JPH04133815A - New roof visor and side visor, and material used for them - Google Patents

Abstract

PURPOSE:To obtain a roof visor and a side visor having excellent washability, durability, and designing, and material used for those visors by providing a fluororesin coating layer on at least the outer surface of a metal-made main body. CONSTITUTION:A roof visor and a side visor are widely utilized for the purpose of preventing raindrops in an automobile, and material used for them has been thin plates of stainless, aluminum, and plastic moldings, etc., so far. However these moldings were not ones concurrently satisfying other functions, that is, washability, durability, and designing though satisfied a function to prevent raindrops. Coping with this, metal-made roof and side visors, using mainly fluororesin contained coating layer, are formed on at least an outer surface. In this case, a fluororesin film is used for a fluororesin contained coating layer, a printing layer is provided on the fluororesin film, and also resin tefrafluoride is used for fluororesin.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel roof visor, a side visor, and materials used therefor, and more particularly to a novel roof visor and side visor having a fluororesin coating layer, and materials used therefor. [Prior Art] Conventionally, roof visors and side visors have been widely used in automobiles for the purpose of protecting against raindrops, and until now, the materials used for these visors have been thin plates such as stainless steel, aluminum, and plastic moldings. However, although these products satisfy the function of preventing raindrops, they do not simultaneously satisfy the other functions of cleanability, durability, and design. For example, if we look at the metals stainless steel and aluminum, stainless steel has excellent durability, but aluminum is not good enough in terms of corrosion. Although it is possible to remove it, there is a problem with simple wiping. Furthermore, there was no design value other than the metallic color, and the limit of design was the extent to which an embossed pattern could be added. In the case of plastic, it is possible to freely select a color to match the color of the car body, but it is not possible to add coloring properties such as designs, and the durability and washability are not good at all. [Problems to be Solved by the Invention] An object of the present invention is to provide a roof visor, a side visor, and materials used therefor, which are rich in design as described above, which the prior art had. [Means for Solving the Problems] The present invention has been made to solve the above-mentioned problems, and provides a novel roof made of metal, characterized in that at least the outer surface mainly consists of a fluororesin-containing coating layer. It also provides visors and side visors. The configuration of the present invention will be explained in more detail below. "Fluorine-containing resin" as used in the present invention is not particularly regulated as long as it contains a fluorine atom in the molecular structure of the resin, but in general, Tetrafluoroethylene resins having four fluorine atoms, trifluoroethylene resins, difluoroethylene resins, -fluoroethylene resins, copolymers containing these resins as constituent units, and mixtures. Among 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 (P
FA), tetrafluoroethylene, hexafluoropropylene,
Perfluoroalkoxyethylene copolymer (EPE) and tetrafluoroethylene/ethylene copolymer (ETFE)
, tetrafluoroethylene, cyclohexyl vinyl ether, hydroxy vinyl ether copolymers, etc. Among them, ETFE. PFA is preferred. In addition, the above-mentioned trifluoroethylene resin specifically refers to, for example, trifluorochloride ethylene resin (
(PCTFE) and trifluorochloroethylene/ethylene copolymer (ECTFE), among others, PCTF
E is preferred. Specifically, the difluoroethylene-based and -fluoroethylene-based resins include, for example, vinylidene fluoride resin (PVDF) and vinyl fluoride resin (PVDF).
C). It goes without saying that the fluorine-containing resin layer used on the outer surface of the present invention is free from damage such as pinholes, but the method for forming this layer is coating with a fluororesin-containing solution, fluororesin dispersion, etc. Coating, powder coating of fluororesin fine powder, lamination of fluororesin film with adhesive, lamination of fluororesin film by heat fusion to metal, etc. Any method may be used, but it is suitable for workability and design. From this point of view, a film laminate system is preferable, and from the viewpoint of durability, a film lamination system by thermal fusion is more preferable. The layer thickness may be any thickness, but generally it is 10-2.
00μ, preferred (or 21)...100μ,, -ζ...
be,. For these, the manufacturing method of fluororesin/ilm is conventionally performed.
