CN106232349B - Coated steel plate and its manufacturing method and cooking appliance component - Google Patents

Coated steel plate and its manufacturing method and cooking appliance component Download PDF

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Publication number
CN106232349B
CN106232349B CN201580017735.8A CN201580017735A CN106232349B CN 106232349 B CN106232349 B CN 106232349B CN 201580017735 A CN201580017735 A CN 201580017735A CN 106232349 B CN106232349 B CN 106232349B
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China
Prior art keywords
steel plate
film
coated steel
coating
silicone
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CN201580017735.8A
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Chinese (zh)
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CN106232349A (en
Inventor
大久保谦
大久保谦一
尾和克美
上田耕郎
上田耕一郎
今川清水
饭田健二
富田裕介
木场繁夫
友弘智
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chugoku Marine Paints Ltd
Mitsui Chemical Industry Co Ltd
Nippon Steel Nisshin Co Ltd
Original Assignee
Chugoku Marine Paints Ltd
Mitsui Chemical Industry Co Ltd
Nisshin Steel Co Ltd
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Publication of CN106232349A publication Critical patent/CN106232349A/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
    • A47J36/00—Parts, details or accessories of cooking-vessels
    • A47J36/02—Selection of specific materials, e.g. heavy bottoms with copper inlay or with insulating inlay
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/10—Metallic substrate based on Fe
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2518/00—Other type of polymers
    • B05D2518/10—Silicon-containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Food Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Cookers (AREA)

Abstract

Coated steel plate (10) of the invention is made up of successively overlapping steel plates (11) and upper painting film (14).Upper painting film (14) includes polyimides (141) and curing silicone (144).The occupied area rate of curing silicone (144) in the upper surface for applying film (14) is 5% or more.Both the heat resistance and soil resistance of coated steel plate (10) are excellent, are suitable for the materials'use as cooking appliance component.

Description

Coated steel plate and its manufacturing method and cooking appliance component
Technical field
The present invention relates to the excellent coated steel plate of heat resistance and soil resistance and its manufacturing method and include the coated steel plate Cooking appliance component.
Background technique
In recent years, it develops to the micro-wave oven for heating indoor supply vapor.Above-mentioned heating room is generally by with heat resistance And the coated steel plate of resistance to food pollution (hereinafter also referred to as " soil resistance ") is constituted.Above-mentioned coated steel plate is for example by metal plate, master The primary coat film and upper painting film to be made of polyether sulfone are sequentially overlapped according to this, and painting film contains tetrafluoro second on this Alkene perfluoroalkyl vinyl ether copolymer (PFA) and PFA is unevenly distributed on surface (for example, referring to patent document 1).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2005-262465 bulletin
Summary of the invention
Problems to be solved by the invention
Both the heat resistance and soil resistance of above-mentioned coated steel plate are excellent.But in recent years, exploitation and to the market supply The micro-wave oven that can be cooked with higher temperature.Therefore, to the coated steel plate for such cooking appliance, it is desirable that heat resistance It further increases.
The present invention is to complete in view of this, and its purpose is to provide with both better heat resistance and soil resistance Coated steel plate.
In addition, another object of the present invention is to provide the cooking appliance components comprising the coated steel plate.
Solution to problem
The inventors discovered that by combining specific silicone into polyimides, in the surface appropriateness of the film of polyimides Ground dispersion exposes silicone, and the film is used for the upper painting film of coated steel plate, make to apply on this film show soil resistance with And excellent heat resistance.And it further studies and completes the present invention.
That is, the present invention relates to coated steel plates below.
[1] a kind of coated steel plate has film on the steel plate, wherein the film includes upper painting film, and the upper painting applies Film contains polyimides and curing silicone, and the content of the curing silicone is 1~10 relative to polyimides described in 100 mass parts The occupied area rate of mass parts, the curing silicone in the upper surface for applying film is 5% or more, described upper to apply film Surface is the island phase island structure of marine facies and the curing silicone based on the polyimides.
[2] coated steel plate as described in [1], wherein it is described it is upper apply film in the curing silicone content relative to Polyimides described in 100 mass parts is 1~10 mass parts.
[3] coated steel plate as described in [1] or [2], wherein the curing silicone in the upper surface for applying film Occupied area rate is 5~70%.
[4] coated steel plate as described in any one of [1]~[3], wherein described in the upper surface for applying film Polyimides and the curing silicone become island structure.
[5] coated steel plate as described in [4], wherein the shape on the island of the curing silicone is that the ratio of major diameter and minor axis is 0.9~1.1 circle, the area on the island of each curing silicone are 300 μm2Below.
[6] a kind of coated steel plate has film on the steel plate, wherein the film includes upper painting film, and the upper painting applies Film contains polyimides and curing silicone, and the content of the curing silicone is 1~10 relative to polyimides described in 100 mass parts The occupied area rate of mass parts, the curing silicone in the upper surface for applying film is 5% or more, will be by based on complete When the infrared spectrum analysis of reflection infrared spectroscopy is measured the upper surface for applying film, 1014cm-1Peak value it is strong Degree is relative to 1375cm-1The ratio of peak strength be defined as A,
And by by the infrared spectrum analysis based on pellet technique to it is described it is upper apply film be measured when, 1014cm-1Peak strength relative to 1375cm-1The ratio of peak strength when being defined as B,
The A is 1.1~100 relative to the ratio of the B.
