JPH04141117A - New tableware and members thereof - Google Patents

Abstract

PURPOSE:To obtain a sufficient washing effect even with a little water due to an effecient washing effect and make it possible to provide various color patters on chinawares, by coating at least the inner face of table wares made of metal with a fluorine-bearing resin film. CONSTITUTION:A fluorine-bearing resin is a thermo-plastic resin including fluorine atoms in the molecular composition of the resin. Especially, tetrafluoroethylene resin is preferable like ethylene perfloro-alcoxiethylene-- tetrafluoroethylene copolymer (PFA) and ethylene-tetrafluoroethylene copolymer (ETFE). And fluorine-bearing fluoride resin film used for the inner wall layer is usually 5-200mu, preferably 10-100mu. Required patterns can be printed on the fluorine-bearing resin film. Any metals can be available for the metal plate. Especially aluminum plates and stainless plates are preferable. The thickness of metal plates is generally 0.1-2mm for instance, preferably 0.1-1mm.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to novel tableware and materials used therein, and more particularly to tableware coated on at least the inner surface with a fluororesin film and used therein. Materials.

[Conventional technology]

Traditionally, metal tableware such as aluminum and 3° stainless steel has been used for meals at home, outdoors, such as on hiking and camping trips, in hospitals, on ships, on trains, and in factories due to its durability, light weight, and ability to be sterilized at high temperatures. It has been widely used in restaurants such as σ restaurants. However, these metal utensils not only lacked color and did not stimulate the appetite, but also had unsatisfactory cleaning properties.

On the other hand, at home, with the increase in the number of housewives working, there is a need to reduce the amount of work required, and cleaning up after cooking is especially frowned upon.
There was a strong desire to make tableware easier to wash. or,
There is a need for something that has good vague cleanliness in automatic dishwashers. Also, when hiking or camping, there is often not enough washing water to keep dishes clean, and even if there is enough water, it often pollutes rivers, lakes, etc. and leads to environmental destruction. There is a strong demand. Also, hospitals,
In factories, it is required that large quantities of tableware be washed by a small number of people in a short period of time, and there is an extremely strong demand for tableware that is easy to clean. In addition, in order to reduce the weight of aircraft, ships, trains, etc., there has been a demand for tableware that can be washed with a small amount of washing water.

In order to improve these cleaning properties, a powder coating of fluororesin has been used for tin products. However, this method is prone to pinholes and requires a thick coating, which not only requires a large amount of expensive fluororesin but also impairs the smoothness of the surface. Currently, it is not possible to simply wash items stuck in the hollow with running water. Furthermore, although these coatings can be colored, they are not only less vivid, but also difficult to add designs and the like.

[Problems to be solved by the present invention]

The purpose of the present invention is to solve the above-mentioned problems that the prior art had, and to provide a novel metal tableware that is highly decorative and has excellent cleaning properties, and its use therein. The purpose is to provide materials for

[Means for solving problems]

The present invention has been made to solve the above-mentioned problems, and provides a novel metal tableware characterized in that at least the inner wall layer of the tableware is mainly composed of a fluororesin film.

The configuration of the present invention will be explained in more detail below.

The term "fluorine-containing resin" as used in the present invention is not particularly regulated as long as it is a thermoplastic resin containing a fluorine atom in the molecular structure of the resin, but generally, the molecular structure of the resin is Tetrafluoroethylene resins having four fluorine atoms in them, trifluoroethylene resins, difluoroethylene resins, -fluoroethylene resins, copolymers of these resins, and mixtures, etc. Of these, tetrafluoroethylene resins and difluoroethylene resins are preferred, and tetrafluoroethylene resins are more preferred. Here, the tetrafluoroethylene resin specifically refers to, for example, tetrafluoroethylene resin (PTFE), tetrafluoroethylene/perfluoroalkoxyethylene copolymer (PFA),
), tetrafluoroethylene/hexafluoropropylene bar 70
There are alkoxyethylene copolymers (EPE) and tetrafluoroethylene/ethylene copolymers (ETFE), etc.
Among them, PFA and ETFE are preferable, and PFA is particularly preferable. Further, the trifluoroethylene resin mentioned above specifically refers to, for example, trifluorochloride ethylene resin (PCTFE).
) and trifluorochloroethylene/ethylene copolymer (E
CTFE) etc. Specifically, the difluoroethylene-based and -fluoroethylene-based resins include, for example, vinylidene fluoride resin (PVDF) and vinyl fluoride resin (P
VF).

