WO2000032680A1

WO2000032680A1 - Colored resin film for metal sheet laminating and colored metal sheet containing the colored resin film

Info

Publication number: WO2000032680A1
Application number: PCT/JP1999/006734
Authority: WO
Inventors: Hiroyuki Iwashita; Koji Taguma; Yoshiyuki Sugimoto
Original assignee: Toyo Kohan Co., Ltd.
Priority date: 1998-12-01
Filing date: 1999-12-01
Publication date: 2000-06-08
Also published as: AU1512200A

Abstract

A colored resin film for metal sheet laminating which has hiding power sufficient to hide the metal sheet to be used as a laminating base and has a beautiful appearance; and a colored metal sheet in which the colored resin film has been laminated. The colored resin film is a single-layer film containing a coloring pigment in such an amount as to have a total light transmittance of 20 % or lower. A resin layer for protecting the colored resin film, a resin layer for improving the adhesion of the colored resin film to the metal sheet, etc. are formed on the front or back side of the colored resin film to produce a multilayered resin film. This multilayered resin film is laminated to the metal sheet.

Description

Description 1 Colored resin film for metal plate lamination and colored metal plate laminated with the colored resin film

TECHNICAL FIELD The present invention relates to a colored resin film for laminating a metal plate, which is high in hardness and excellent in moldability, design properties, chemical resistance and the like.

The present invention also relates to a colored metal plate on which the colored resin film is laminated. Background art

Conventionally, as a decorative material for exterior panels or internal parts of building materials, furniture, electrical and electronic equipment, audio equipment, office equipment, etc., polyolefins containing polyethylene or polypropylene as a main component, including soft plasticized polyvinyl chloride resin Metal plates made by laminating resins and their films, such as biaxially stretched films of resin, thermoplastic acrylic resin, fluorine resin containing fluorine, or polyester resin, are used.

Polychlorinated vinyl resin has excellent properties such as economy, embossability and moldability, but usually contains a large amount of plasticizer.

For this reason, it is soft when formed into a resin film, bleeds the plasticizer onto the surface over a long period of time, and generates hydrogen chloride gas during combustion and disposal, causing harmful substances that cause environmental pollution. The impact is a problem.

Therefore, polyolefin resins containing polyethylene or polypropylene as the main component are being studied as a resin to replace polyvinyl chloride.

These resins alone have excellent properties such as embossability and chemical resistance.

In addition, although it is harder than plasticized polyvinyl chloride resin, when it is laminated and formed on a base material such as a metal plate, the processed portion becomes white and the design is impaired. In order to suppress the whitening phenomenon, a rubber component may be blended in some cases. However, the obtained resin film is as soft as a plasticized polyvinyl chloride resin. Further, the thermoplastic acrylic resin and the fluororesin each have characteristic characteristics, but when formed into a resin film, they are as soft as the plasticized polyvinyl chloride resin.

On the other hand, in recent years, polyester resin films, such as biaxially stretched films of polyester resins containing polyethylene terephthalate resin as a main component, have attracted attention as a laminating material obtained by laminating a resin film on a metal plate or the like. In order to improve the design of these resin films, it is necessary to color the resin films.

(D However, the effect of the type and concentration of the coloring pigment contained in the polyester resin and the thickness of the colored resin film on the concealment of the metal substrate base to be laminated is unclear, and sufficient base concealment is provided. However, it was difficult to adjust the pigment concentration in the resin and the thickness of the colored resin film so as to have sufficient workability as a resin film.

\ An object of the present invention is to provide a colored resin film for laminating a metal plate, which has a sufficient concealing property of a metal substrate base to be laminated and a beautiful appearance. Another object of the present invention is to provide a colored metal plate on which the colored resin film is laminated.

Disclosure of the invention

1) The colored resin film for metal plate lamination of the present invention contains a colored pigment in the resin film such that the total light transmittance represented by the following formulas (1) to (3) is 20% or less. It is characterized by letting you let it.

Total light transmittance [%] = 6 (& zu (pigment concentration product) 1 Ζ 2) Χ 100 (1) Pigment concentration product = pigment concentration [wt%] X resin film thickness [μm] (2), -9 ≤a≤- 0.5 (a: unique value depending on pigment type) (3)

The film has a lower layer made of a resin film containing no coloring pigment, It is characterized by being composed of two upper layers composed of a colored resin film.

