JPH11245332A - Polyvinyl chloride resin-coated metal plate and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyvinyl chloride resin-coated metal plate having a sense of a protrusion and recess state even in a thin film by simply and inexpensively forming a protrusion and recess pattern without using an engraved metal roll or the like by covering a surface layer of the plate with a polyvinyl chloride resin film containing a coarse particle polyvinyl chloride resin. SOLUTION: In the polyvinyl chloride resin-coated metal plate comprising a polyvinyl chloride resin film 3 having a protrusion and recess pattern on a surface layer of the surface-treated metal plate 1 via an adhesive layer 2, the film 3 contains one type or more of the polyvinyl chloride resin having a mean particle size of 1 to 10 μm, one type or more of a crosslinked coarse particle polyvinyl chloride resin having a mean particle size of 20 to 100 μm, and one type or more of a non-crosslinked coarse particle polyvinyl chloride resin having a mean particle size of 20 to 200 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal plate coated with polyvinyl chloride resin used for building materials, electric products and the like, and a method for producing the same. By being covered,
The present invention relates to a polyvinyl chloride resin-coated metal plate having an uneven pattern on the surface and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a polyvinyl chloride resin-coated metal sheet coated with a polyvinyl chloride resin has a design property by forming various patterns on the surface of the film, and is used mainly in the fields of building materials, home electric appliances and the like. Have been.

[0003] As a method of giving a design property to a polyvinyl chloride resin-coated metal plate, there are a method of forming a pattern by printing on the surface of a polyvinyl chloride resin film and imparting the design property, and various kinds of patterns. The engraved metal roll is pressed against the surface of the heated resin film and the engraved pattern is transferred to the film to impart a design, or the two methods are used in combination to impart the design. Used.

[0004] However, the method of imparting the design by printing increases the cost due to the addition of a printing step, and the method of imparting the design by a metal roll involves:
The production cost of the metal roll is high, and in order to transfer the pattern to the film, it is necessary that the film thickness is somewhat thick, which increases the film cost.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned drawbacks, and engraves a metal roll engraved by coating a surface of a metal plate with a polyvinyl chloride resin film containing coarse polyvinyl chloride resin. It is an object of the present invention to provide a polyvinyl chloride resin-coated metal sheet which can easily and inexpensively form an uneven pattern without using such a method and has an uneven feeling even when the film thickness is small, and a method for manufacturing the same.

[0006]

SUMMARY OF THE INVENTION The present invention is directed to a metal sheet coated with a polyvinyl chloride resin having a concavo-convex pattern excellent in design, workability, and economy by devising the constitution and manufacturing conditions of the polyvinyl chloride resin film. And a method for producing the same. That is, the polyvinyl chloride resin-coated metal plate of the present invention is a polyvinyl chloride-coated metal plate having a surface-treated metal plate having an uneven polyvinyl chloride resin film via an adhesive layer on a surface layer of the metal plate. The vinyl resin film is composed of at least one kind of polyvinyl chloride resin having an average particle diameter of 1 to 10 μm, and at least one kind of crosslinked coarse polyvinyl chloride resin having an average particle diameter of 20 to 100 μm, and having an average particle diameter of 20 to 2 μm.
00 μm uncrosslinked coarse polyvinyl chloride resin 1
It is characterized by containing more than one species. In this metal plate, the ratio of the coarse polyvinyl chloride resin crosslinked with the polyvinyl chloride resin in the polyvinyl chloride resin coating and the coarse polyvinyl chloride resin not crosslinked was an average particle diameter of 1 to 10.
μm polyvinyl chloride resin 10-90%, average particle size 20
~ 100 µm cross-linked coarse-grained polyvinyl chloride resin
Desirably, it is 85% and the non-crosslinked coarse polyvinyl chloride resin having an average particle diameter of 20 to 200 μm is 5 to 85%. Then, the maximum value x (μm) of the thickness of the convex portion of the uneven pattern satisfies the relationship represented by the following equation, and the minimum value y of the thickness of the concave portion is
(Μm) preferably satisfies the relationship represented by the following equation. 20 ≦ x ≦ 400... 0.10 ≦ y / x ≦ 0. 95 ... Further, the method for producing a polyvinyl chloride resin-coated metal sheet of the present invention is characterized in that the polyvinyl chloride resin 1 having an average particle size of 1 to 10 μm
10 to 90 parts by weight of seed or more and average particle size of 20 to 100 μm
5 to 8 of at least one kind of crosslinked coarse-grained polyvinyl chloride resin
5 parts by weight and 5 to 85 parts by weight of a non-crosslinked coarse-grained polyvinyl chloride resin having an average particle diameter of 20 to 200 μm, and a total of 100 parts by weight of a polyvinyl chloride resin mixture and a plasticizer of 10 to 100 parts by weight, A sol is manufactured by mixing and stirring 5 to 100 parts by weight of a diluent, and the sol is applied to the surface of a baked metal plate by applying an adhesive with an arbitrary coater, heated, and then cooled and solidified. I do.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The surface-treated metal plate used in the present invention may be Zn, Ni, Cr, Al, Cu, Sn alone or alloy plating, composite plating, chromate treatment, phosphate treatment or the like containing these metals. And those subjected to a coating-type chemical conversion treatment. Further, these surface treatments may be combined. Of course, the front and back of the metal plate may have different surface treatments.

