organic solvent type or emulsion type resin coating. In the present invention, since the molded article substrate is formed of a material having low heat resistance such as a polyvinyl chloride resin material, generally a room temperature dry type resin or a low temperature dry type resin having a drying temperature of 100 ° C. or less is used. To be However, these resins may be inherently insufficient in wear resistance, weather resistance, etc. Therefore, when used under severe conditions such as outdoors,
It is preferable to use a transparent baking type resin coating for the top coat layer. That is, a resin that absorbs and hardens far infrared rays in the wavelength range of 10 μm to 100 μm is used. Such a resin can be selected from an epoxy resin, a polyester resin, a polyvinylidene chloride resin, a melamine resin, a urethane resin, an acrylic resin, a silicon-modified urethane resin, a silicon-modified acrylic resin, a fluorine-modified acrylic resin, or the like.

Reverse roll coating, air knife coating, rod coating,
A coating method appropriately selected from spray coating and the like can be used. The thickness of the top coat layer is 1-10
It is preferably in the range of 0 μm.

If the thickness of the top coat layer is less than 10 μm, the durability and wear resistance are poor, and if it exceeds 100 μm, cracks are likely to occur. One of the features of the method of the present invention is that the top coat layer is formed by baking by far-infrared heating.

The far-infrared heater used in the method of the present invention is an electric far-infrared heater, for example, a pipe type or a plate type in shape, and the structure is a nichrome wire which is a heating element and a sheathed heater made of an electric insulating material on the outer surface of the ceramics. A far-infrared heater covered with a gas, a far-infrared radiant ceramics heated by a high-temperature combustion gas, a steam-type far-infrared heater, for example, a heat source of condensation heat of steam. The far-infrared radiation ceramics used here is not particularly limited, and MnO ₂ , Fe ₂
It is composed of a mixture of O ₃ , CoO, CuO, CrO ₃ , ZrO ₂ , SiO ₂ , TiO, Al ₂ O _{3 and the} like. The heating condition with the far-infrared heater is appropriately determined depending on the characteristics of the top coat resin material and the coating film thickness, but it is preferably carried out under the heating condition of 50 to 10,000 Kcal / m ² · hr. In the method of the present invention, the effect of infrared reflection by the metal thin film layer prevents the heat influence on the substrate and promotes the heating effect of the top coat layer. Further, the smooth outer surface of the top coat layer forms the outer surface of the molded article of the present invention, and exhibits good antifouling property and durability.

〔Example〕

 The invention is further described by the following examples.

Example 1 100 parts by weight of polyvinyl chloride resin (trademark: Denka SS-103), 45 parts by weight of DOP (dioctyl phthalate), 3 parts by weight of EPS (epoxidized soybean oil), and 2 parts by weight of a Ba-Zn stabilizer are blended. The above composition was formed into a film having a thickness of 0.2 mm by a heating roll. Polyester multifilament 1000 denier yarns were used as warp and weft, respectively, on both sides of a woven fabric with a density of 11 yarns / 25.4 mm, and the above film was heat-bonded to form a polyvinyl chloride resin sheet, which is a molded article substrate. And

Next, as an undercoat agent, a urethane resin (trademark: U
-MX-1, manufactured by Seiko Kasei Co., Ltd.) is applied onto one surface of the molded article substrate using a 100-mesh gravure roll.
It was dried with hot air at a temperature of 0 ° C. for 2 minutes to form an undercoat layer having a film thickness of 20 μm. The undercoat surface of the laminate of the substrate and undercoat layer is heated to 160 ° C, and the plate depth 5
Embossing was performed using a 0 μm engraving roll to form a common uneven pattern on the substrate and the undercoat layer.

In this way, vacuum deposition of metal Al was performed on the undercoat layer surface of the laminate of the substrate and the undercoat layer on which the uneven pattern was formed. The vacuum evaporation was performed on the uneven surface by the resistance heating evaporation method to form a metal Al thin film layer with a thickness of 400 Å.

Next, as a top coat agent on the surface of the metal thin film layer, acrylic-silicon resin (trademark: UA-90, manufactured by Sanyo Chemical Industries) 1
00 parts by weight, catalyst (trademark: Cat65MC, Sanyo Kasei Co., Ltd.) 7.
A composition consisting of 5 parts by weight and 20 parts by weight of methyl ethyl ketone was applied using a clearance bar coater of 20 μm,
This was baked by far infrared heating to form a top coat layer having a smooth outer surface and a thickness of 20 μm. For baking with a far-infrared heater, a ceramic component heater 403SS (manufactured by Nippon Light Metal Co., Ltd.) with a radiation density of 0.83 W / cm ² was used, the distance between the heater and the molded product was 30 cm, and the surface temperature of the heater was 30.
The temperature was set to 0 ° C., and the temperature was reached at 120 ° C. for the reached substrate surface for 2 minutes. This product was tested for adhesion, abrasion resistance, stain resistance, and weather resistance.