The film is characterized by comprising two layers, an upper layer made of a resin film containing no coloring pigment, and a lower layer made of the colored resin film.

The film is a colored resin film for metal plate lamination comprising three layers, an upper layer, an intermediate layer, and a lower layer, wherein the upper layer is a layer composed of the above colored resin film.

The film is a colored resin film for laminating a metal plate composed of three layers of an upper layer, an intermediate layer and a lower layer, wherein the intermediate layer is a layer composed of the colored resin film.

IC The above film is a colored resin film for laminating a metal plate composed of four layers of an upper layer, an upper intermediate layer, a lower intermediate layer, and a lower layer, wherein the upper intermediate layer or the lower intermediate layer is made of the above colored resin film. Characterized in that it is a layer.

The film is characterized in that the uppermost layer is a resin film to which an anti-glare agent is added.

i The film is characterized in that the resin film is a polyester resin film.

The colored metal plate of the present invention is characterized in that the above-mentioned film is laminated on at least one side of the metal plate.

The colored metal plate of the present invention is characterized in that an adhesive layer is interposed between the metal plate and the film, and the film is laminated. BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, the metal film is laminated by including a color pigment in the resin film so that the total light transmittance represented by the following formulas (1) to (3) is 20% or less. A colored resin film for laminating a metal plate having a sufficient concealing property of the substrate base and a beautiful appearance was obtained. Total light transmittance [%] = exp (aX (pigment concentration product) 1/2) X100 (1) Pigment concentration product = pigment concentration [wt%] X resin film thickness [μm] (2)

-9≤a≤-0.5 (a: specific value depending on the type of pigment) (3) Further, the colored resin film for laminating a metal plate of the present invention comprises the above-mentioned colored resin film and another resin film containing no colored pigment. By combining with, resin films having various configurations shown below can be obtained.

1) A colored resin film for laminating a metal plate comprising two layers: a lower layer of a resin film containing no coloring pigment and an upper layer of the colored resin film.

2) A colored resin film for laminating metal plates consisting of two layers, an upper layer of a resin film containing no coloring pigment and a lower layer of the colored resin film.

3) A colored resin film for laminating metal plates, consisting of an upper colored resin film, an intermediate layer, and a lower layer.

4) A colored resin film for laminating a metal plate consisting of three layers, an upper layer, an intermediate layer, and a lower layer.

5) Coloring for metal plate lamination consisting of 4 layers: upper layer, upper intermediate layer or lower intermediate layer, colored resin film, lower intermediate layer or upper intermediate layer containing no color pigment, resin film, and lower layer Resin film.

6) The colored resin film for laminating metal plates according to 2), 4) and 5) above, wherein the uppermost layer is made of a resin film to which an anti-glare agent is added.

By laminating the colored resin film for laminating a metal plate directly or via a bonding agent layer on a metal plate, a colored metal plate having a sufficient concealing property of a metal substrate base and a beautiful appearance can be obtained. Was.

Hereinafter, the content of the present invention will be described.

(Structure of resin film)

The colored resin film of the present invention is constituted by any of the following.

1) A single-layer film consisting only of a resin film containing a color pigment. 2) A two-layer film consisting of a lower layer of a resin film containing no coloring pigment and an upper layer of the colored resin film.

3) A two-layer film consisting of an upper layer of a resin film containing no coloring pigment and a lower layer of the colored resin film.

If 4) A three-layer film consisting of an upper colored resin film, an intermediate layer, and a lower layer.

5) A three-layer film consisting of an upper layer, an intermediate layer colored resin film, and a lower layer.

6) A four-layer finolem comprising a colored resin film of the upper layer, the upper intermediate layer or the lower intermediate layer, a resin film containing no colored pigment of the lower intermediate layer or the upper intermediate layer, a resin film, and a lower layer.

IC 7) The film according to 3), 5) or 6) above, wherein the uppermost layer contains an anti-glare agent.

The colored layer of the present invention is provided for hiding the underlying metal substrate and improving the design.

Further, by providing a resin layer containing no coloring pigment on the surface layer, it is possible to prevent the pigment from bleeding to the outermost layer, and to prevent the coloring layer from being damaged and the design property from being impaired.