Next, an adhesive is applied to the surface-treated metal plate before a polyvinyl chloride resin film containing coarse polyvinyl chloride resin is formed.

The adhesive used in the present invention is not particularly limited, but generally an acrylic or polyester adhesive is suitable.

A polyvinyl chloride resin film containing a coarse polyvinyl chloride resin is formed on the surface of the metal plate. The formation of the polyvinyl chloride resin film is performed by heating and cooling after applying the polyvinyl chloride sol.

The polyvinyl chloride sol is blended with an average particle size of 1
10 to 90 parts by weight of a polyvinyl chloride resin having a particle size of 10 to 10 μm, 5 to 85 parts by weight of a crosslinked coarse polyvinyl chloride resin having an average particle size of 20 to 100 μm, and a crosslinked polyvinyl resin 5 having an average particle size of 20 to 200 μm. -100 parts by weight of a polyvinyl chloride resin mixture, 10-100 parts by weight of a plasticizer, 5-100 parts by weight of a diluent, and other optional additives such as a coloring agent. No problem.

The method for producing a polyvinyl chloride resin having an average particle size of 1 to 10 μm is not particularly limited. When the average particle size is smaller than 1 μm, the sol viscosity increases, and the coatability is deteriorated. Unfavorably, when the average particle size is larger than 10 μm, it becomes difficult to form a sol. Further, the compounding amount is preferably 10 parts by weight to 95 parts by weight, and if it is less than 10 parts by weight, the flow characteristics of the sol deteriorate, and the coating property deteriorates. The proportions of the vinyl chloride resin and the coarse-grained acrylic resin are reduced, and the feeling of unevenness is poor, which is not preferable.

The method for producing a crosslinked coarse-grained polyvinyl chloride resin having an average particle size of 20 to 100 μm is not particularly limited. When the average particle size is smaller than 20 μm, the unevenness formed on the film surface becomes small, so that the unevenness is destroyed at the time of scratching and the like, and the scratch is easily made, and the fingerprint mark is easily left when touched by hand. It is not preferable. Also,
If the thickness exceeds 100 μm, the unevenness formed on the film surface becomes large, and the effect of lowering the gloss decreases, which is not preferable. The compounding amount is preferably 5 to 85 parts by weight,
If the amount is less than 5 parts by weight, the effect of lowering the gloss is lowered, which is not preferable. If the amount is more than 85 parts by weight, the total amount of the uncrosslinked coarse polyvinyl chloride resin exceeds 90 parts by weight, so that the flow characteristics of the sol deteriorate. Therefore, the coating property is deteriorated, which is not preferable.

The crosslinked coarse-grained polyvinyl chloride resin may be colored. When colored, a pattern pattern can be formed in addition to the concavo-convex pattern.