[7] coated steel plate as described in any one of [1]~[6], wherein the glass transition temperature of the polyimides Degree is 270~400 DEG C.
Moreover, it relates to the manufacturing method of coated steel plate below.
[8] a kind of manufacturing method of coated steel plate, comprising: coat coating, shape on the coating raw sheet comprising steel plate At the process of the layer of coating；And it is heated and is roasted in the coating original by the layer to the coating Plate, so that the process for applying film on being formed, the coating contain the presoma of polyimides, curability silicone, Yi Jirong Agent, the content of the curability silicone of the presoma relative to polyimides described in 100 mass parts in the coating More than 1.0 mass parts, since by the coating be coated on time of the coating raw sheet to ing until the heating be 5 ~70 seconds, so that the arrival temperature of the steel plate is 180 DEG C or more and reaches the arrival temperature from the heating is started Until time be 30~240 seconds modes, at least part of the curability silicone is floated on described on surface The layer for applying coating is heated, and the upper painting film is formed.
[9] manufacturing method of the coated steel plate as described in [8], wherein be coated on the coating from by the coating Time of the raw sheet until starting the heating is 5~60 seconds.
[10] manufacturing method of the coated steel plate as described in [8] or [9], wherein reached from the beginning heating described Time until reaching temperature is 30~240 seconds.
[11] manufacturing method of the coated steel plate as described in any one of [8]~[10], wherein the arrival of the steel plate Temperature is 200 DEG C or more.
[12] manufacturing method of the coated steel plate as described in any one of [8]~[11], wherein so that the upper painting applies The film thickness of film is that 2~20 μm of mode coats the coating.
[13] manufacturing method of the coated steel plate as described in any one of [8]~[12], wherein in the coating The curability silicone content relative to polyimides described in 100 mass parts presoma be 1~10 mass parts.
[14] manufacturing method of the coated steel plate as described in any one of [8]~[13], wherein the steel plate is in its table Face has chemical conversion treatment epithelium.
Also, the present invention relates to the cooking appliance components comprising above-mentioned coated steel plate.
Invention effect
Compared with the existing coated steel plate for exposing fluororesin, coated steel plate of the invention can embody higher heat-resisting Property, same or superior soil resistance.Coated steel plate of the invention is suitable for the cooking device used at relatively high temperatures as a result, The component of tool.
Detailed description of the invention
Fig. 1 is the figure for schematically showing the structure of coated steel plate of one embodiment of the present invention.
Fig. 2A is the figure for schematically showing the trend of the ingredient in the layer of coating, and Fig. 2 B is to schematically show admittedly SiClx ketone is dispersedly present in the figure of the state in the surface of the layer of coating, and Fig. 2 C is to schematically show curing silicone to exist The figure of the state of the surface aggregation of the layer of coating.
Fig. 3 A be the surface of the upper painting film in the coated steel plate 3 for indicate embodiment, shot by scanning electron microscope Backscattered electron image electron micrograph, Fig. 3 B be indicate curability silicone aggregation after upper painting film surface, By the electron micrograph of the backscattered electron image of scanning electron microscope shooting.
Fig. 4 is the figure for schematically showing the island structure applied in film and the fluid contaminants for being attached to the film.
Description of symbols
10 coated steel plates
11 steel plates
12 chemical conversion treatment epitheliums
13 primary coat films
14, film on 51
The layer of 31 coatings
131 resins
132 additives
141,513 polyimides
142 alumina particles
143 inorganic additives
144,512 curing silicone
311 solvents
312 curability silicone
514 pollutants
Specific embodiment
Coated steel plate of the invention has film on the steel plate.For film, as long as such as including aftermentioned upper painting film Film as most surface.Above-mentioned film for example also may further include steel plate surface formation primary coat film, Or the middle painting film formed on the surface of primary coat film.For example, as shown in Figure 1, coated steel plate 10 of the invention is by successively weighing Folded steel plate 11, chemical conversion treatment epithelium 12, primary coat film 13 and upper painting film 14 and constitute.Primary coat film 13 is mainly by resin 131 are constituted, can be as described later comprising additives 132 such as various pigment.As described later, upper painting film 14 is mainly by polyamides Imines 141 is constituted, and may include the additives such as alumina particles 142 or inorganic additive 143.In addition, upper painting film 14 includes at least The curing silicone 144 existing for its surface.