Further, by providing a resin layer containing no color pigment in the intermediate layer, the texture of the resin layer is improved, and the workability and adhesiveness of the entire resin film are also improved.

The adhesive layer resin layer is _{this> 0} and is preferably a resin having excellent adhesive properties to bond the metal plate.

Further, by providing a resin layer to which an anti-glare agent is added on the uppermost layer of the colored resin film, the gloss of the surface of the resin layer is controlled and a soft texture can be obtained.

(Resin film)

i) ¾ "color layer

In the resin films having various configurations described in 1) to 7) above, the resin used for the colored resin film in which the pigment is contained in the resin film includes film hardness and processability. In view of the above, it is preferable to use a polyester resin. For example, polyethylene terephthalate, polybutylene terephthalate, a copolymerized polyester resin in which part of terephthalic acid constituting both of these resins is replaced with isophthalic acid, and a resin in which two or more of these resins are blended are used. Can be.

ii) Resin layer containing no color pigment

In the resin films having various configurations of the above 2) to 7), the upper layer of the resin film not containing the coloring pigment of 3), the resin layer of the intermediate layer and the lower layer of 4) containing no coloring pigment, and the resin film of 5) As the resin used for the upper and lower resin films containing no color pigment, and for the upper layer of 6) and the resin film containing no color pigment to be the upper intermediate layer or the lower intermediate layer, polyester used for the colored layer is used. The same polyester resin as the resin can be used.

When a resin layer not containing these coloring pigments is used as a surface layer, a polycarbonate resin or a polyarylate resin having excellent transparency and scratch resistance may be used.

iii) Adhesive layer

In the resin films of various configurations 2) and 4) to 7) of the present invention, the resin layer serving as the lower layer is preferably a resin having excellent adhesiveness for bonding to a metal plate.

As the resin having excellent adhesiveness, the same polyester resin as the polyester resin used for the above-mentioned colored resin layer or the resin layer containing no colored pigment can be used. In order to improve the processability of the adhesive layer and the adhesiveness to a metal plate, a resin obtained by blending 1 to 20% of an ionomer resin with these polyester resins may be used.

iv) Top layer with anti-glazing agent

In the resin film having the configuration of the above 7), the resin used for the resin layer containing no coloring pigment of the above ii) is applied as the uppermost resin layer to which the anti-glare agent is added. it can.

As the anti-glare agent, fine particles made of an inorganic material such as myriki, silica, alumina, calcium carbonate, diatomaceous earth, silica sand, and shirasu balloon, or fine particles made of an organic material such as cross-linked polystyrene can be used.

If These fine particles preferably have a particle size in the range of 1 to 10 / zm, and are preferably contained in the resin in a range of 10 to 50% by weight.

(Color pigment)

As the coloring pigment to be contained in the coloring resin layer, a usual pigment used for a paint can be used as it is. For example, carbon-based pigments such as carbon black, titanium-based pigments such as ID titanium white and titanium yellow, inorganic pigments such as red iron, lead white, gunjiyo, cadmium yellow, azo compound pigments such as para-red, and cyanine blue One or two or more pigments such as cyanine-based pigments and anthraquinone can be used. The above pigments preferably have a particle size of 0.01 to 5 // m.

, ff (Relationship between resin film thickness and coloring pigment content)

As can be inferred from the above equations (1) to (3), the larger the pigment concentration product, which is the product of the color pigment and the resin film, the smaller the total light transmittance, and the better the concealment of the underlying metal substrate. I do.

Therefore, by including a large amount of the coloring pigment in the thick resin film, a colored resin film for laminating a metal plate excellent in concealing property of a base metal substrate having a small total zero light transmittance can be obtained.

However, it is economically disadvantageous to make the resin film thicker than necessary, and if an extremely large amount of coloring pigment is contained in the resin film, the film-forming property is reduced or the flexibility of the colored resin film is poor. It becomes a hard and brittle film and is resistant to various forming processes

^ It becomes a colored resin film that cannot be obtained.

Therefore, a resin film with a thickness that is not economically disadvantageous It is necessary to contain a coloring pigment to such an extent that a sufficient concealing property of the underlying metal substrate is obtained within a range that does not impair the film properties and workability.

