JPH04140136A - Metallic thin film laminated polyvinyl chloride resin molding excellent in designing property, and manufacture thereof - Google Patents

Abstract

PURPOSE:To obtain a molding having metallic luster, clear recession and protrusion patterns, and an excellent durability and contaminating property by forming recession and protrusion patterns in common between a base body and undercoat layer laminated body, and forming a metallic thin film layer and topcoat layer on the undercoat layer. CONSTITUTION:The titled molding is comprised of a molding base body 1 consisting of polyvinyl chloride resin material, and an undercoat layer 2, metallic thin film layer 3, and topcoat layer 4 which are formed successively thereon. The undercoat layer 2 consists of synthetic resin material and, on the laminated body of the molding base body 1 and undercoat layer 2, recession and protrusion patterns by stamping are formed. The metallic thin film layer 3 covering the recession and protrusion patterns of the undercoat layer 2 has recession and protrusion patterns corresponding to the recession and protrusion patterns of the undercoat layer 2, and the topcoat layer 4 formed on the metallic thin film layer 3 consists of a transparent synthetic resin material, and the surface thereof is smooth.

Description

[Detailed Description of the Invention] C. Industrial Application Field] The present invention relates to a thin metal film laminated vinyl resin molded product with excellent design and a method for producing the same, and particularly to durable housing,
It has excellent stain resistance and can be used not only for indoor applications such as decorative boards, wallpaper, blinds, and label stickers, but also for outdoor applications such as tents, truck tops, and advertising signs for sun shades that are exposed to wind and rain. This invention relates to an excellent metal thin film laminated vinyl resin molded product and a method for manufacturing the same.

[Conventional technology]

Currently, metal thin film laminates using vacuum deposition technology are often used in the fields of clothing, packaging materials, and decorative items to give a sense of luxury and eccentricity.

For convenience of processability, these metal thin film laminates are often made of materials that have low volatile components in a vacuum chamber, such as resins such as polyester or polyethylene, with metal thin films laminated thereon.

However, it is difficult to impart fine uneven patterns to these resin materials, and thermoplastic polyvinyl chloride resins, which can easily be formed into uneven patterns, are generally used for such applications. be.

When producing a metal thin film laminate having an uneven pattern on a polyvinyl chloride resin as a base material, a step of applying the uneven pattern to the base material or to the final product is required.

One method for imparting an uneven pattern is to print an ultraviolet curable resin onto the base material or the final product, but this is not a good idea due to its high cost. In general,
A simple method is to use polyvinyl chloride resin as a base material and emboss it using an engraving roll.

In order to obtain a metal thin film laminate with an uneven pattern, it is necessary to perform an embossing process before or after the metal thin film forming process.

For example, when embossing is performed after the formation of a metal thin film, an undercoat treatment is performed on a base made of polyvinyl chloride resin, a metal thin film is formed on this by vacuum evaporation, and then a top coat layer is provided. One possible method is to emboss the laminate. However, when a concavo-convex pattern is formed on the outermost layer, dirt tends to adhere to the concavo-convex portion, making it difficult to maintain a good metallic luster.

In addition, the heat and pressure during the final embossing process often cause cracks in the metal thin film layer, resulting in loss of metallic luster and an unsatisfactory product.

On the other hand, as disclosed in JP-A No. 53-36559, a method of performing embossing treatment before forming a metal thin film;
That is, there is a method in which a polyvinyl chloride resin base is subjected to an undercoat treatment, and then this laminate is subjected to an embossing treatment, and then a metal thin film layer and a top coat layer are sequentially formed. In this method, it is unavoidable that the baking of the topcoat layer is sometimes affected by a considerable amount of heat, which extends to the base material and the undercoat layer. The effect of the heat may cause the texture of the base material to return, making it impossible to obtain a product that meets the intended purpose. In particular, when the top coat layer is formed from a resin material that requires high-temperature baking, baking at a predetermined temperature will result in significant back-graining of the base material and the disappearance of the metallic luster uneven pattern on the second edge. Furthermore, when baked at a low temperature, the original characteristics of the resin are impaired, and the desired performance of the top coat layer, such as abrasion resistance, weather resistance, and adhesion, is significantly reduced.