[steel plate]
Above-mentioned steel plate can suitably be selected from well known steel plate according to the purposes of coated steel plate or desired characteristic etc. It selects.It (is passed through after hot dip galvanizing as the example of steel plate, including galvanized steel plain sheet (plating Zn, hot dip galvanizing), alloy galvanized steel plate The alloyed hot-dip of Alloying Treatment plates Zn), galvanized alloy steel plate (hot dip galvanizing-Mg, hot dip galvanizing-Al-Mg, hot dip galvanizing- Al), hot dipping Al-plated steel sheet, hot-dip Al-Si steel plate, stainless-steel sheet and hot-dip Al stainless-steel sheet.From raising high temperature From the point of view of corrosion resistance viewpoint under environment, preferably hot dipping Al-plated steel sheet or hot-dip Al-Si steel plate, stainless-steel sheet, from into one From the viewpoint of step improves the reflectivity of corrosion resistance and microwave, preferred hot-dip Al stainless-steel sheet.
[chemical conversion treatment epithelium]
From the viewpoint of the corrosion resistance and film adhesion for improving coated steel plate, steel plate also can have chemical conversion Handle epithelium.Chemical conversion treatment epithelium is the thin layer formed by the matrix processing of coating.Example as chemical conversion treatment Son, including chromic acid salt treatment, chromium-free treatment and phosphate treated.The adhesion amount of chemical conversion treatment epithelium can be effective It is suitably determined in the range of raising corrosion resistance and film adhesion.For example, the adhesion amount of chromate epithelium is to change full Cr Calculation adhesion amount is 5~100mg/m2Amount.In addition, the adhesion amount of Chrome-free epithelium, such as Ti-Mo composite film is to make full Ti and Mo Conversion adhesion amount is 10~500mg/m2Amount, the adhesion amount of fluoracid system epithelium is that fluorine is made to convert adhesion amount or total metallic element Conversion adhesion amount is 3~100mg/m2Amount.Also, the adhesion amount of phosphate coating is to make phosphorus conversion 0.1~5g/ of adhesion amount m2Amount.
Chemical conversion treatment epithelium can be formed by well known method.For example, chemical conversion treatment solution is passed through roller coating The methods of method, spin-coating method, stick coating method, spray coating method are coated on the surface of steel plate, make it dry without washing.For dry Dry temperature and drying time are not particularly limited as long as moisture can be made to evaporate.From the viewpoint of productivity, preferably Drying temperature is with the arrival temperature of steel plate for 60~150 DEG C, and preferably drying time is 2~10 seconds.
[primary coat film]
From the viewpoint of the corrosion resistance and film adhesion for improving coated steel plate, coated steel plate can also be in steel plate table Further there is primary coat film on face or the surface of chemical conversion treatment epithelium.In general, primary coat film contain based on tree Rouge and rust resisting pigment.The resin of primary coat film can be identical as resins on basis of other films such as upper painting films, can also With difference.The example of the type of resin as primary coat film, comprising: polyester resin, epoxy resin, acrylic resin, benzene oxygen The inorganic resins such as resin and silicate resin.The example of type as above-mentioned rust resisting pigment, including magnesium phosphate, basic zirconium phosphate, Trbasic zinc phosphate, aluminium triphosphate, phosphomolybdic acid zinc, barium metaborate and silica based compound.
Primary coat film can also further contain other compositions.For example, primary coat film can also be containing to above-mentioned organic tree The crosslinking agent that rouge is crosslinked.The example of type as crosslinking agent, comprising: melamine resin and isocyanate resin.Separately Outside, primary coat film can also further contain coloring pigment, metallic pigments or filler pigment.As the example of coloring pigment, packet It includes: titanium dioxide, carbon black, chromium oxide, iron oxide, colcother, titan yellow, cobalt blue, cobalt green, nigrosine and phthalocyanine blue.As metal face The example of material, comprising: aluminium flake (non-floating type), latten(-tin), copper sheet, stainless steel substrates and nickel sheet.As the example of filler pigment, including Barium sulfate, silica and calcium carbonate.
Also, primary coat film can also contain pigment dispersing agent.Example as pigment dispersing agent, comprising: unsaturated carboxylic The solution (solvent is, for example, alkylbenzene/ethylene glycol monobutyl ether=5/1) of polyaminoamide of acid, polyether ester acid amine salt, with And low molecular weight polycaprolactone ester compounds.
The film thickness of primary coat film is, for example, 0.5~30 μm.
[above film]
The upper surface for applying film and constituting coated steel plate.Upper painting film contains polyimides and curing silicone.
[polyimides]
Above-mentioned polyimides can be one kind be also possible to it is two or more.Film strength is applied from raising heat resistance and upper painting From the point of view of viewpoint, preferably the polyimides contains aromatic group in main chain.From the viewpoint of heat resistance and cementability, lead to Often, the glass transition temperature (Tg) of above-mentioned polyimides is preferably 270~400 DEG C, and more preferably 300~380 DEG C, further Preferably 320~360 DEG C.The Tg of above-mentioned polyimides can be measured using measurement of dynamic viscoelasticity device.