The method for producing a non-crosslinked coarse polyvinyl chloride resin having an average particle size of 20 to 200 μm is not particularly limited. If the average particle size is smaller than 20 μm, the unevenness of the coating surface becomes poor, which is not preferable. If the average particle size exceeds 200 μm, the coating becomes too thick and the coating cost increases, which is not preferable. The amount is 5
When the amount is less than 5 parts by weight, the unevenness is poor, and when the amount is more than 85 parts by weight, the total amount of the crosslinked coarse polyvinyl chloride resin exceeds 90 parts by weight. Because the flow characteristics deteriorate,
It is not preferable because the paintability deteriorates.

Further, the crosslinked coarse-grained polyvinyl chloride resin may be colored. When colored, a pattern pattern can be formed in addition to the concavo-convex pattern.

Examples of the plasticizer include phthalate esters such as di (2-ethylhexyl) phthalate (hereinafter abbreviated as "DOP") and dibutyl phthalate (hereinafter abbreviated as "DBP"), and dioctyl adipate (hereinafter referred to as "DOA"). Linear dibasic acid ester such as diisodecyl adipate (hereinafter abbreviated as "DIDA"), tricresyl phosphate (hereinafter abbreviated as "TCP"), cresyl diphenyl phosphate (hereinafter abbreviated as "CDP") If it is generally used as a plasticizer for polyvinyl chloride sol, it may be a phosphoric acid ester such as Trimellitic acid, or a trimellitic acid ester such as Trimethyl-2-ethylhexyl (hereinafter abbreviated as "TOTM"). No problem,
Two or more kinds may be used as a mixture. The compounding amount is preferably from 10 to 100 parts by weight, and if the amount is less than 10 parts by weight, the processability is deteriorated. If the amount is more than 100 parts by weight, the plasticizer may bleed to the surface of the film over time, which is not preferable.

The diluent is not particularly limited, and may be any diluent generally used as a diluent for polyvinyl chloride sol, such as ethyl cellosolve, naphtha, mineral spirit and the like. Also, two or more kinds may be used as a mixture. The compounding amount is preferably 5 to 100 parts by weight, and if it is 5 parts by weight or less, the heating residue after heating gelation becomes large and the feeling of unevenness is poor, and if it is 100 parts by weight or more, boiling of the diluent at the time of heating gelation occurs. This is not preferable because fine pores are formed in the film after gelation.

The coloring agent is not particularly limited as long as it is used as a coloring agent for the polyvinyl chloride sol, and comprises an inorganic or organic pigment and a dispersant. Examples of the inorganic pigment include titanium dioxide and titanium black. Organic pigments include phthalocyanine blue, dioxazine violet, and the like. Examples of the dispersant include plasticizers and the like generally used in polyvinyl chloride sols. The compounding amount is preferably 5 to 50 parts by weight. If the amount is less than 5 parts by weight, the concealing property of the film is inferior.
It is not preferable because it results in excessive blending and an increase in film cost.

The method of applying the polyvinyl chloride sol to the surface of the metal plate is not particularly limited, but a coating method using a roll coater, a curtain flow coater or the like generally used for coating a metal plate can be used. FIG. 2 shows a schematic diagram of a manufacturing process using a roll coater. After applying an adhesive to the surface of the metal plate 1 with an adhesive applying roll 5, baking is performed in a baking heating furnace 6, cooling is performed in a cooling device 7, and an adhesive layer 2 is formed. The polyvinyl chloride sol 8 containing the coarse-grain polyvinyl chloride resin 9 is applied by the roll 10. At this time, the gap between the sol coater roll 10 and the doctor roll 11 is
It is necessary to set the film after gelling so as to satisfy the formula and the conditions of the formula.
After heating at 200 to 220 ° C. at the reached plate temperature in 2 and gelling, the mixture is cooled by the cooling device 13 to produce a polyvinyl chloride resin-coated metal plate having an uneven pattern.

In the manufacturing process shown in FIG. 2, the roll coater constituted by the sol coater roll 10 and the doctor roll 11 can be changed to a curtain flow coater or another coating apparatus. Similarly to the roll coater, the gap between the sol coater roll 10 and the doctor roll 11 is adjusted so that the film after gelation satisfies the formula and the relationship of the formula. It is necessary to adjust the film after gelling so as to satisfy the formula and the relationship of the formula. In other coaters, it is necessary to set the coating conditions so that the film after gelation satisfies the formula and the conditions of the formula.