In addition, coating with ultraviolet curable resins may be considered as a means of providing a top coat layer that does not require heat treatment, but the use of these resins is costly and furthermore, shrinkage during curing may cause peeling of the metal thin film layer. So it's hard to say it's a good idea.

[Problems to be Solved by the Invention] The present invention provides the following features: (a) The baking of the top coat layer does not cause the base material to become grainy during processing, and (b) it has a metallic luster and an uneven pattern is clearly defined. The object of the present invention is to provide a metal thin film laminated polyvinyl chloride resin molded product with excellent design, which satisfies the requirements of durability and antifouling properties, and a method for producing the same.

[Means and actions to solve the problem]

The metal thin film laminated vinyl resin molded product with excellent design according to the present invention includes a molded product base made of a polyvinyl chloride resin material, and is laminated and bonded on at least one surface of the base,
and an undercoat layer made of a synthetic resin material, a metal thin film layer formed and laminated on the undercoat layer, and a top coat layer laminated and bonded on the metal thin film layer and made of a transparent synthetic resin material. The laminate of the base body and the undercoat layer has a common uneven pattern formed on at least one surface thereof, and the metal thin film layer has the uneven pattern of the undercoat layer. It is characterized by covering the surface and having a corresponding uneven pattern.

In addition, the method of the present invention for producing the metal thin film laminated polyvinyl chloride resin molded article with excellent design features includes applying an undercoating agent made of a synthetic resin material on at least one surface of the molded article base made of a polyvinyl chloride resin material. is coated and baked to form an undercoat layer, and the substrate-undercoat layer laminate is subjected to a stamping treatment from at least one side thereof to form a common uneven pattern on both sides, A metal thin film layer having a corresponding uneven pattern is coated on the surface of the coat layer laminate having an uneven pattern, and a coating liquid containing a transparent synthetic resin material is applied onto the metal thin film layer. , is characterized in that it is baked using far infrared heating to form a top coat layer.

The present invention will be explained in detail below.

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

This molded product includes a molded product base l made of a polyvinyl chloride resin material, an undercoat layer 2 formed thereon,
It consists of 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 product base 1 and the undercoat layer 2 is coated from at least one surface thereof (in the case of FIG. 1, from the surface of the undercoat layer 2). A concavo-convex pattern is formed by stamping (from ), and this concave-convex pattern is common to both the substrate 1 and the undercoat layer. A metal thin film layer 3 is formed on the uneven surface of the undercoat layer 2 to cover it.

Naturally, this metal thin film layer 3 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 its surface is preferably smooth.

The polyvinyl chloride resin material forming the base of the molded product is soft polyvinyl chloride resin; hard polyvinyl chloride resin; vinyl chloride and olefins such as ethylene, propylene,
or a copolymer resin with inbutylene, a copolymer resin with vinyl chloride and styrene; a copolymer resin with vinyl chloride and dienes, such as butadiene, or isoprene;
A copolymer resin of vinyl chloride and acrylic acid, halogenated olefin, or vinyl acetate; and the above resin and a modifying resin such as ABS, 5BR1 or NB.
You can choose from mixed resins with rubbers such as R.

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

The polyvinyl chloride resin material used in the present invention includes:
Depending on the purpose, suitable amounts of stabilizers, fillers, flame retardants, flame retardants, antioxidants, ultraviolet absorbers, fungicides, lubricants, pigments, etc. may be included.

The molded product substrate used in the present invention is made of a polyvinyl chloride resin material by any appropriate method such as extrusion molding, injection molding, calendar molding, inflation molding, compression molding, coating, or dipping. It can be obtained by molding into the desired shape and dimensions using the molding method described above. Additionally, the molded article substrate may include a suitable fibrous material made of synthetic fibers, semi-synthetic fibers, natural fibers, etc., combined 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. There are no particular limitations on the method for forming the undercoat layer, and any conventional coating method, such as gravure roll coating, reverse roll coating, air knife coating, rod coating, or spray coating, can be used.