Polyimides by being mixed to get the reaction product (forerunner of polyimides for diamines and tetracarboxylic dianhydride in a solvent Body), and the reaction product is solidified and is obtained.The combination or containing ratio of used diamines and tetracarboxylic dianhydride can be passed through Deng being designed to the glass transition point (Tg) of above-mentioned polyimides.For example, being 270~400 DEG C as being suitable for preparing Tg The example of the diamines of polyimides, comprising: amino as 4,4 '-oxygroup diaminobenzenes (4,4 '-diamino-diphenyl ether) exists The diamines of contraposition or 1,3- bis- (3- amino-benzene oxygen) benzene, 4, amino as 4 '-bis- (3- amino-benzene oxygen) biphenyl is in meta position Diamines.In particular, 4 '-is bis- it is preferred that above-mentioned diamines includes 4,4 '-oxygroup diaminobenzenes (4,4 '-diamino-diphenyl ether) or 4 (3- amino-benzene oxygen) biphenyl.The example of tetracarboxylic dianhydride as the polyimides for being suitable for preparing above-mentioned Tg, comprising: equal benzene four Acid anhydrides (1,2,4,5- benzene tertacarbonic acid's dianhydride), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides and 3,3 ', 4,4 '-biphenyltetracarboxyacid acids Dianhydride.Wherein, preferably above-mentioned tetracarboxylic dianhydride includes 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides.
[curing silicone]
The cured silicone such as heating when curing silicone is by the upper roasting for applying film.Curing silicone can be by rear The heat cure etc. for the curability silicone stated obtains.
If it is upper apply film in curing silicone content it is very few, sometimes be located at it is upper apply film surface curing silicone by In coated steel plate reuse and scraped by relatively early.Therefore, it is difficult to keep long-term soil resistance sometimes.If in upper painting film The content of curing silicone is excessive, then contains uncured silicone in curing silicone sometimes.Therefore, sometimes on the upper surface for applying film Generate viscous, the processability of coated steel plate is reduced since this is viscous.If also, the upper content mistake for applying the curing silicone in film It is more, then since polyimides is different from the linear expansion coefficient at a high temperature of curing silicone, thus the upper solidification applied in film sometimes The adhesion of silicone is insufficient, and curing silicone is peeled off from upper painting film.Therefore, the soil resistance of coated steel plate is insufficient sometimes.From From the viewpoint of in this way, the preferably upper content for applying the curing silicone in film is 1~10 matter relative to 100 mass parts of polyimides Measure part, more preferably 2~6 mass parts.
In the range of can be realized effect of the invention, upper painting film can also further contain other compositions.As The example of other compositions, including alumina particles, above-mentioned coloring pigment, pigment dispersing agent and inorganic additive.
Alumina particles are mixed into coating in order to assign design (metal sense) to upper painting film.It is not specially limited The purity of aluminium in alumina particles.For example, alumina particles can be only made of aluminium, can also be made of acieral.As alumina particles Shape example, including flakey (flake), granular, plate and bulk.From the viewpoint for assigning metal sense to upper painting film From the point of view of, preferably the shape of alumina particles is flakey.The content of alumina particles in upper painting film is for example relative to 100 matter of polyimides Amount part is 0.1~50 mass parts.
In order to improve the upper hardness and wearability for applying film, inorganic additive can also be mixed in coating.As The flakeys such as the example of inorganic additive, including glass flake, graphite flake, synthetic mica thin slice, silica thin slice are inorganic Additive；And potassium titanate fibre, wollastonite fibre, silicon carbide fibre, alumina fibre, aluminosilicate fibre, silica The inorfils such as fiber, asbestos, mineral wool, glass fibre, carbon fiber.
The film thickness for applying film is not specially limited, if but upper painting film is excessively thin, the heat resistance of coated steel plate sometimes And soil resistance is insufficient, if blocked up, although heat resistance and soil resistance can fully be obtained, sometimes from the upper of manufacturing cost Rise or other reasons such as the reduction of the processability of coated steel plate from the viewpoint of, be undesirable.From this point of view, excellent Choosing and applying the film thickness of film is 2~20 μm, more preferably 3~15 μm, further preferably 5~10 μm.
The occupied area rate of curing silicone in the upper surface for applying film is 5% or more.If above-mentioned occupied area rate is less than 5%, then anti-fouling effect as aftermentioned lotus-effect is insufficient sometimes.If above-mentioned occupied area rate is excessive, as described above, Since polyimides is different from the linear expansion coefficient at a high temperature of curing silicone, so that curing silicone is shelled from upper painting film sometimes It falls, the soil resistance of coated steel plate is less abundant.From this point of view, preferably above-mentioned occupied area rate is 5~70%.
Additionally, it is preferred that the upper surface for applying film includes the island structure based on polyimides and curing silicone.In addition, " sea " Refer to the continuous phase in the surface for applying film, " island " refers to the dispersed phase in the surface for applying film.Polyimides both can be with Be above-mentioned island structure " sea ", be also possible on " island ", curing silicone either above-mentioned island structure " island ", be also possible to " sea ".From the viewpoint of the excessive caused viscous reduction of processability of generation and coated steel plate of content for preventing curing silicone etc. From the point of view of, in preferably above-mentioned island structure, polyimides is " sea ", and curing silicone is the island structure on " island ".