Then, if necessary, pigment,
Dye, 4-glass powder, glass resin, non-mechanical filler such as glass fiber, "aluminum" oxide, rum, talc, mica, silica, etc. are blended. - You can also print the desired design on the surface. Furthermore, the metal plate 1 referred to in the present invention is not particularly limited, and any metal plate can be used, but -
・For boat fishing, for example, iron-based, r-luminium-based 1, copper-based,
These are natan-based and 2...kel-based metal plates, and among them, iron-based, 7'ru, -, and ram-based metal plates are preferred.
The above-mentioned iron-based metal plate may be any metal plate as long as it has a composition of 11 (56 iron), and specifically, for example, a cold-rolled steel plate, a curved lead-plated steel plate, etc. , l ■ Lead alloy plated steel plate, Al1 aluminum plated steel plate, Copper Metsu 1 steel plate, Suge 1, What 2, ], Steel plate, Phosphoric acid treated steel plate and 1'
Rumi, “-Rum-” Jl! &') '8' Kinmetsu 1
“There are steel plates, etc., including hollow steel plates, zinc plated steel plates, 1II
Ii ('iρ, gold meso old steel analysis ξ1, doru 2-"2, umme y 4' lead steel plate, aluminum, -, um~ sacrificial lead alloy Messe steel plate & spoon l,... I like steel plates:'i
1. ,,stomach. "6. Said Al.]-1/, series metal plate and [7. Compositional A, - Mainly R2 Ram metal or saw (Sai1
It's like a metal plate, but A.1 metal plate - (1 is also good? - For boat fishing, for example, Showa B7 '1ε) Month 30
E3. It is a Y-luminium 9゜ plate, described on pages 1 to 22 of ``Norushi, Uno, Hunt'' Book (2nd edition) published by the Light Metals Association, Inc., and specifically, pure aluminum. 'Rumini, Um, (AICu) system, (AI-Mri) system,
(Al-: 悄) system, (AL-・Mg) system, (Al
-Mg-8i) system and (AI-Zn-Mg
) system board, etc. 1゜ book fi'l: clearly (, 'Rirukin ((1g of the board is not particularly prescribed 4 power ζt, but -
・For boat fishing (j, for example, 005--2m/m, preferably 5
, 01-=-1v'm'TF. Next, we will explain the heat-sealing lamination method that has the preferable J properties of the fluororesin layer. However, for boat fishing,
For example, pre-treatment step 11, heating step, "film lamination,"
It can be obtained by steps such as pressurization, reheating, cooling, and cooling. The above first step will be explained below. (1) Pretreatment 1', the culm process, consists of a metal plate and a fluorine-containing resin film.
In order to coat the surface more strongly, it is necessary to apply a soft coat (I9'j). ■Pre-treatment process of metal plate Cleaning and removing foreign substances, oxide films, etc., exposing the base metal to the surface by polishing, etc., performing surface treatments such as surface plating and acid treatment, and if necessary, The surface is roughened, etc. a. Surface cleaning is not particularly limited, and the cleaning method conventionally used for specific metals 7F is used, for example, the degreasing jj method. Degreasing 1 and cleaning 4 with organic solvents, nopalkaline aqueous solutions, surfactants, etc. Surface polishing 11 Surface polishing, for example, by mechanical and chemical polishing, etc.