From these viewpoints, the thickness of the resin film is preferably in the range of 50 to 300 // m, and the content of the coloring pigment is preferably in the range of 2 to 30% by weight. if (metal plate used)

As the metal plate used for the colored metal plate of the present invention, any metal plate such as a steel plate, an aluminum plate, an aluminum alloy plate, a copper plate, and a copper alloy plate can be used.

The metal plate is preferably a cold rolled ordinary steel plate having a thickness of 0.10 to 0.12 Omm. Among them, a cold rolled steel plate of ordinary steel having a thickness of 0.10 to 0.50 mm is preferable.

(Among C cold rolled steel sheets, low carbon or ultra low carbon aluminum killed steel sheets are preferably used.

Non-aging steel to which Nb, Ti or the like is added, a steel sheet containing chromium of 3 to 18% by weight, a stainless steel sheet having various compositions, and the like can also be used. Surface-treated steel sheets obtained by subjecting the surface of these cold-rolled steel sheets to surface treatment can also be used. The ily surface treatment includes plating and chemical treatment.

Examples of plating include zinc plating, zinc-aluminum alloy plating, zinc-cobalt-molybdenum plating, tin plating, nickel plating, chrome plating, nickel plating-phosphoric plating, nickel plating-nickel plating , Plating, nickel plating, nickel plating, aluminum plating, etc.

As the chemical conversion treatment, there are electrolytic chromic acid treatment in which electrolytic treatment is carried out in a bath mainly composed of chromic acid, and chromate treatment in which immersion treatment or electrolytic treatment is carried out in a chromate bath.

In addition, there is a phosphoric acid chromate treatment in which a dip treatment or an electrolytic treatment is performed in a chromate bath and a bath containing phosphate.

In addition, there is a non-chromium treatment that is immersed in a bath containing a salt of titanium or zirconium.

In addition, alumite treatment applied to aluminum plates and aluminum alloy plates, etc. There is power ^s .

(Lamination method)

The above colored resin film is laminated on a metal plate using a known heat fusion method or the like. That is, the metal plate is heated to a temperature not lower than the melting point of the resin constituting the lowermost layer of the colored resin film »Γ, the colored resin film is brought into contact with the metal plate, and the two are sandwiched between a pair of laminating rolls. Immerse and quench.

For those requiring a high degree of adhesion to the metal plate, an adhesive layer is provided on the colored resin film, or an adhesive layer is provided on the metal plate, and the adhesive layer is interposed between the metal plate and the metal plate. It is also possible to laminate a colored resin film.

IP (Evaluation of concealment of underlying metal)

In a colored metal plate obtained by laminating a colored resin film on a metal plate as described above, the concealability of the underlying metal substrate by the colored resin film is determined by the total light transmission of the colored resin film layer defined as follows. It is possible to evaluate by rate.

By controlling the thickness of the colored resin film layer and the amount of the colored pigment contained in the colored resin film layer so that the total light transmittance falls within a certain range, a preferable base metal substrate is formed. Is obtained.

That is, the specific constants for the total light transmittance shown in the following equation (1), the pigment concentration product shown in the equation (2), and the type of the pigment shown in the equation (3) measured based on ASTM D1003 are as follows: In a relationship.

_ Total light transmittance [%] = exp (aX (pigment concentration product) 1/2) X100 (1)

Pigment concentration product = pigment concentration [weight. /. ] X resin film thickness [/ xm] (2) -9≤a≤-0.5 (a: unique value depending on pigment type) (3) Total light transmittance measurement method, and formulas (1) to (3) Was derived as follows.

^ (Total light transmittance measurement method)

Direct haze combination manufactured by Suga Test Machine Co., Ltd. based on ASTM D 1003 Using Uter HGM-2 DP, the total light transmittance was measured for a test piece obtained by cutting a colored metal plate obtained by laminating a colored resin film on a metal plate into a piece of 55 mm x 55 mm. This measurement was performed on three test pieces.

(Derivation of expression)

ペレット Pellets of polyethylene terephthalate resin and pigments of various colors are kneaded in an extruder and then extruded to obtain a pigment content (pigment concentration) of 0.1 to 30% by weight and a thickness of 20 to 1%. An unstretched colored film of 50 μm was prepared.