There is no particular restriction on the thickness of the undercoat layer, but it is generally preferably 5 to 50 an. This thickness is 5
- If the thickness is less than 5C, the gloss of the metal thin film may be impaired due to the influence of additives such as plasticizers that migrate from the polyvinyl chloride resin material forming the base, and the thickness may be less than 5C). If the temperature exceeds tm, the properties of the substrate made of polyvinyl chloride resin material, such as flexibility, will not be fully utilized. For the laminate of the molded product base and undercoat layer,
An uneven pattern by imprinting is imparted to at least one surface thereof, generally from the undercoat layer surface. The uneven pattern can be engraved by embossing using an engraving roll, or by printing a three-dimensional pattern on a hard film using a hard resin, such as by UV curing on a 100 mm thick polyester film. A sheet printed with polyester resin in a three-dimensional pattern and cured is thermally laminated onto the molded product base undercoat layer laminate, cooled, and the three-dimensional pattern sheet is peeled off to form the molded product base-undercoat layer. A method of forming an uneven pattern on the laminate can be used.

As a method for forming the metal thin film layer, known methods such as a vacuum evaporation method and a sputtering method can be used. Regarding the metal material used in the present invention, it is preferable to select a metal having infrared reflective ability in order to prevent induction heating of the polyvinyl chloride resin base by infrared rays and to provide a high heating effect to the top coat resin. preferable. Such metal materials include ^R, b, Ni, Cr, and u
, A g , A u , F e ,
! , l n .

There are metals such as 2n, Sn, etc., and 2nO.

)n2D3.5n02, etc. are also included. The material for forming the metal thin film layer is selected depending on the purpose of the molded product and the required functions. These metal thin film layers may be composed of one layer or a laminate of multiple layers, or a laminate of a layer made of these metal materials and another metal layer that does not have infrared reflective ability, For example, a thin film such as Aβ-MgFe-Aβ, 2nS-A
A rudemirror type stack such as g-2nS can be used.

The thickness of the metal thin film layer is preferably within the range of 100 to 3500 mm). If the film thickness is less than 100 mm, the reflection efficiency of infrared rays will decrease, causing a phenomenon of embossment returning to the polyvinyl chloride resin material base, and if it exceeds 3,500 mm, cracks will occur in the metal thin film layer, resulting in a significantly poor aesthetic appearance. is damaged.

The top coat layer is intended to protect the metal thin film layer and make the product antifouling, and is generally formed from an organic solvent type or emulsion type resin paint. In the present invention, since the molded product base is made of a material with low heat resistance such as a polyvinyl chloride resin material, a room temperature drying type resin or a low temperature drying smoke type resin with a drying temperature of 100°C or less is generally used. used. However, these resins inherently have insufficient abrasion resistance, weather resistance, etc., and for this reason, when used under harsh conditions such as outdoors, the top coat layer is coated with transparent resin. It is preferable to use a type of resin paint. That is, the resin that absorbs well and hardens far infrared rays in the wavelength range of 10 to 100 degrees is highly dyed. Such resins include Epoquine resin, polyester resin, polyvinylidene chloride resin, melamine resin, urethane resin, acrylic resin, and silicone modified resin.
You can choose from tan resin, phosphor-modified acrylic resin, fluorine-modified acrylic resin, etc.

Formation of the top coat layer includes reverse roll coating, air knife coating, rod coating,
An appropriately selected coating method such as spray coating can be used. The thickness of the top coat layer is 1 to 1
It is preferable that the distance be within the range of 00 m.

If the thickness of the top coat layer is less than 10 7 -, the durability and abrasion resistance will be poor, and if it exceeds 10 7 -, cracks will be likely to occur. One of the features of the method of the present invention is that the top coat layer is formed by baking using far-infrared heating.