, the bare metal can be exposed on the surface. Is surface treatment required i;::as required?], Meyer treatment, coating treatment to install a metal oxide film layer, chemical conversion treatment such as anti-corrosion treatment on the surface of Ilm 4 coating? 1°・To be able to do ζ・To be able to do 1, example λ
For example, specific examples of chemical conversion treatments for iron-based metals include adhesive treatment such as zinc phosphate, calcium phosphate, etc., and chromate treatment using reaction-type chromium-1 and coating-type chromate 1. d) Surface roughening methods such as physical steps such as brushing, pen/dblasting, and shot plus l-, or chemical and electrochemical etching methods. The surface can be roughened by a surface roughening method using a combination of these methods. ■ Film pre-treatment process Removal of oily matter, foreign matter, etc. adhering to the film surface, corona discharge treatment, straw material treatment In addition, it is possible to perform treatments such as applying an oxide film, etc., and applying various surface treatment agents, such as aminosilane, vinylsilane, mercaptosilane, etc. (2) Pretreatment for heating step This is a process of heat-treating the processed metal plate in the air or in an atmosphere substantially free of oxygen, and if necessary, a process of heat-treating the film at the same time. "Atmosphere in which oxygen does not exist" 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 for boat fishing, 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. In addition, the vacuum state is 5 Torr or less, preferably I
Torr or less. ■ Heating temperature The optimum heating temperature is determined depending on the type of fluorine-containing resin film and metal plate to be coated.
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, tetrafluoride For ethylene/perfluoroalkoxyethylene copolymer, -280 to 400℃ for boat fishing.
, in the ethylene-tetrafluoroethylene copolymer,
- 260-370°C for boat fishing, - 220-350°C for boat fishing for ethylene-chlorotrifluoroethylene copolymer
°C, and 250 to 300 °C for polyvinylidene fluoride. ■Heating time Heating time is not something that should be specified in particular, but it needs to be the time required for at least the surface of the metal plate to reach the heating temperature, and may be determined as appropriate depending on the type and thickness of the metal plate. , - 1-20 minutes for boat fishing, preferably 3-15 minutes
minutes, more preferably about 5 to 10 minutes. (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 preferably similar to that in the previous step (2). ■ 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/cm.
Preferably it is 10-20 kg/am'. (4) Reheating step This step is a reheating step that is performed as necessary to further strengthen the fusing force between the metal plate and the film of the film-coated metal plate obtained in the previous step. (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 appropriate heating temperature is determined depending on the type of fluorine-containing resin film and metal plate to be coated, but in general, the softening point of the 7-7-containing resin/film is 1 t. (m
p) or above, preferred)9. < is (mp +2O) ℃ or more,
Even better

[(rnp + 30) '(',: It is desirable that the temperature be above the thermal decomposition temperature or below (., <, Specifically, in the case of a fluorine-containing resin film, the tetrafluoride f- In general, 280 to 400°C, 21-
+ Difluoroethylene copolymer e is generally 26 (
)~360℃, Ejishiku/・-ri "j Lotriflu A Roenale:/ system copolymer, ~・generally 220...3
50℃ and 200-250℃ for polyvinylidene fluoride
etc. ■ Heating time The heating time does not have to be specified in particular; it must be at least enough time for the film to fully adapt to the metal plate, and is determined as appropriate depending on the type and thickness of the metal plate. is typically 1 to 20 minutes. (Re) Cooling process book] The culm is cooled to room temperature by cooling the reheated film-coated metal plate to room temperature. Since deformation occurs in the plate (uneven cooling), uniform cooling is desirable. In the film-coated metal plate of the present invention, the metal plate and the fluorine-containing resin film are heated 5 and fused and bonded 4 , so the metal plate and the fluorine-containing resin film have a strong fusion force. It is expected that the product will be able to be used for a long period of time. Below, 1. The process of adding the metal plate having the fluororesin-containing coating layer obtained by the method described above to the roof visor and guide visor includes the conventional cutting process and molding process. The R-method for forming a metal plate with a fluororesin-containing coating layer involves cutting it into the desired shape using methods such as a shearing saw and ink, and then bending, processing, etc. to form a roof visor. ,
Raise the soil to the side visor. In addition, since the roots visor/side visor of the present invention has a fluororesin-containing layer on at least its outer surface, it is excellent in cleaning, has good weather resistance and corrosion resistance, and is also resistant to discoloration. However, since it is also provided with printing m, it has an extremely rich design quality that could not be obtained in the past.
It is preferable to provide a printed layer as described in No. 73899 and Japanese Patent Application No. 1-139155. For example, as the printing layer of a Japanese patent application, 1...73 s 99, a fluororesin layer is formed by thermal fusion on the metal surface, and the top layer has a dixotrobi index (rl value) of 2.-・This is a printed layer formed by printing using an ink made of a fluororesin composition of No. 8, and is disclosed in Japanese Patent Application No.