FIG. 1 shows a cross-sectional view of a polyvinyl chloride resin-coated metal plate produced by the above method. The polyvinyl chloride resin-coated metal plate having a concavo-convex pattern of the present invention satisfies the relationship where the maximum value x (μm) of the film thickness of the convex part of the concavo-convex pattern shown in FIG. Is required to satisfy the relationship represented by the equation.
In the formula, since the minimum value of the average particle size of the coarse-grained polyvinyl chloride resin to be blended is 20 μm, the minimum value of x is 20 μm, and the maximum value of the average particle size of the coarse-grained polyvinyl chloride resin is 200 μm. Therefore, the maximum value of x needs to be 400 μm in order to obtain a film having an uneven feeling satisfying the condition of the equation. The maximum value of x is 4
If it exceeds 00 μm, the coarse polyvinyl chloride resin having an average particle size of 200 μm is buried in the film, and it is not possible to obtain a surface having unevenness satisfying the condition of the formula.
In the formula, when y / x is smaller than 0.1, the convex portion formed of the coarse-grain polyvinyl chloride resin easily falls off the film, and when y / x is larger than 0.95, the feeling of unevenness is poor,
Unevenness equivalent to that of an uneven film transferred by a general engraved metal roll cannot be obtained, and the design is inferior.

The polyvinyl chloride resin-coated metal sheet of the present invention was evaluated for sol coating properties, unevenness, bendability, and adhesion to a coarse polyvinyl chloride resin film by the following methods. The ratio y / x of the maximum value x of the film thickness of the convex portions to the minimum value y of the film thickness of the concave portions, and the glossiness were measured. (1) Method of evaluating sol coating property The surface state of the polyvinyl chloride sol after coating was visually evaluated. (2) Evaluation method of feeling of unevenness The center line average roughness Ra of the film surface was measured and evaluated using a two-dimensional roughness meter. As the evaluation standard, the standard embossed polyvinyl chloride resin film on which the pattern of the metal roll obtained by engraving the grain pattern was transferred, having the lowest center line average roughness (Ra = 1.0 μm) was used as the standard. When the average roughness of the center line was more than this, the unevenness feeling was good, and when it was less than this, it was bad. (3) Method of evaluating bending workability A 90 ° bending test was used to visually evaluate film cracks in the processed portion. (4) Method of Evaluating Adhesion of Coarse-Grained Polyvinyl Chloride Resin to Coating The surface of the coating was scratched with coins, and the state of the projections of the surface irregularities of the coating was visually observed. (5) Method of measuring the ratio y / x of the maximum value x of the thickness of the convex portion of the uneven film and the minimum value y of the thickness of the concave portion The maximum value x of the film thickness of the convex portion of the uneven film is the thickness by a micrometer. It was determined by measurement. The minimum value y of the film thickness of the concave portion is
The maximum height Rmax was determined using a two-dimensional roughness meter, and the maximum height Rmax was determined by subtracting Rmax from x. The value of y / x was determined from the values of x and y determined by the above method. (6) Method of measuring glossiness The glossiness (60 ° gloss) was measured with a glossmeter.

[0024]

The present invention will be described below with reference to examples.

Examples 1 to 8 After a plating treatment, an adhesive was applied to the surface of a 0.5 mm thick mild steel sheet subjected to a chemical conversion treatment to a thickness of 5 μm (dry film thickness), and then baked in a gas oven at a sheet temperature of 220 ° C. After air cooling, a polyvinyl chloride sol having the composition shown in Tables 1 and 2 was applied using a roll coater, and then a sheet temperature of 20 was applied in a gas oven.
Heating was performed at 0 ° C. to 220 ° C., followed by cooling with water to produce a polyvinyl chloride resin-coated metal plate.

[0026]

[Table 1]

[0027]

[Table 2]

As shown in Table 3, Examples 1 to 8 of the present invention
The polyvinyl chloride resin-coated metal sheet was excellent in sol paintability, unevenness, and bending workability.