From the pigment concentrations of these various color films and the thickness of the resin film, a pigment concentration product was obtained from the above formula (2).

Then, this colored film was laminated on an electro-galvanized steel plate, and the total light transmittance of the obtained colored resin film laminated metal plate was measured as described above.

The relationship between the pigment concentration product for each color and the measured value of the total light transmittance was subjected to curve fitting by the least squares method, whereby the coefficient a in the above formula (1) was obtained for each color. .

^ In the present invention, a colored resin film in which the amount of the colored pigment contained in the colored resin film and the thickness of the colored resin film are variously changed is prepared, and after lamination on a chromated electrogalvanized steel sheet. The degree of hiding of the underlying metal substrate by the colored resin film was evaluated by visual observation.

Further, the total light transmittance was measured by the above method. As a result, it was found that the hiding property of the underlying metal substrate was excellent when the total light transmittance was 20% or less, although the degree was slightly different depending on the color of the colored resin film. If the total light transmittance exceeds 20%, the underlying metal substrate is not completely concealed, resulting in an appearance with poor design.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples.

^ (Example 1)

Available with polyethylene terephthalate resin pellets and six different colors as listed in Table 1. The extruded pigment is extruded after being kneaded in the extruder, and the content of the colored pigment (pigment concentration)

An unstretched colored film having a thickness of 0.1 to 30% by weight and a thickness of 20 to 150 μm was prepared.

As a base metal substrate, a 0.5 mm thick cold-rolled steel sheet was electroplated with zinc if to a thickness of 0.02 mm, and then heavy chromium was added so that the total chromium amount was 20 mg Zm2. Electrolytic treatment was performed in an acid soda solution to produce a zinc-plated steel sheet with a chromate film formed on the zinc plating.

The electroplated zinc-coated steel sheet was heated to 280 ° C., the colored film was brought into contact with one side of the sheet, sandwiched between a pair of laminate rolls, and immediately immersed in water if. In this way, a metal plate on which 42 types of single-layer colored resin films shown in Table 1 were laminated was obtained.

Table 1 shows the pigment concentration product and the total light transmittance of these 42 types of colored resin film laminated metal plates.

Further, these colored resin film laminated metal plates were visually observed, and the concealability of the lower lij-ground metal substrate was evaluated based on the following criteria.

A: No underlying metal is observed.

〇: The underlying metal is slightly recognized through the colored resin film, but there is no practical problem.

Δ: Base metal is recognized through the colored resin film.

^ X: The underlying metal is clearly seen through the colored resin film.

Table 1 shows the evaluation results. table 1

Sample coloring material Total light transmittance Base metal J »Plate number Type Color a value (o / o) GS shielding evaluation

1 2

2 5 (Q)

3 10

4 Power—phone rappu 黑 15

5 20 o

6 30

7 40 X

8

o

9 (5) n u U

-2.907 I

n

U

1 ν n

c

17 Π

i o

on

twenty one

twenty two

twenty three

24 i n

25 Titanium * Wight White-0.6343 15 Δ

26 20 χ

27 30 χ

28 0 χ

29

30

31 10 ο

32 Anthraquinone yellow-0.5597 15 △

33 20 X

34 30 X

35 40 X

36 2 ©

37 5 ©

38 10 〇

39 Titanium yellow t>-yellow-0.5275 15 〇

40 20 Δ

41 30 X

42 40 X As shown in Table 1, it can be seen that the concealability of the underlying metal substrate by the colored resin film varies depending on the color of the colored pigment and the constituent materials.

That is, in the case of a metal plate on which a dark black or brown resin film is laminated, if the total light transmittance is 20% or less, the underlying metal substrate is concealed.

T In the case of a metal plate laminated with a neutral resin blue or yellow resin film using titanium yellow, the underlying metal substrate is concealed if the total light transmittance is 15% or less. In the case of a metal plate on which a light-colored white or yellow resin film using anthraquinone is laminated, if the total light transmittance is 10% or less, the underlying metal substrate is concealed.

Further, if the total light transmittance is 5% or less, concealing properties as high as 10 j C can be obtained irrespective of colors and constituent materials.

(Example 2)

Next, a metal plate on which a colored resin film composed of two or more layers described in 2) to 7) above was laminated was prepared as follows.