Also, from the point of view, more preferably above-mentioned island is roughly circular, and the area on each island is 300 μm2With Under.About the shape on island, " roughly circular " refers to that the ratio of major diameter and minor axis is 0.9~1.1.Ratio about generally circular island Example, if the shape on island with above-mentioned " roughly circular " representative, for example, 80% or more of whole islands meet it is above-mentioned substantially Circle.
It is upper apply film surface in curing silicone configuration can by it is as shown in Figure 3A, use scanning electron microscopy The backscattered electron image that mirror (SEM) obtains is confirmed.Above-mentioned occupied area rate, the shape on island and the area on island can pass through the back The image procossing of scattered electron picture acquires.
In addition, preferably aftermentioned A is 1.1~100 relative to the ratio (A/B) of aftermentioned B in upper painting film.Here, " A " refers to, By red based on ATR method (ATR method: Attenuated Total Reflection Method, In situ ATR-FTIR method) When external spectrum analysis is measured the upper surface for applying film, 1014cm-1Peak strength relative to 1375cm-1Peak value The ratio of intensity.In addition, " B " refers to, upper painting is applied by the infrared spectrum analysis based on KBr method (KBr method: pellet technique) When film is measured, 1014cm-1Peak strength relative to 1375cm-1Peak strength ratio.No matter for above-mentioned A also It is above-mentioned B, 1014cm-1Peak strength all derive from silicon atom (Si-O-Si), the curing silicone applied in expression in film is deposited It is measuring.In addition, 1375cm-1Peak strength derive from nitrogen-atoms (C-N), the presence of the polyimides in film is applied in expression Amount.
Above-mentioned peak strength can be surveyed by infrared spectroscopy, such as FT-IR of detection peak strength It is fixed.In addition, as it is well known, ATR method is the method for carrying out the infrared spectrum analysis on surface.As it is well known, KBr method is The sample of above-mentioned slice is clamped as sample by the tablet of the evenly dispersed KBr for having the upper slice for applying film or using the plate of KBr, Method to carry out infrared spectrum analysis.For the slice of the upper painting film in KBr method, can be used the upper painting film peeled, Or use 80% or the deeper part that upper painting film is applied to coating thickness from the scraping of its surface.It is being made alternatively, can be used Make the sample of the upper painting film in addition prepared when applying film.
The case where above-mentioned ratio A/B is less than 1.1 indicate, have also been uniformly dispersed curing silicone in the upper inside for applying film. If above-mentioned ratio A/B is less than 1.1 as a result, the amount of the curing silicone occurred sometimes on the upper surface for applying film is insufficient.Cause This, cannot fully obtain the soil resistance of coated steel plate sometimes.In addition, it is upper painting film inside existing for curing silicone amount compared with More, the upper adhesion for applying film reduces, and the upper film that applies peels off sometimes.On the other hand, upper to apply if above-mentioned ratio A/B is more than 100 The amount of curing silicone near the surface of film is more, generates sometimes and expands system by the line of polyimides under high temperature and curing silicone The reduction of number different caused, above-mentioned peelings and soil resistance.
From embody it is above-mentioned it is upper apply film film part peel off prevent with from the viewpoint of soil resistance the two, preferably Above-mentioned A is 0.1~1.0.If above-mentioned A is less than 0.1, soil resistance is insufficient sometimes.If above-mentioned A is more than 1.0, generate sometimes State the part peeling for applying film.For above-mentioned B, it is not particularly limited, but since curing silicone is usually applied in upper painting Its surface is non-uniformly distributed in film, therefore above-mentioned B is usually 0.01~0.09.
[manufacturing method of coated steel plate]
Above-mentioned coated steel plate can manufacture by the following method, this method comprises: first step, in the coating comprising steel plate Coating is coated on raw sheet, forms the layer of coating；And the second step, it is heated by the layer to coating, It is roasted in coating raw sheet, forms above-mentioned upper painting film.In the range of can be realized effect of the invention, the manufacturing method Also other processes be may further include.
[first step]
Coating raw sheet can be steel plate itself, be also possible to the steel plate with above-mentioned chemical conversion treatment epithelium, can also be with It is the steel plate with above-mentioned primary coat film.Primary coat film can be by being coated on steel plate or chemical conversion treatment skin for bottom-coating The surface of film, and roasted to make.
Bottom-coating for example can be by by materials such as the resin of above-mentioned primary coat film or its presoma, additive and molten Agent is mixed to prepare.
Above-mentioned solvent can be one kind be also possible to it is two or more.Example as solvent, comprising: N- methyl -2- pyrroles Alkanone (NMP) or n,N-Dimethylformamide (DMF), n,N-dimethylacetamide (DMAc), N, N- dimethyl-imidazolinone (DMI), the aprotic polar solvents such as hexone (MIBK)；Diethylene glycol dimethyl ether (DMDG) or diethyl carbitol (DEDG) ethers such as；The halogenated aliphatic hydrocarbons such as methylene chloride or carbon tetrachloride；The hydrocarbon such as dimethylbenzene；And alcohol.