The test results are shown in Table 1.

Comparative Example 1 The same operation as in Example 1 was performed. However, the top coat layer was baked by hot air heating. The hot-air drying was performed by using a hot-air constant temperature dryer DZ-50 (manufactured by Asahi Kagaku Kikai Co., Ltd.) and baking at an ambient temperature of 120 ° C. for 2 minutes. The obtained product had insufficient drying of the coating film, had tack (adhesiveness), caused a blocking phenomenon, and was not suitable for practical use.

The test results are shown in Table 1.

Comparative Example 2 The same operation as in Example 1 was performed. However, the top coat layer was baked by hot air heating. This hot air drying is
Using a hot air constant temperature dryer DZ-50 (manufactured by Asahi Kagaku Kikai Co., Ltd.), it was carried out under the conditions of an atmospheric temperature of 120 ° C. for 15 minutes. In this case, although the coating film was dried well, the embossing treatment previously performed causes unevenness to appear in the uneven pattern of the substrate and the undercoat layer, making the unevenness unclear, and at the same time the gloss of the metal thin film It became a molded article that felt less and less blurry. It has been difficult to say that such a product is excellent in design.

The test results are shown in Table 1.

Comparative Example 3 The same operation as in Example 1 was performed. However, as a material for forming the top coat layer, acrylic resin dialnal (trademark: LR
-574, manufactured by Mitsubishi Rayon Co., Ltd.) was applied onto the surface of the metal thin film layer using a clearance bar coater of 20 μm. Further, baking was performed by hot air heating. This hot-air drying was performed using a hot-air constant temperature dryer (trademark: DZ-50, manufactured by Asahi Kagaku Kikai Co., Ltd.) at an ambient temperature of 100 ° C. for 2 minutes. The thickness of the top coat layer was 20 μm. In this case, the coating film was dried well and the metallic luster was excellent, but the weather resistance was poor.

The test results are shown in Table 1.

Comparative Example 4 The same operation as in Example 1 was performed. However, the laminated body of the molded article substrate and the undercoat layer is not embossed,
It was directly subjected to vacuum deposition. The vacuum deposition and the top coat treatment were performed in the same manner as in Example 1, and the top coat surface of the obtained product was embossed. The embossing condition is that the surface of the top coat layer of the molded article substrate-top coat layer laminate is
The laminate was heated to 180 ° C. and embossed with an engraving roll having a plate depth of 150 μm to form an uneven pattern on the surface of the laminate of the molded product substrate and the undercoat layer. This product was inferior in metallic luster due to cracks generated in the metal thin film layer due to heat and pressure during embossing.

The test results are shown in Table 1.

Example 2 The same operation as in Example 1 was performed. However, the print surface of the GY sheet (manufactured by Goyo Paper Co., Ltd.) is 160 ° C on the undercoat surface.
Heat lamination was performed at the temperature of, and after cooling, the GY sheet was peeled off to form an uneven pattern on the substrate and the undercoat surface.

Thus, the laminated body of the substrate and the undercoat layer provided with the uneven pattern was subjected to the vacuum deposition operation. This vacuum vapor deposition is performed by resistance heating vapor deposition on the undercoat layer surface.
After a 4400 Å Al layer, a 1000 Å MgF ₂ layer, and a 150 Å Al layer were sequentially laminated, a top coat treatment was applied thereon in the same manner as in Example 1. This product has an elegant lustrous pattern using the principle of Fabry-Perot etalon, and it has a high design due to the synergistic effect with the uneven pattern.

The test results are shown in Table 1.

Adhesion test Put 100 pieces of 1mm square scoring cut into the top coat layer with a cutter, strongly stick cellophane adhesive tape (trade name "Cellotape" manufactured by Nichiban Co., Ltd.) to this, peel off rapidly in 90 directions, and mold The adhesiveness of the top coat layer was judged by the number of crevices in the coating film remaining on the product.

Abrasion test The abrasion test was performed according to the JIS-L-1096 Taber method. Wear wheel CS-17
Was used, the load was 1000 gf, and the rotation speed was 100 times. The wear resistance was judged from the weight loss (g) of the sample.

Dirt test Performed in accordance with JIS-L-1021, rotation speed 100 times, absorption power 1.1
cm ³ / min, and the degree of contamination was judged using JIS-L-0805 Contamination Gray Scale.

Example 3 100 parts by weight of polyvinyl chloride resin (trademark: Denka SS-103), 40 parts by weight of DOP (dioctyl phthalate), 3 parts by weight of EPS (epoxidized soybean oil), and 2 parts by weight of a Ba-Zn stabilizer are blended. A film having a thickness of 0.3 was formed from the composition prepared above using a heating roll, and this was used as a molded article substrate.