[1] A metal plate obtained by laminating a two-layer film consisting of a lower layer of a resin film containing no colored pigment and an upper layer of the colored resin film of 2)

The same resin as used in Example 1 was used as the resin for the colored resin film as the upper layer, and the same mixture as in Example 1 was melt-blended with brown bengalara using a twin-screw extruder. melting the terephthalic acid 8 0 mol% and isophthalic Tal acid 2 0 mole ^_0/0 polyester the acid and ethylene glycol were copolymerized consisting> 0榭脂serving as both two layers of these two kinds of molten resin Continuously, and extruded from the die nozzle so that the thickness of the upper brown colored resin layer is 40 m and the thickness of the lower resin layer is 10 μπι. A two-layer unstretched film colored brown was prepared.

The amount of red iron oxide to be contained in the colored resin layer is such that the total light transmittance is 5 to 10% when the thickness of the colored resin layer is 40 μm. Was mixed. The two layers of the colored resin film were applied to the same zinc-plated steel sheet as used in Example 1 so that the copolymerized polyester resin layer containing no bengal was in contact with the galvanized steel sheet. Lamination was performed in the same manner as in Example 1 except that the layers were heated to 40 ° C.

If the colored resin film-laminated metal plate thus obtained was observed with the naked eye, no underlying metal substrate was observed, indicating good concealment.

Also, a beautiful glossy appearance was obtained.

[2] A metal plate obtained by laminating a two-layer film consisting of an upper layer of a resin film containing no colored pigment and a lower layer of the colored resin film of 3)

As the resin used in the colored resin film serving as the ID underlayer, using terephthalic acid 8 0 mol% and isophthalic acid 2 0 mole ^_0/0 port Riesuteru resin acid and ethylene glycol were copolymerized consisting of twin-screw extruder The mixture is melt-blended with brown bengala using a polyethylene resin, and a separate twin-screw extruder is used to melt polyethylene terephthalate resin as the upper layer resin, and these two types of molten resin are continuously connected to a two-layer co-extrudable die. Typically

I Inject, extrude from the die nozzle so that the thickness of the brown colored resin layer as the lower layer is 20 m, and the thickness of the upper resin layer is 30 μππι. It was created.

The amount of bengara contained in the colored resin layer is such that the total light transmittance is 10 to 15% when the thickness of the colored resin layer is set to 20. Mixed.

The two layers of the colored resin film were applied to the same zinc-coated steel sheet as used in Example 1 so that the copolymerized polyester resin layer containing Bengala was in contact with the zinc-coated steel sheet. Were stacked in the same manner as in Example 1 except that the sample was heated to 240 ° C.

^ When the colored resin film-laminated metal plate thus obtained was observed with the naked eye, no underlying metal substrate was observed, showing good concealing properties. In addition, a beautiful appearance with a three-dimensional effect was obtained.

[3] 4) Metal plate laminated with a three-layer film consisting of an upper colored resin film, an intermediate layer, and a lower layer

As the resin used for the upper colored resin film, the same polyethylene terephthalate resin as in Example 1 was melt-mixed with blue cyanine blue using a twin-screw extruder, and the intermediate layer was formed using another twin-screw extruder. melting the same polyethylene terephthalate resin as in example 1 to be further by another twin-screw extruder, consisting of a lower layer to become tele phthalate 8 0 mole weight ^_0/0 and Isofutaru acid 2 0 mole ^_0/0 acid The polyester resin obtained by copolymerizing ethylene resin and ethylene glycol is melted, and these three types of molten resins are continuously fed into a co-extrudable die (D) to form a blue colored resin layer as an upper layer. Extruded from the die nozzle so that the thickness is 40 μπι, the thickness of the intermediate resin layer is 20 μππ, and the thickness of the lower resin layer is 1 μμπι, and the three layers are colored blue. Unstretched It created the Lum.

The amount of cyanine blue contained in the colored resin layer is such that the total light transmittance is 5 to 10% when the thickness of the colored resin layer is 40 μm, and the amount of cyanine blue is set in the polyethylene terephthalate resin. Mixed. The three layers of the colored resin film were applied to the same galvanized steel sheet as used in Example 1 while the lower layer of the copolymerized polyester resin was in contact with the galvanized steel sheet. Lamination was performed in the same manner as in Example 1 except that the layers were heated to 0 ° C.