The far-infrared heater used in the method of the present invention is an electric far-infrared heater, such as a pipe type or a plate type.The structure is a sheathed heater made of nichrome wire as a heating element and an electric insulating material, and the outer surface of the sheathed heater is made of ceramic. The heater can be selected from the following: a gas-type far-infrared heater, such as a heater that heats far-infrared radiating ceramics with high-temperature combustion gas, and a steam-type far-infrared heater, such as a heater that uses the condensation heat of steam as the heat generation source. There is no particular restriction on the far-infrared emitting ceramic used here, and Mn[l
, Fe2O3,Cub, CrO2,Z
rO2,5i02. It consists of a mixture of Ti, Aβ203, etc. The heating conditions using the far-infrared heater are appropriately determined based on the characteristics of the top coat resin material and the coating film thickness, but it is preferable to carry out the heating under conditions of 50 to 10,000 Kcaβ/mr·hr. In the method of the present invention, the effect of infrared reflection by the metal thin film layer prevents thermal effects on the substrate and promotes the heating effect of the top coat layer.

〔Example〕

The present invention will be further explained by the following examples.

Example 1 Polyvinyl chloride resin (trademark: Denka SS-1,0300
0 parts by weight, DOP (dioctyl phthalate) 45 parts by weight, EPS (epoxidized soybean oil) 3 parts by weight, Ba-Z
A composition containing 2 parts by weight of an n-type stabilizer was formed into a film with a thickness of 0.2 mm using a heated roll. Polyester multifilament 1000 as warp and weft
The above films were heat-affixed on both sides of a fabric using denier yarns at a density of 11 yarns/25.4 m+n each to create a polyvinyl chloride resin sheet, which was used as a molded article substrate.

Next, as an undercoat agent, urethane resin (trademark:
MX-1, manufactured by Seiko Kasei Co., Ltd.) was coated on one surface of the molded product substrate using a 100 mesh gravure roll, and dried with hot air at a temperature of 120°C for 2 minutes to form an undercoat with a thickness of 20 Ja. formed a layer. The undercoat surface of the substrate-undercoat layer laminate was heated to 160° C. and embossed using an engraving roll having a plate depth of 150° C., thereby carving a common uneven pattern on the substrate and the undercoat layer.

In this manner, metal A was vacuum-deposited on the undercoat layer surface of the substrate-undercoat layer laminate in which the uneven pattern was formed. Vacuum deposition was performed on the uneven patterned surface by resistance heating vapor deposition to form a metal Aβ thin film layer with a thickness of 400 μm.

Next, 100 parts by weight of an acrylic-silicon resin (trademark: UA-90, manufactured by Sanyo Chemical Industries, Ltd.) and 7.5 parts by weight of a catalyst (trademark: Cat65MC1, manufactured by Sanyo Chemical Industries, Ltd.) were applied as a top coat agent on the surface of the metal thin film layer. , methyl ethyl ketone 2
A composition consisting of 0 parts by weight was coated using a 20-mm clearance bar coater and baked by far infrared heating to form a top coat layer with a thickness of 20 IM.

Baking with a far infrared heater has a radiation density of 0.83W
/crl Ceracompo Heater 403SS (manufactured by Nippon Light Metal Co., Ltd.) was used, the distance between the heater and the molded product was set to 30 cm, the surface temperature of the heater was set to 300 °C, and the treatment was carried out for 2 minutes at the final substrate surface temperature of 120 °C. Ta. 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 heating with hot air.

This hot air drying was performed using a constant temperature hot air dryer DZ~50 (manufactured by Asahi Kagaku Kikai Co., Ltd.) at an ambient temperature of 120° C. for 2 minutes. The resulting product had a tack (adhesiveness) due to insufficient drying of the coating film, which caused a sticking phenomenon, making it difficult to put it to 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 heating with hot air. This hot air drying
The drying was carried out using a hot air constant temperature dryer D2-50 (manufactured by Asahi Kagaku Kikai Co., Ltd.) at an ambient temperature of 120° C. for 15 minutes.