As for the printing layer of No. 899, the fluororesin FILNO, which forms the printing layer on the metal surface, is the mark! With the 111th layer inside,
A preferred embodiment is a thermally fused printed layer. ζ is listed. 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] Previously, as an aluminum base material (T'X JISH40
A3004P~H34 specified in 00 (thickness 1cm) using a aluminum plate, the surface 48 of the aluminum plate
, sandblasting treatment (reduced iron powder 80 mesh), use 1
1,"',,-,l:L-7Pressure 3 kg/an
After roughening Ra (center line average roughness) to 18 μm (), the roughness was electrolytically etched in a 4% aqueous solution of hexatriunochloride at a current density of 3.3 A/a rrr.
3. This aluminum plate was heated to a temperature of 350°C to form a silk surface with a diameter of 35 μm.
, 50μrn thick ethylenetetra 5-
．． 7 J.
A fluororesin laminated aluminum plate was obtained. The above-mentioned thermal fusion bonding is performed by applying a pressure of 15 k to the heated metal plate and the above-mentioned film using a silicone roll with a diameter of 10 cm.
The test was carried out under the conditions of g/Cm. The resin-laminated aluminum plate formed as described above was obtained, cut into a predetermined shape, and then molded with a press so that the fluororesin surface was exposed to the outside to produce a roof visor. Example 2 One side of a 40μ transparent film of tetrafluoroethylene/ethylene copolymer was subjected to surface treatment using a corona discharge device (Kasuga Denki Gen) under the treatment conditions of discharge power 120W/i・min. The surface of the film was surface activated to a wettability index of 42 dyne, and the ink described below was used to form an aperture of 270 dynes.
Ethylene-
Printing was performed on the above transparent film made of a tetrafluoroethylene copolymer. This printed material was heat-dried for 10 minutes in a hot air circulation dryer at 120° C. to obtain a printed film in which a 10 μm thick printed layer made of a thin film of the ink was formed in close contact with the fluororesin layer. On the other hand, one side of a 1100 series aluminum rolled plate specified in JIS-H-4000 with a thickness of 0 and 6 mm was sandblasted to an average unevenness depth of 10 to 15E crons (surface roughness) and an uneven period of 10 to 20 microns. After that, the surfaces other than the above-mentioned one side are masked with vinyl chloride resin, and the above-mentioned sandblasted surface is electrolytically etched. This electrolytic etching treatment was carried out using a 3% NaCn aqueous solution at a temperature of 40°C, an electrolytic density of 4 amperes/dm, and a current flow of 35 coulombs/cm. After washing the etched surface with water and drying, the aluminum plate was was preheated to 310°C, the transparent film was placed on the etched surface, and the film was pressed with a pressure of 20 kg/cTll.
Subsequently, heat treatment was performed at 315°C for 10 minutes to thermally fuse the
A resin-coated metal plate of the present invention was obtained in which a fluororesin layer was formed on the aluminum plate, and the printed layer was laminated on the back side of the fluororesin layer. The obtained metal plate was cut into a predetermined shape and then molded using a press to produce a side visor. (Production method of ink) A copolymer of tetrafluoroethylene, cyclohexyl vinyl ether, ethyl vinyl ether, and hydroxybutyl vinyl ether was obtained by a conventional method. This copolymer has a molar ratio of each component of 50:22:10 (according to the magnetic resonance method), and a
The intrinsic viscosity of the copolymer at °C was 0.4 dl/g. 100 g of this copolymer was mixed with 80 carpitol acetate.
g, 50 g of titanium oxide dissolved in 20 g of toluene
6 g of colloidal silica was 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 Tr value was 5. Example 3 First, an aluminum plate of A 3004P-H34 (thickness 0.6 mm) specified in JISH4000 was used as an aluminum base material, and a current density of 3.3 A/drr? in a 4% sodium chloride aqueous solution was used. A rough surface with an Ra of 3.5 μm was formed by electrolytic etching under the following conditions. This surface was printed using the ink described in Example 2. This aluminum plate was heated to a temperature of 350°C, and a 50 μm thick ethylenetetrafluoroethylene copolymer film (melt flow index 30 m” 7 seconds) was heat-sealed on the printed surface to form a fluororesin lamination. An aluminum plate was obtained. The heat fusion bonding was performed by bonding the heated metal plate and the film together using a silicon roll with a diameter of 10 cm at a pressure of 15 k.