Furthermore, it goes without saying that the fluororesin film used for the inner wall layer in the present invention should not have any damage such as pinholes, but should also completely cover the metal plate that will become the outer wall layer. The film thickness may be any value, but is generally 5 to 200 microns, preferably 10 to 100 microns.

These fluororesin films can be produced by conventional methods, for example, by hot melt extrusion and casting, and if necessary, pigments and dyes can be added. Compounding and coloring, inorganic fillers such as glass powder, glass beads, glass fiber, etc.
By incorporating aluminum butyride, talc, mica, and silica, film strength can be improved. It is also possible to print desired designs. Furthermore, the "metal plate" as used in the present invention is not particularly limited and can be any metal, but generally includes iron-based, aluminum-based, copper-based metal plates, etc. , especially iron-based 7/
1. Miniram metal plates are preferred, and aluminum metal plates are particularly preferred. The above-mentioned iron-based metal plate may be any metal plate that mainly contains iron in its composition, and specifically includes, for example, a cold rolled steel plate, a galvanized steel plate, and a zinc alloy plated steel plate. , aluminum plated steel plate, copper plated steel plate, stainless steel plate, phosphate treated steel plate, aluminum-zinc alloy plated steel plate, etc. Among them, stainless steel plate is preferable.

Further, the aluminum-based metal plate may be any metal as long as it contains mainly aluminum metal in its composition, but generally, for example, on September 30, 1981, ) Aluminum plate described in pages 13 to 22 of "Aluminum Handbook (2nd edition)" published by the Light Metals Association, specifically, pure aluminum, (AI-C
u) system, (AI-Mn) system, (AI-Si) system, (Al
-Mg) system, (AI-Mg-5i) system and (A
There are I-Zn-Mg) type plates.

Further, the copper-based metal plate may be any metal as long as it mainly contains copper, but generally, for example, pure copper-based, brass-based, bronze-based, and brass-based metal plates are used. There are metal plates such as

The thickness of the metal plate in the present invention is generally, for example, 0
．． 1-2 m/m, preferably 0.2-Lm/m.

Depending on the design, line patterns, markings, or printing with heat-resistant ink can be used.

Next, it is desirable that the fluorine-containing resin film that will become the inner wall layer and the metal plate that will become the outer wall layer be joined and substantially integrated. As a joining method, there is mainly a method of bonding the film by heat fusion welding.

Films can be bonded by heat fusion welding using conventional methods, but generally, for example,
It can be obtained through processes such as a pretreatment process, a heating process, film lamination, a pressurizing process, a reheating process, and a cooling process. The above steps will be explained below.

(1) Pre-treatment step This step is performed as necessary to more strongly coat the metal plate and the fluorine-containing resin film.

■ Pre-treatment process of metal plates The purpose of pre-treatment of metal plates is to remove oily substances that adhere to the surface.
Cleaning and removing foreign substances, oxide films, etc., exposing bare metal to the surface by polishing, etc., surface plating,
Apply surface treatment such as acid treatment, and if necessary,
Add roughness to the surface, etc.

88 Surface cleaning There are no particular limitations, and cleaning methods conventionally used for specific metals may be used. For example, as a degreasing method,
Degrease and clean using organic solvents, alkaline aqueous solutions, surfactants, etc.

51 Surface Polishing The surface can be polished to expose the bare metal on the surface, for example, by mechanical and chemical polishing.

C1 Surface Treatment If necessary, chemical conversion treatments such as plating treatment, coating treatment for installing a metal oxide film layer, and antirust treatment can be performed on the surface covered with the film. For example, specific examples of chemical conversion treatments for iron-based metals include phosphate treatment with zinc phosphate, calcium phosphate, etc., and chromate treatment with reactive chromate, coating type chromate, and the like.

d) Surface Roughening The surface can be roughened by a surface roughening method using physical means such as brushing, sandblasting, and shotblasting, or by a surface roughening method using a chemical or electrochemical etching method or a combination thereof.

■ Film pre-treatment process Removing oily matter, foreign matter, etc. adhering to the film surface, applying an oxide film etc. by corona discharge treatment, straw material treatment, etc., and using various surface treatment agents. For example, treatments such as coating aminosilane, vinylsilane, mercaptosilane, etc. can be performed.