In this case, the coating film dried well, but the uneven pattern on the substrate and undercoat layer due to the previously applied embossing process returned to grain, making the unevenness unclear and at the same time reducing the luster of the metal thin film. The molded product looks blurry.

Such products could no longer be said to have excellent design.

The test results are shown in Table 1.

Comparative Example 3 The same operation as in Example 1 was performed. However, acrylic resin Dianal (trademark: L) is used as the top coat layer forming material.
R-574 (manufactured by Mitsubishi Rayon Co., Ltd.) was used to coat the surface of the metal thin film layer using a 20 μm clearance bar coater. Baking was also performed by heating with hot air. This hot air drying was performed using a constant temperature hot air 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 20J-. This product had a coating film that dried well and had excellent metallic luster, but its 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 molded article substrate-undercoat layer laminate was not subjected to embossing treatment, but was directly subjected to vacuum deposition. Vacuum deposition and top coat treatment were performed in the same manner as in Example 1, and the top coat surface of the obtained product was subjected to embossing treatment. The embossing conditions were such that the surface of the top coat layer of the molded product base-top coat layer laminate was
It was heated to 0° C., and embossing was performed using an engraving roll having a depth of 150 mm to create an uneven pattern on the surface of the molded product substrate-undercoat layer laminate. In this product, cracks occurred in the metal thin film layer due to the heat and pressure during the embossing process, resulting in poor metallic luster.

The test results are shown in Table 1.

Example 2 The same operation as in Example 1 was performed. However, the printed side of GY Receipt (manufactured by Goyo Shiko Co., Ltd.) must be placed on the undercoat side.
Thermal lamination was performed at a temperature of 0° C., and after cooling, the GY receipt was peeled off and an uneven pattern was carved on the substrate and undercoat surface.

The substrate-undercoat laminate thus provided with an uneven pattern was subjected to a vacuum deposition operation. This vacuum evaporation is performed on the undercoat layer surface to a thickness of 400 mm by resistance heating evaporation method.
After laminating the A1 layer of 1,000 people, the MgF2 layer of 1000 people, and the A1 layer of 150 people in sequence, a top coat treatment was applied thereon in the same manner as in Example 1.

This one is FabryP-Etalon (FabryP
It has an elegant luminous pattern that utilizes the principle of erot etalon, and its synergistic effect with the uneven pattern makes it highly decorative.

The test results are shown in Table 1.

Adhesion test 100 1 mm square goban-like cuts were made with a cutter in the top coat layer, and cellophane adhesive tape (trade name: "Cello Tape" manufactured by Nichiban Co., Ltd.) was firmly attached to these.
It was rapidly peeled off in a 90 degree direction, and the adhesion of the top coat layer was judged by the number of gobbles in the coating film remaining on the molded product.

Abrasion test was carried out according to the Taber type method of JIS-L-1096. A worn wheel C3-17 was used, the load was 10100O, and the number of rotations was 100 times. Wear resistance was determined from the weight loss (g) of the sample.

Dirt test was conducted according to JIS-L-1021, the number of revolutions was 100 times, the absorption capacity was 1.1 cnf/min, and the degree of contamination was JIS-L-1021.
Judgment was made using the SL-0805 gray scale for contamination.

Example 3 Polyvinyl chloride resin (trademark: Denka 5S-103) 1
00 parts by weight, DOP (dioctyl phthalate) 40 parts by weight, EPS (epoxidized soybean oil) 3 parts by weight, Ba-
A film having a thickness of 0.3 was prepared using a heating roll from a composition containing 2 parts by weight of a 2n stabilizer, and this was used as a molded article substrate.

Next, undercoat treatment and embossing treatment were performed in the same manner as in Example 1.

Next, an ITD film (In20,95%, 5n02
5%) was laminated.