The test was conducted under the condition of g/cm. A roof visor was produced in the same manner as in Example 1 using the resin laminated aluminum plate formed as described above. Example 4 5US30 specified in JIS G4304
4. The surface of the (stainless alloy) plate was cut using a milling machine to which a circular metal plate with a diameter of 50 mm to which sandpaper with a roughness of No. 200 was attached was fixed, and the rotation speed of the milling machine was 1100 rpm and the scribing speed was ioam/min. I processed the brats. The scribing depth of the obtained linear scribing pattern was 1 μm. ”, add annotation 11->ノ', :, S U S
After degreasing the surface of the 304 board with a 1% Ih sodium aqueous solution, a 19-504 copolymer resin film was prepared in the same manner as in Example 7. A resin laminated metal is obtained by heat fusing (5), a roof visor is made, and a roof visor is produced. Using a silicone roll with a diameter of 10 cm, apply the heat to the above-mentioned metal plate with a force of 15 cm.
After pressurizing at 0 kg, post-treatment was performed at 340° C. for 10 minutes. Performance evaluations for each of Examples 1 to 4 are as follows: 1. The results are shown in entry-1 below. Leave it outside for a month. If it can be thoroughly wiped off with only a cloth soaked in some machine oil and then wiped off with a dry cloth, mark it as ○.
W S shown in Weather Resistance J Is A1415-1977
'! An accelerated exposure test was conducted for 5000 hours using M'J Sun Yain Carbon (manufactured by Suga Test Instruments), and the appearance was compared with the preserved test piece. 0 and L indicate cases where the appearance is almost the same as that of the preserved test piece, and × indicates a change of [1] and
(Also. 3 Processability test pieces were cut into 100 pieces by the cross-cutting method with a width of 1 w, and then cut into 100 pieces of J by an Erichsen testing machine (manufactured by Tokyo Shikenki Seisakusho, ESM No. 1). A steel ball is used to draw for 7 minutes.The test piece after this drawing is subjected to a cellophane tape peeling test.
I chose the one without peeling M. 4 Mark as ○ if the external printed design or scratched pattern is clearly visible.
Ta. It is clear from Entry 1 that the roof visor, which has a fluororesin-coated metal layer according to the present invention, has extremely excellent performance and excellent design. Special applicant F] Ippon Karubai

Claims (1)

[Scope of Claims] 1. A novel roof visor and side visor made of metal, characterized in that at least the outer surface mainly consists of a fluororesin-containing coating layer. 2. The novel roof visor and side visor according to claim 1, wherein the fluororesin-containing coating layer is a fluororesin film. 3. The roof visor and side visor according to claim 2, wherein the fluororesin film has a printed layer. 4. The novel roof visor and side visor according to claim 2, wherein the fluororesin is a tetrafluoride resin. 5. The novel roof visor and side visor according to claim 3, wherein the tetrafluorocarbon resin is an ethylene-tetrafluoroethylene copolymer. 6. The novel roof visor and side visor according to claim 1, wherein the fluororesin coating has a thickness of 10 to 200 μm. 7. The novel roof visor and side visor according to claim 1, wherein the metal is an aluminum metal. 8. The novel roof visor and side visor according to claim 1, wherein the metal is a stainless metal. 9. The novel roof visor and side visor according to claim 1, items 6 and 7, wherein the metal is plate-shaped with a thickness of 0.05 to 2 mm/m. 10. A material used for roof visors and side visors, characterized by having a coating layer mainly containing a fluororesin on at least the outer surface of the roof visor and side visors.