Bottom-coating can be applied by method well known to rolling method, flow coat method, curtain stream method, stick coating method and spray coating method etc. It covers.For the maturing temperature of primary coat film, such as preferably make 150~400 DEG C of arrival temperature of temperature of steel plate, it is preferably above-mentioned Calcining time is 30~180 seconds.
Above-mentioned coating contains the presoma of polyimides, curability silicone and solvent.Coating can also be into one Step contains the other compositions such as above-mentioned alumina particles.The presoma of polyimides is made up of heating in the second step etc. The polymer for applying film, e.g. synthesizes the polymer of above-mentioned polyimides by hot closed loop or is dissolved in coating Polyimides etc..That is, the example of the presoma as polyimides, including polyamic acid and soluble polyimide.
Curability silicone is for example made of the silicone and functional group constituted with siloxanes component unit.The functional group passes through Heat, active energy beam, catalyst etc. are bonded to each other in conjunction with silicone or by functional group.Example as functional group, comprising: second Alkenyl or (methyl) acryloyl group etc. have the hydroxyls silicyls, methoxyl group such as group, the monohydroxy silicyl of carbon-carbon double bond The alkoxysilyls such as silicyl, hydroxyl, methanol-based, phenolic group, epoxy group, amino, isocyanate group.
For the molecular weight of above-mentioned curability silicone, if too small, there are the tendencies that the curability of silicone reduces, if mistake Greatly, it is likely that viscosity improves, and appears in being unable to fully on the surface for applying film.From this point of view, on preferably The quantity for stating the siloxanes component unit in curability silicone is 2~5000, more preferably 10~2000.Above-mentioned component unit Quantity can be measured by gel permeation chromatography (GPC).
In addition, the equivalent (g/mol) of the above-mentioned functional group in preferred consolidation silicone is 2 from the viewpoint of reactivity ~60000, more preferably 10~30000.The equivalent of above-mentioned functional group can for example be surveyed by nuclear magnetic resonance optical spectroscopy (NMR) It is fixed.
Example as the example of curability silicone, including various modified silicones, as the modified silicone, comprising: amino It is modified silicone, carbinol-modified silicone, acrylic modified silicone, ethylene modified silicone, silanol-modified silicone, phenol-modified Silicone, epoxy-modified silicone, isocyanate group modified silicone, polyether modified silicone.From the point of long-term resistance to food pollution From the point of view of, particularly preferably polyether modified silicone.
Solvent can be one kind be also possible to it is two or more.From the presoma of polyimides and the intermiscibility of curability silicone Raising or the viewpoints such as the adjustment of viscosity of coating come using solvent.For the solvent of coating, can be used with it is upper State the identical solvent of solvent of bottom-coating.The solvent of coating can be one kind and be also possible to more than one, can be the bottom of with The solvent of painting coating is identical to be can also be different.Furthermore it is possible to by method identical with the coating method of bottom-coating, by upper painting Coating is coated on the surface of steel plate, chemical conversion treatment epithelium or primary coat film.
The above-mentioned curability silicone of the presoma relative to the above-mentioned polyimides of 100 mass parts in above-mentioned coating Content is 1.0 mass parts or more.If above-mentioned content less than 1.0 mass parts, above applies the curing silicone in the surface of film sometimes Occupied area rate less than 5%.As described above, from the reduction or upper painting film for preventing the soil resistance caused by reusing From the viewpoint of the reduction of soil resistance caused by part is peeled off, the content of the above-mentioned curability silicone preferably in coating is opposite In 100 mass parts polyimides presoma be 1~10 mass parts, more preferably 2~6 mass parts.
It is preferred that by coating by make it is upper apply 2~20 μm of film thickness of film in a manner of coated on steel plate, chemical conversion at Manage epithelium or primary coat film.The upper thickness for applying film can be adjusted by the thickness (coated weight of the coating) of the layer of coating It is whole.The thickness of the layer of coating can pass through the coating time of the viscosity of coating or the coating method of the coating, the coating The adjustment such as number.
[the second step]
In the second step, in the way of 180 DEG C of arrival temperature or more that make steel plate, at least one of curability silicone Divide the layer of the coating floated on surface to be heated, film is applied in formation.Here, " at least one of curability silicone Divide the layer of the coating floated on surface " refer to, the layer that a part of curability silicone is just occurring on its surface, this Outside, also a part including curability silicone gradually reaches its surface but and (is substantially believed that just in the layer of surface appearance In the layer that surface occurs).
In the case where curability silicone has Thermocurable, the forerunner of polyimides can be carried out by above-mentioned heating The solidification of the imidizate and curability silicone of body.In the case where curability silicone does not have above-mentioned Thermocurable, above-mentioned system It makes method also and may further include the process for making curability silicone cure.For example, there is photo-curable in curability silicone In the case of, it can be by carrying out above-mentioned heating process, furthermore further to the polyimide film irradiation light formed by the heating process And make curability silicone cure.Also, in the case where curability silicone has both Yin Re and light and cured property, on Stating manufacturing method can also further comprise making curability silicone to the upper surface irradiation for applying film after above-mentioned heating process The process of cured light.The curability silicone on the surface for applying film can in this case cured sufficiently, thus preferably.Make For the example of the light of irradiation, including ultraviolet light.