Next, 100 parts by weight of an acrylic-silicon resin (trademark: UA-90, manufactured by Sanyo Chemical Industries, Ltd.) and a catalyst (trademark: Cat65MC, manufactured by Sanyo Chemical Industries, Ltd.)7.
A composition consisting of 5 parts by weight, 0.2 parts by weight of a weathering agent (trademark: Tinuvin P, manufactured by Civer-Geigy), and 20 parts by weight of methyl ethyl ketone was coated using a 20-mm clearance bar coater, and then heated by far infrared rays. Baked on,
A top coat layer having a thickness of 20 mm was formed. For baking with a far-infrared heater, use Ceracombo Heater 403SS (manufactured by Nippon Light Metal Co., Ltd.) with a radiation density of 0.83 W/ci.
For baking, the distance between the heater and the surface was set at 30 cm, the surface temperature of the heater was set at 300°C, and the final substrate surface temperature was 120°C.
The test was carried out for 3 minutes. The obtained molded product has an uneven texture and is not only rich in design, but also has high light transmittance and high far-infrared reflectance, so it can be used as a transparent heat insulating material and as a window film. Table 2 shows the measurement results of the heat insulation rate and light transmittance of this product after one year of outdoor exposure.

In addition, in the examples, the term "thermal insulation rate" refers to a heat flow meter (Sho
Therm HFM (Showa Denko) is used to calculate the amount of absorbed heat when nothing is placed between the calorimeter sensor and the heat source.
00, and when the amount of heat absorbed after the heat flow stabilizes by placing the test sample between the two is a, (100-a/10
0)
The surface of the top coat layer of the product of the present invention was directly exposed to a heat source.

In addition, the light transmittance in Examples refers to the transmittance for light having a wavelength of 550 nm. The heat insulation rate and light transmittance after exposure were measured after lightly wiping off dirt adhering to the surface with a soft cloth (cotton) moistened with water.

Table 2 [Effects of the Invention] The metal laminated vinyl resin molded product of the present invention has an elegant metallic luster, a stable uneven pattern, and excellent weather resistance, so that the molded product can be used outdoors. Can be used for a long time.

Due to the effects of the present invention described above, the metal laminated vinyl resin molded product with excellent design obtained by the method of the present invention is extremely useful for sunshades, tents, truck hoods, advertising signs, etc.
It can also be widely used indoors for wall materials, blinds, label stickers, window insulation films, etc.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an explanatory cross-sectional view of an example of the metal thin film laminated polyvinyl chloride resin molded product of the present invention. 1... Molded product base, 2... Undercoat layer,
3...Metal thin film layer, 4...Top coat layer.

Claims (1)

[Scope of Claims] 1. A molded product substrate made of a polyvinyl chloride resin material, an undercoat layer made of a synthetic resin material and laminated and bonded on at least one surface of the substrate, and the undercoat layer A laminate of the base and the undercoat layer, comprising a metal thin film layer formed and laminated thereon, and a top coat layer laminated and bonded on the metal thin film layer and made of a transparent synthetic resin material. A common uneven pattern is formed on at least one surface of the undercoat layer, and the metal thin film layer covers the uneven pattern surface of the undercoat layer and has a corresponding uneven pattern. Metal thin film laminated polyvinyl chloride resin molded product with excellent design. 2. Applying 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 and baking it to form an undercoat layer, the substrate-undercoat layer laminate. is stamped from at least one side thereof to form a common uneven pattern on both sides, and the surface of the substrate-undercoat layer laminate having the uneven pattern is coated with this, and a corresponding uneven pattern is formed on the surface of the substrate-undercoat layer laminate. A top coat layer is formed by forming a metal thin film layer having the following properties, applying a coating liquid containing a transparent synthetic resin material onto the metal thin film layer, and baking the coating liquid by far infrared heating. Item 1. A method for producing a thin metal film laminated polyvinyl chloride resin molded article with excellent design.