_{> 0 When} the colored resin film-laminated metal plate thus obtained was observed with the naked eye, no underlying metal substrate was recognized, and good concealing properties were exhibited.

Also, a beautiful glossy appearance was obtained.

[4] 5) Metal plate laminated with a three-layer film consisting of an upper layer, an intermediate layer colored resin film, and a lower layer

, ^ Bisphenol A-polycarbonate resin is used as the upper layer resin, melted using a twin screw extruder, and used as the resin for the colored resin film as the intermediate layer. Using the same polyethylene terephthalate resin as in Example 1, using another twin-screw extruder, melt-mixing with white titanium white, and then using another twin-screw extruder, terephthalic acid as a lower layer of 80 mole weight melting the ^_0/0 and Isofutaru acid 2 0 mole ^_0/0 acid and Echire glycol polyester resin obtained by copolymerizing consisting, successively these three molten f resin together coextrudable die 3 layers The thickness of the upper resin layer is 30 μππ, the thickness of the white colored resin layer as the intermediate layer is 60 / m, and the thickness of the lower resin layer is 10 / m. It was extruded from a die nozzle so as to produce a three-layer unstretched film colored white.

The amount of titanium white to be contained in the colored resin layer is such that the thickness of the colored layer is 60 / xm.

The mixture was mixed in the polyethylene terephthalate resin so that the total light transmittance was 5 to 10% when I C was applied. The three layers of the colored resin film were applied to the same galvanized steel sheet as used in Example 1, and the lower layer of the copolyester resin layer was brought into contact with the galvanized steel sheet. The lamination was performed in the same manner as in Example 1 except that the layers were heated to ° C.

When the colored resin film-laminated metal plate thus obtained was observed with the naked eye, no underlying metal substrate was observed, indicating good concealing properties.

In addition, a beautiful appearance with a three-dimensional effect was obtained.

[5] 6) The metal plate laminated with a four-layer film consisting of an upper layer, upper intermediate layer, lower intermediate layer colored resin film, and lower layer

0 Using the bisphenol A _ polycarbonate resin as an upper layer and comprising a resin, melted with a twin-screw extruder, with another twin-screw extruder, polyethylene terephthalate 5 0 weight as the upper intermediate layer ⁰ /. And polybutylene terephthalate 5 0 wt ^_0/0 by melting the blended Poryesuteru resin, using a similar polyethylene terephthalate Ichito resin as in Example 1 as a tree fat used in the colored resin film comprising a lower intermediate layer, further another | using a twin-screw extruder f melt mixed with black carbon black, according to a further twin-screw press extruder, terephthalic acid 8 becomes lower 0 mole weight ⁰ /. And 20 mol of isophthalic acid. /. Melts a polyester resin obtained by copolymerizing acid and ethylene dalicol, and continuously feeds these four types of molten resin together into a four-layer co-extrudable die, and the thickness of the upper resin layer 10 m, the thickness of the upper intermediate resin layer is 30 // m, the thickness of the lower colored black resin layer is 20 // m, and the lower resin layer is It was extruded from a die nozzle so that the thickness If became 10 m, and four layers of unstretched film colored black were created.

The amount of carbon black contained in the colored resin layer is such that the total light transmittance is 10 to 15% when the thickness of the colored layer is 20 / in. Mixed.

ID The four layers of the colored resin film were applied to the same zinc-plated steel sheet as used in Example 1 so that the lower copolymerized polyester resin layer was in contact with the zinc-plated steel sheet. Lamination was carried out in the same manner as in Example 1 except that heating was performed at 240 ° C.

When the colored resin film-laminated metal plate thus obtained was observed with the naked eye, no underlying metal substrate was observed, and good concealing properties were exhibited.

ΙΙΓ In addition, a beautiful appearance with a three-dimensional effect was obtained.