If above-mentioned arrival temperature is less than 180 DEG C, even if curability silicone has Thermocurable, the solidification of curability silicone Also insufficient, the sometimes upper film that applies shows viscous sense, and the processability of coated steel plate due to the uncured of curability silicone and It reduces.In addition, caused by generating the difference due to the linear expansion coefficient of polyimides and curability silicone under high temperature sometimes The reduction of peeling and soil resistance.If above-mentioned arrival temperature is 200 DEG C or more, from the presoma for promptly carrying out polyimides Polyimides from the viewpoint of, be preferred.
It is heated by the layer to above-mentioned coating so that it reaches above-mentioned arrival temperature or by behind into one Step includes the cured appropriate process for curability silicone, can suitably be gone out on the upper surface for applying film in curability silicone In the state of existing, the heat cure of the polyimides and curability silicone of the presoma of the polyimides in this layer is carried out, is formed Above-mentioned upper painting film.In this layer, curability silicone emersion amount can pass through the heating speed after the layer of formation coating Waiting time or above-mentioned arrival temperature before degree, heating are adjusted.That is, can both be heated on one side to the layer of coating Make curability silicone emersion on one side, can also make curability silicone after the abundant emersion of layer of coating to keep the state Mode heat rapidly.It is excellent from the viewpoint of the desired distribution for steadily realizing the curability silicone in painting film Select the latter.
In the former case, excellent from the viewpoint of the distribution of the curability silicone in the surface for applying film in control Selecting the time (heating time) for reaching above-mentioned arrival temperature from the temperature that coating is coated on coating raw sheet to steel plate is 30 ~240 seconds.If above-mentioned heating time, less than 30 seconds, the amount of the curability silicone occurred sometimes on the upper surface for applying film is not filled Point.If above-mentioned heating time is more than 240 seconds, the amount of the curability silicone occurred sometimes on the upper surface for applying film is excessive.From From the viewpoint of in this way, preferably above-mentioned heating time is 30~240 seconds.
In the latter case, since the time preferably coating is coated on coating raw sheet to heating (when waiting Between) it is 5~60 seconds.If the above-mentioned waiting time, less than 5 seconds, curability silicone can not be in the surface of the layer of coating sometimes Fully occur, the amount of the curability silicone of the inside of this layer is more.In this case, as described above, sometimes upper apply The adhesion of film reduces, and upper painting film peels off.If the above-mentioned waiting time is more than 60 seconds, the curability silicone of substantial full dose exists Occur in the surface of the layer of coating, is generated sometimes due to the linear expansion coefficient of polyimides and curing silicone under high temperature The reduction of peeling and soil resistance caused by different.The above-mentioned waiting time for example can by coating unit in coating and The conveying speed of steel plate between the heating device of steel plate is adjusted.
In addition, heating time in the latter case, reaching from the temperature after the above-mentioned waiting time to steel plate Time until above-mentioned arrival temperature is 30~180 seconds, this is preferred from the viewpoint of identical as the former heating time , more preferably 30~150 seconds.
Fig. 2A is the figure for schematically showing the trend of the ingredient in the layer of coating.As shown in Figure 2 A, it is applied in upper painting In the layer 31 of material, the solvent 311 indicated by white triangle (△) in Fig. 2A evaporates, being consolidated in Fig. 2A by what white circle (zero) indicated The property changed silicone 312 is mobile to the surface of this layer by the surface free energy difference with base resin (presoma of polyimides).This When be believed that the liquid particles of curability silicone are moved to the surface of this layer on one side on one side aggregation each other.
Fig. 2 B is be present in the state on the surface of layer of coating figure with schematically showing curability dispersion. As shown in Figure 2 B, can by the surface of the layer in coating occur curability silicone aforesaid liquid particle aggregation not When sufficiently carrying out, which is heated, makes its solidification, is produced on the upper painting film that its surface has subtle island structure, The island structure is dispersed with subtle island (island is curability silicone) (referring to Fig. 3 A).
Fig. 2 C is the figure for schematically showing state of the curability silicone after the surface aggregation of the layer of coating, Fig. 3 B It is backscattered electron image indicating the surface of the upper painting film after the aggregation of curability silicone, being shot by scanning electron microscope Electron micrograph.As shown in Figure 2 C, if making the aforesaid liquid of the curability silicone occurred on the surface of the layer of coating Particle is sufficiently assembled, then as shown in the photo of Fig. 3 B, can be produced on its surface with there are the island structures on bigger island Upper painting film.No matter the island in which kind of island structure, thickness is all thin to number 10nm degree.
The upper heat resistance for applying film is mainly brought by polyimides, and the soil resistance on the upper surface for applying film is mainly by solidification silicon Ketone is brought.To solidify silicon due to existing in the upper painting film formed by such as layer of Fig. 2 B or coating shown in fig. 2 C The island of ketone, so higher soil resistance can be embodied.