(2) Heating process This is a process in which the pretreated metal plate is heat treated in the air or in an atmosphere substantially free of oxygen, and if necessary, the film is also heat treated at the same time.

■ Heating atmosphere: air or, if oxidation is a concern, use an atmosphere that is substantially free of oxygen.

The above-mentioned "substantially oxygen-free atmosphere" means:
There are no particular restrictions on the atmosphere as long as it can be heated while substantially maintaining the surface condition of the metal plates and films that have undergone the pretreatment process, but specifically, the atmosphere is such that the oxygen content is 1% or less. It has a certain atmosphere. To create this heating atmosphere, it can be filled with an inert gas or heated in a vacuum state. Any type of inert gas may be used, but in general, nitrogen gas, argon gas, neon gas, helium gas, etc. are used, among which nitrogen gas,
Argon gas is preferred, and nitrogen gas is particularly preferred.

Further, the vacuum state is 5 Torr or less.

■Heating temperature The optimum heating temperature is determined depending on the type of fluororesin film and metal plate to be coated, but in general, the softening point temperature (mp) of the fluororesin film
Above, preferably (mp +30) 'C or higher, more preferably (mp +50) 'C or higher, and lower than the thermal decomposition temperature. Specifically, in the case of a fluorine-containing resin film, tetrafluoroethylene・For perfluoroalkoxyethylene copolymers, generally 280 to 400°C
, in the ethylene-tetrafluoroethylene copolymer,
Generally 260-370°C, for ethylene-chlorotrifluoroethylene copolymer, generally 220-350°C.
°C, and 250 to 300 °C for polyvinylidene fluoride.

(2) Heating time The heating time is not particularly specified; it must be the time required for at least the surface of the metal plate to reach the heating temperature, and is appropriately determined depending on the type and thickness of the metal plate.

(3) Lamination step This step is a step of covering a heated metal plate with a fluorine-containing resin film by lamination and pressing.

(2) Lamination Atmosphere The lamination atmosphere is not particularly limited, but it is preferable that the atmosphere be similar to that of the previous step, at least until the film is laminated and placed on the heated metal plate.

■ A film laminated and placed on a press-heated metal plate, for example,
This is a process of continuously pressing with a book roll or the like to strongly coat the material. Here, the roll in contact with the film is preferably a roll that does not stick to the film, such as a rubber roll or a metal roll, and the pressing force is 5 to 30 kg/an''.
Preferably it is 10-20 kg/cm2.

(4) Reheating process This process is a reheating process that is performed as necessary to further strengthen the fusion force between the metal plate and the film of the film-coated metal plate obtained in the previous process.

(2) Heating Atmosphere The heating atmosphere is not particularly limited, and may be in the air, but is preferably an atmosphere similar to that in the previous step (2).

■ Heating temperature The optimum heating temperature is determined as appropriate depending on the type of fluororesin film and metal plate to be coated, but generally it is higher than the softening point temperature (mp) of the fluororesin film, preferably (mp +20) 'C or higher, more preferably (mp +30) 'C or higher and lower than the thermal decomposition temperature. Specifically, in the case of a fluororesin film, tetrafluoroethylene perfluoroalkoxy For ethylene copolymers, generally 280 to 400°C,
For ethylene-tetrafluoroethylene copolymers, the temperature is generally 260 to 360°C, and for ethylene-chlorotrifluoroethylene copolymers, it is generally 220 to 350°C.
and 200 to 250°C for polyvinylidene fluoride.

■ Heating time The heating time is appropriately determined depending on the type and thickness of the film metal plate, but after reaching the desired temperature, it is generally 1 to 20 minutes, preferably 3 to 10 minutes, more preferably 5 minutes. ~7 minutes.

(5) Cooling Step This step is a step of cooling the reheated film-coated metal plate to room temperature, and can be cooled, for example, with an air cooling fan, water, or the like.

The film-coated metal plate of the present invention obtained through the above process heats the metal plate and the fluorine-containing resin film to fuse and bond the metal plate and the fluorine-containing resin film, so the metal plate and the fluorine-containing resin film have a strong fusion force. It is believed that this product will exhibit excellent processability and be usable for a long period of time.

The process of making tableware from the bonded body of the metal and fluorine-containing resin film obtained through the above steps includes conventional processes such as a cutting process, a tableware forming process, and, if necessary, a bonding process. There is.