[0029]

[Table 3]

(Comparative Examples 1 to 4) After the plating treatment, the surface of a mild steel sheet having a thickness of 0.5 mm subjected to a chemical conversion treatment was coated with an adhesive of 5 μm.
(Dry film thickness) After applying, plate temperature 220 in gas oven
After baking at ℃ and air cooling, apply polyvinyl chloride sol of the composition shown in Tables 4 and 5 with a roll coater, then heat at 200 ° C to 220 ° C in a gas oven, and then water cool A metal plate coated with a polyvinyl chloride resin was produced.

[0031]

[Table 4]

[0032]

[Table 5]

As shown in Table 6, none of the polyvinyl chloride resin-coated metal plates of Comparative Examples 1 to 4 simultaneously satisfied the sol coating property, the feeling of unevenness, and the bending property.

[0034]

[Table 6]

[0035]

According to the present invention, the metal sheet coated with a polyvinyl chloride resin having a concavo-convex pattern is excellent in design and workability.
According to the production method of the present invention, an uneven pattern can be formed without using a metal roll or the like on which the pattern is engraved. Because it can give a feeling,
It is also economical and can be used as decorative steel for building materials and home appliances.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a polyvinyl chloride resin-coated metal plate of the present invention.

FIG. 2 is a schematic view of a process for producing a metal plate coated with a polyvinyl chloride resin according to the present invention.

[Explanation of symbols]

 Reference Signs List 1 metal plate, 2 adhesive layer, 3 polyvinyl chloride resin, 4 decoiler, 5 adhesive coating roll, 6 baking heating furnace, 7 cooling device, 8 polyvinyl chloride sol, 9 coarse-grain polyvinyl chloride resin, 10 sol coater roll , 11 doctor roll, 12 baking heating furnace, 13 cooling device, 14 coiler.

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshiyuki Sugimoto 1296, Higashi-Toyoi, Kudamatsu-shi, Yamaguchi Pref.

Claims (4)

[Claims] 1. A polyvinyl chloride resin-coated metal plate having a surface-treated metal plate having an uneven polyvinyl chloride resin film via an adhesive layer on the surface layer, wherein the polyvinyl chloride resin film has an average particle size. 1 to 10 μm of polyvinyl chloride resin and at least one kind of crosslinked coarse-grained polyvinyl chloride resin having an average particle size of 20 to 100 μm;
A metal sheet coated with a polyvinyl chloride resin, comprising at least one kind of coarse-grained polyvinyl chloride resin not crosslinked to a thickness of 200 μm. 2. The method according to claim 1, wherein the ratio of the coarse polyvinyl chloride resin crosslinked with the polyvinyl chloride resin and the non-crosslinked coarse polyvinyl chloride resin in the polyvinyl chloride resin film has an average particle diameter of 1 to 3.
10 to 90% of 10 μm polyvinyl chloride resin, 5 to 85% of crosslinked coarse polyvinyl chloride resin having an average particle size of 20 to 100 μm, and non-crosslinked coarse polyvinyl chloride resin 5 having an average particle size of 20 to 200 μm. The metal plate according to claim 1, wherein the content of the metal plate is about 85%. 3. The maximum value x (μm) of the thickness of the convex portion of the uneven pattern satisfies the relationship represented by the following equation, and the minimum value y of the film thickness of the concave portion:
3. The metal plate according to claim 1, wherein a ratio with respect to (μm) satisfies a relationship represented by the following expression. 20 ≦ x ≦ 400... 0.10 ≦ y / x ≦ 0. 95 ・ ・ ・ 4. An amount of at least one polyvinyl chloride resin having an average particle size of 1 to 10 μm in an amount of 10 to 90 parts by weight and an average particle size of 20 to 100
5 μm of at least 1 μm crosslinked coarse polyvinyl chloride resin
-85 parts by weight and 5-85 parts by weight of a non-crosslinked coarse-grained polyvinyl chloride resin having an average particle size of 20-200 μm, and a total of 100 parts by weight of a polyvinyl chloride resin mixture and 10-100 parts by weight of a plasticizer A sol is manufactured by mixing and stirring 5 to 100 parts by weight of a diluent, and the sol is applied to the surface of a baked metal plate by applying an adhesive with an arbitrary coater, heated, and then cooled and solidified. A method for producing a polyvinyl chloride resin-coated metal sheet.