Then, an undercoating treatment and an embossing treatment were applied in the same manner as in Example 1.

Next, an ITO film (In ₂ O ₃ 95%, SnO ₂ 5%) having a film thickness of 1000 Å was laminated on the undercoat layer by a sputtering method.

Next, on the surface of the metal thin film layer, 100 parts by weight of acrylic-silicon resin (trademark: UA-90, manufactured by Sanyo Chemical Industry Co., Ltd.), 7.5 parts by weight of catalyst (trademark: Cat65MC, manufactured by Sanyo Chemical Industry Co., Ltd.), weathering agent (trademark) 20 parts by weight of a composition comprising 0.2 parts by weight of TINUVIN P, manufactured by Ciba-Geigy) and 20 parts by weight of methyl ethyl ketone.
m clearance bar coater was used for coating, and baking was performed by far-infrared heating to form a top coat layer having a film thickness of 20 μm. For baking with a far-infrared heater, use a ceramic component heater 403SS (manufactured by Nippon Light Metal Co., Ltd.) with a radiation density of 0.83 W / cm ² and set the distance between the heater and the baking surface.
It was carried out under the conditions of 30 cm, the surface temperature of the heater was set to 300 ° C., and the reached substrate surface temperature was 120 ° C. for 3 minutes. The obtained molded product has a feeling of unevenness and is not only rich in design,
It has a high light transmittance and a high reflectance for far infrared rays, and can be applied as a window film as a transparent heat insulating material. Table 2 shows the measurement results of the heat insulation rate and the light transmission rate of this product after being exposed outdoors for one year.

In addition, in the examples, the heat insulation rate means that the heat flow meter (Shothe
rm HFM: Showa Denko), the heat absorption is assumed to be 100 when nothing is placed between the calorimeter sensor and the heat source, and the test sample is placed between the two to stabilize the heat flow. When the amount is a, it is represented by (100−a / 100) × 100 (%). A tungsten lamp was used as the heat source. Unless otherwise specified, this measurement was performed by directly exposing the surface of the topcoat layer of the present invention to a heat source, assuming actual use conditions.

In addition, the light transmittance in the examples means the transmittance with respect to a light ray having a wavelength of 550 nm. In addition, the heat insulation rate and the light transmission rate after the exposure were measured after gently wiping off the dirt adhering to the surface with a soft cloth (cotton) wet with water.

[Effect of the Invention] The metal thin film-laminated polyvinyl chloride resin molded product of the present invention has an elegant metallic luster, its uneven pattern is stable, and its weather resistance is also excellent. It can be used for a long time.

Due to the effects of the present invention described above, the metal thin film laminated polyvinyl chloride resin molded article excellent in design obtained by the method of the present invention is extremely useful for awning tents, truck hoods, advertising signs, etc., and for indoor use. It can also be widely used in applications such as wall materials, blinds, label stickers, and window insulating films.

[Brief description of drawings]

FIG. 1 is a sectional explanatory view of an example of a metal thin film laminated polyvinyl chloride resin molded product of the present invention. 1 ... Molded article substrate, 2 ... Undercoat layer, 3 ... Metal thin film layer, 4 ... Topcoat layer.

Claims (2)

[Claims] 1. A molded article substrate made of a polyvinyl chloride resin material, and an undercoat which is laminated and bonded on at least one surface of the substrate, is made of a synthetic resin material, and has a thickness of 5 to 50 μm. A layer, a metal thin film layer formed and laminated on the undercoat layer, and a top coat layer laminated and bound on the metal thin film layer and made of a transparent synthetic resin material, And the laminate of the undercoat layer, by engraving made from the undercoat layer surface, the uneven pattern common to both is formed, the metal thin film layer covers the uneven pattern surface of the undercoat layer, Having an uneven pattern corresponding to it, the top coat layer is baked by far infrared heating,
And it has a smooth outer surface. A metal thin film-laminated polyvinyl chloride resin molded product with excellent design characteristics, characterized in that 2. An undercoat agent made of a synthetic resin material is applied onto at least one surface of a molded article substrate made of a polyvinyl chloride resin material and baked to form an undercoat layer having a thickness of 5 to 50 μm. Formed, the laminate of the substrate and the undercoat layer is subjected to a stamping process from the undercoat layer surface to form an uneven pattern common to both, and the uneven pattern of the laminate of the substrate and the undercoat layer is formed. On the surface having, coating this, to form a metal thin film layer having a corresponding uneven pattern, apply a coating solution containing a transparent synthetic resin material on the metal thin film layer, baking it by far infrared heating A method for producing a metal thin film-laminated polyvinyl chloride resin molded article having excellent design characteristics, which comprises subjecting a top coat layer having a smooth outer surface to form a top coat layer.