The forming process of the fluororesin film laminated metal plate includes cutting into the desired shape (cutting process) by shearing, cutting (milling, sawing), etc., followed by bending, drawing, ironing, etc. After forming into a tableware shape using a method such as spatula drawing (tableware making process), it is joined by methods such as welding (arc welding, plasma welding, electron beam welding), brazing, soldering, riveting, etc. as necessary. Processing (joining process) can be performed.

The thus obtained tableware of the present invention has an inner wall layer that is a continuous, uniform layer of fluorine-containing resin film without any pinholes, so oil, sauce, pressure oil, fruit juice, etc. do not penetrate into the metal layer and it lasts for a long time. Not only is it durable, but its water-repellent and oil-repellent properties reduce the amount of adhesion and make it extremely easy to clean.It is also highly heat resistant and can be heated directly or cooked in a range or oven. Become.

In particular, the tableware of the present invention is suitable as tableware for group lunches such as school lunches. Further, the tableware of the present invention can be easily washed in an automatic dishwasher, and the tableware was not damaged even after being used several thousand times in a row.

Hereinafter, the present invention will be explained in more detail with reference to examples, but it goes without saying that the present invention should not be limited only to the examples.

Example 1 First, an aluminum plate of A 3004P-H34 (thickness 0.8 m) specified in JISH4000 was used as an aluminum base material, and the surface of the aluminum plate was sandblasted (using 80 meshes of reduced iron powder, After roughening the Ra (center line average roughness) to 1.8 μm using a 4% sodium chloride aqueous solution at a current density of 3.3 A/dnf, the Ra A rough surface of 3.5 μm was formed.

This aluminum plate was heated to a temperature of 350°C, and a 50 μm thick ethylenetetrafluoroethylene copolymer film (melt flow index 3) was formed on the rough surface.
0 m'' (7 seconds)) to obtain a fluororesin laminated aluminum plate having the same shape as shown in FIG.

The above-mentioned heat fusion bonding is carried out by applying a pressure of 15 kg to the heated metal plate and the above-mentioned film using a silicone roll having a diameter of 10 mm.
/cm condition.

A resin laminated aluminum plate formed as described above was obtained. The thus obtained resin-laminated aluminum plate was cut into a predetermined size, and a plate was formed using a press.

Example 2 Instead of the ethylene/tetrafluoroethylene copolymer film in Example 1, a film with a printed layer prepared as follows was used and heat fused so that the printed surface adhered to the metal surface. A resin-laminated aluminum plate was obtained and a plate was produced.

[Production method of printing film]

One side of a 40μ transparent film of tetrafluoroethylene/ethylene copolymer was subjected to surface treatment using a corona discharge device (Kasuga Denki type) under treatment conditions of discharge power 120W/rrr-min, and the surface of the film was was surface activated to a wettability index of 42 dyne, and printed on the transparent film made of ethylene-tetrafluoroethylene copolymer using the ink described below and a Tetron screen with an opening of 270 mesh. Heat this printed material to 120℃
The fluororesin layer is dried by heating for 10 minutes in a hot air circulation dryer, and the thickness of the thin film of the ink is 10 minutes.
A printed film was obtained in which a printed layer of μ was formed in close contact with each other.

(Production method of ink) A copolymer of tetrafluoroethylene, cyclohexyl vinyl ether, ethyl vinyl ether, and hydroxybutyl vinyl ether was obtained by a conventional method. In this copolymer, the molar ratio of each component is 50: 18: 22: 10 (according to the magnetic resonance method), and the intrinsic viscosity of the copolymer at 30°C in tetrahydrofuran is 0.4 d.
It was l/g. 100 g of this copolymer was dissolved in 80 g of carpitol acetate and 20 g of toluene, and 50 g of titanium oxide and 6 g of colloidal silica were added thereto and thoroughly mixed using a three-roll mill to obtain an ink composition. The viscosity of this composition was 270 ps, and the TI value was 5.

Example 3 An aluminum plate whose surface had been roughened by pretreatment as in Example 1 was printed using the ink described in Example 2 to obtain an aluminum plate having a printed layer. A transparent film (thickness: 60 μm) of perfluoroalkoxyethylene copolymer was similarly heat-sealed.

A tray was made using the obtained resin laminated aluminum plate.