[6] 7) A metal plate obtained by laminating a three-layer film consisting of an upper layer, an intermediate layer colored resin film, and a lower layer to which an anti-glare agent is added via an adhesive layer

Using bisphenol A-polycarbonate resin as the resin for the upper layer, melt-mixing silica powder with a particle size of 1 // m using a twin-screw extruder, and using it as a resin for the colored resin ₀ film as the intermediate layer Using the same polyethylene terephthalate resin as in Example 1, using another twin-screw extruder, melt-mixing with yellow titanium yellow, and further using another twin-screw extruder, terephthalic acid as a lower layer 80 mole weight ⁰ / ₀ and the acid and ethylene da recalled consisting of isophthalic acid 2 0 mole ^_0/0 melting a polyester resin obtained by copolymerizing these three molten resins together continuously to coextrudable die 3 layers (infeed, the thickness of the resin layer serving as the upper layer becomes 3 0 _M m, the thickness of the colored resin layer of yellow an intermediate layer 8 0 μ πα, the 1 0 mu m thickness of the lower layer becomes a resin layer Like die nozzle To produce a three-layer unstretched film colored yellow.

The amount of titanium yellow contained in the colored resin layer is such that the total light transmittance is 5 to 10% when the thickness of the colored resin layer is 80 μm. Mixed.

| r Next, an adhesive made of a thermosetting epoxy resin was applied to the surface of the copolymerized polyester resin as the lower layer of the three-layered colored resin film, and the same zinc plating as used in Example 1 was applied. The steel sheet was laminated in the same manner as in Example 1 except that the zinc-coated steel sheet was heated to 240 ° C. so that the lower copolymerized polyester resin layer was in contact with the galvanized steel sheet.

I When the colored resin film-laminated metal plate thus obtained was observed with the naked eye, it showed a soft appearance with suppressed surface gloss and no underlying metal substrate, showing good hiding properties. . Industrial applicability

^ The resin film of the present invention is a single-layer colored resin containing a color pigment in the resin film so that the total light transmittance represented by the formulas (1) to (3) is 20% or less. It is a film.

The resin film of the present invention has a resin layer for protecting the colored resin film, a resin layer for improving the adhesiveness of the colored resin film to a metal plate, and the like. Film.

The colored metal plate of the present invention is obtained by laminating these resin films. When these resin films are laminated on the metal plate, a beautiful appearance in which the underlying metal substrate is sufficiently concealed is obtained.

Claims

The scope of the claims

1. A colored resin film for laminating a metal plate, wherein a colored pigment is contained in a resin film such that the total light transmittance represented by the following formulas (1) to (3) is 20% or less.

Total light transmittance [%] = exp (a X (pigment concentration product) 1/2) X 100 (1) Pigment concentration product = pigment concentration [wt%] X resin film thickness [μm] (2) — 9≤ a≤—0.5 (a: unique value depending on pigment type) (3)

2. A colored resin film for laminating a metal plate, comprising a lower layer composed of a resin film containing no coloring pigment and an upper layer composed of the colored resin film according to claim 1.

3. A colored resin film for laminating a metal plate, comprising: an upper layer composed of a resin film containing no coloring pigment; and a lower layer composed of the colored resin film according to claim 1.

4. A colored resin film for laminating a metal plate, comprising a three-layered colored resin film of an upper layer, an intermediate layer, and a lower layer, wherein the upper layer is a layer composed of the colored resin film of claim 1. if

5. A colored resin film for laminating a metal plate, comprising a three-layered colored resin film of an upper layer, an intermediate layer, and a lower layer, wherein the intermediate layer is a layer composed of the colored resin film of claim 1.

6. A colored resin film for laminating a metal plate comprising four layers of an upper layer, an upper intermediate layer, a lower intermediate layer, and a lower layer, wherein the upper intermediate layer or the lower intermediate layer comprises the colored resin film according to claim 1. The layer is a colored resin film for metal plate lamination.

7. The colored resin film for laminating metal plates according to any one of claims 3, 5, or 6, wherein the uppermost layer comprises a resin film to which an anti-glare agent is added.

8. The colored resin film for laminating metal plates according to any one of claims 1 to 7, wherein the resin film is a polyester resin film.

9. A colored metal plate obtained by laminating the colored resin film for laminating a metal plate according to any one of claims 1 to 8 on at least one surface of the metal plate. 1 o. The colored metal plate according to any one of claims 1 to 8, wherein the colored metal plate is laminated with an adhesive layer interposed between the metal plate and the colored resin film for laminating a metal plate.