Example 4 SUS specified in JIS G4304
The surface of the 304 (thickness, 0.1 m/m stainless alloy) plate was cut using a milling machine to which a circular metal plate with a diameter of 50+ na was fixed with sandpaper with a roughness of No. 200, and the rotation speed of the milling machine was 100 rpa+ and scribing. The marking process was performed at a speed of 100 cm/win.

The scribing depth of the obtained linear scribing pattern was 1 μ.

After degreasing the surface of the 5US304 plate with the above scribing process with a 1% caustic soda aqueous solution, the same thickness as in Example 1 was prepared.
A resin laminated metal was obtained by heat-sealing a 0μ ethylene-tetrafluoroethylene copolymer resin film.

The conditions for the heat fusion are as follows: After pressing the metal plate and the film, which have been preheated to 360°C, using a silicone roll with a diameter of 10 cm at a pressure of 150 kg,
Post-treatment is performed at 340°C for 10 minutes. A plate was produced using the obtained resin laminated stainless steel plate.

Example 5 A similar printed film was heat-sealed to the surface of Example 2 on which the resin was not laminated to obtain an aluminum plate laminated with a double-sided printed film. A bento box and a cup were made using the obtained resin laminated film.

Each of the products 1 to 5 of the present invention was tested for cleanability, corrosion resistance, design, and heat resistance, and each was evaluated according to the following criteria, and the evaluation results are shown in Table 1 below.

As is clear from the results shown in Table 1 below, the invention product 1
It was found that samples No. 5 to 5 were excellent in all physical properties.

Furthermore, although product 1 of the present invention was washed 3000 times in an automatic dishwasher, the dishes were not damaged.

Table-1 Performance evaluation * There were no pinholes in either case.

(Evaluation method) 1. Cleanability Method A: 1 cc of salad oil in which carbon is dispersed is spread on the tableware obtained in each example.

Then I wiped it off with tissue paper.

After that, check whether there is a pinhole or not and check with your finger. Confirmed that oil remained. The evaluation criteria is I did it as follows.

Oil does not stick to fingers O Oil slightly sticks to fingers △ Oil sticks to fingers × Method B: Rice and curry were rubbed on the tableware obtained in each example and dried. Then I wiped it off with tissue paper.

The evaluation criteria were as follows.

Easy to remove ○ Can be removed by rubbing Δ Cannot be removed without rubbing with force × 2. Corrosion resistance As a test to accelerate corrosion resistance, a container with a diameter of 5 cm and a depth of 2 cm was made using the fluororesin-coated plates obtained in each example. ,
3 cc of aqua regia was added and kept at 70°C for 3 days, and the amount of metal eluted into the aqua regia was measured by atomic absorption spectrometry.

3. Design Judging printed and engraved designs with the naked eye.

The evaluation criteria were as follows.

Visible clearly ○ Appears blurry △ Not visible
The sample was heated for an hour and then cooled to room temperature for 1 hour, and a 1O cycle was performed to observe changes in appearance.

No change O Changed It is highly resistant to corrosion, and allows for various ingenuity when designing, making it possible to create richly colored patterns on ceramics, etc., making it suitable for use in portable tableware, various vehicles, airplanes, etc., and tableware used in hospitals, factories, etc. It is suitable for

Claims (1)

[Claims] 1. A novel tableware made of metal whose at least the inner surface is coated with a fluororesin film. 2. The novel tableware according to claim 1, wherein the fluororesin film has a printed layer. 3. Patent claim No. 1 in which the fluororesin is a tetrafluoride resin
New tableware as described in section. 4. The novel tableware according to claim 3, wherein the tetrafluoride resin is a tetrafluoroethylene-ethylene copolymer (ETFE). 5. The novel tableware according to claim 3, wherein the tetrafluorinated resin is a tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer (PFA). 6. The novel tableware according to claim 1, wherein the film has a thickness of 5 to 200μ. 7. The novel tableware according to claim 1, wherein the metal is an aluminum metal plate. 8. The novel tableware according to claim 1, wherein the metal is a stainless steel metal. 9. The novel tableware according to claims 1, 7, and 8, wherein the metal plate has a thickness of 0.1 to 2 m/m. 10. Claim 1, wherein the tableware is a portable tableware.
- Novel tableware described in item 9. 11. A material used for tableware, which is a metal plate coated with a fluorine-containing resin film at least on the inner surface of the tableware.