Fig. 4 is the figure for schematically showing the island structure applied in film and the fluid contaminants for being attached to the film. The upper film 51 that applies has the subtle island structure being made of the dispersed phase of the continuous phase of polyimides 513 and curing silicone 512.
As shown in figure 4, the pollutant 514 of liquid is attached to the surface for applying film 51.With the drop phase of pollutant 514 Than the island of the curing silicone 512 in island structure is sufficiently small.In addition, the island of the curing silicone 512 in the upper surface for applying film 51 Density it is sufficiently high.Therefore, the drop of pollutant 514 crosses over multiple islands, is attached to the surface for applying film 51.
Compared with as the polyimides 513 in sea, the surface tension of the curing silicone 512 as island is smaller, therefore pollutes Work of the drop of object 514 on the direction that the contact surface with the island island structure Zhong Ge is become larger by the contact angle with the contact surface With.Accordingly, it is believed that excellent liquid repellency is embodied on the upper surface for applying film 51, it is easy to remove the drop of pollutant 514, separately Outside, it is not easy when heated pollutant is cooked-on.
In this way, from the viewpoint of the contact relative to the drop of attachment, it is believed that above the anti-fouling effect of painting film 51 is By (in concave-convex subtle asperities, generating multiple gaps that liquid can not penetrate into, the apparent contact angle with liquid with lotus-effect The phenomenon that becoming larger) identical effect bring.
According to the above description, by being distributed in curing silicone steadily with the upper painting of the basic resin of polyimides The surface of film is capable of forming with excellent heat resistance and all has to hydrophily and lipophilic liquid component excellent The upper painting film of soil resistance.Especially from the viewpoint of the durability and uniformity for improving soil resistance, in the upper table for applying film Face building is more effective by the subtle island structure on island of curing silicone.
As described above, both heat resistance and soil resistance of coated steel plate of the invention are excellent.As a result, especially for antifouling Property, by using above-mentioned subtle island structure, thus the soil resistance more excellent relative to the dirty embodiment of liquid.It fits as a result, In as can in the utensil for cooking such as steam-heated micro-wave oven, for being constituted as the heating room of the micro-wave oven 350 DEG C or so at a temperature of using and generate drop attachment part component or its pre-coated steel plate come using.
Hereinafter, the present invention is described in detail referring to embodiment, but the present invention is not limited to these Examples.
[embodiment]
[preparation of polyimide precursor A~E]
In the delivery flask of 300mL, it is taken into as DMAc (n,N-dimethylacetamide) 120.3g of solvent and conduct Bis- (3- amino-benzene oxygen) benzene (Mitsui Chemicals, Inc's system) 23.0g (78.7mmol) of 1,3- of diamines simultaneously make it dissolve.? Wherein pyromellitic dianhydride (1,2,4,5- benzene tertacarbonic acid dianhydride) (Co., Ltd. Daicel system) of the addition as tetracarboxylic dianhydride 17.1g (78.3mmol) has obtained the varnish A containing polyimide precursor (polyamic acid) A.
DMAc138.3g has been used, and has used the 4 of 78.7mmol, 4 '-bis- (3- amino-benzene oxygen) biphenyl (Mitsui Chemicals Co. Ltd. system) it has been obtained in addition to this in method identical with varnish A containing the clear of polyimide precursor B as diamines Paint B.
DMAc103.1g has been used, has used 4,4 '-oxygroup diaminobenzenes (4,4 '-diamino hexichol according to molar ratio 9:1 Base ether) (Nippon Seika K.K.'s system) and (1,3- bis- (3- amino-benzene oxygen) benzene amount to 78.7mmol as diamines, and according to Molar ratio 9:1 has used pyromellitic dianhydride (1,2,4,5- benzene tertacarbonic acid's dianhydride) and 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides (Co., Ltd.'s Daicel system) amounts to 78.3mmol as tetracarboxylic dianhydride, in addition to this, obtains in method identical with varnish A Varnish C containing polyimide precursor C.
DMAc101.0g has been used, the 4 of 78.7mmol, 4 '-oxygroup diaminobenzenes (4,4 '-diamino-diphenyls have been used Ether) it is used as diamines, pyromellitic dianhydride (1,2,4,5- benzene tertacarbonic acid's dianhydride) and 3 have been used according to molar ratio 9:1,3 ', 4,4 '-two Benzophenonetetracarboxylic dianhydride (Co., Ltd.'s Daicel system) amount to 78.3mmol as tetracarboxylic dianhydride, in addition to this, with it is clear The identical method of paint A has obtained the varnish D containing polyimide precursor D.
DMAc98.7g has been used, the 4 of 78.7mmol have been used, 4 '-oxygroup diaminobenzenes are as diamines, in addition to this, with Method identical with varnish A has obtained the varnish E containing polyimide precursor E.
Raw material, that is, diamines (DA) of obtained polyimide precursor (PIpre) A~E and tetracarboxylic dianhydride (TD) and The glass transition temperature Tg of the presoma is as described in Table 1.The content of polyimide precursor A~E in varnish A~E For 25.0 mass %.
[table 1]
[preparation of coating]
Curability silicone F~H shown in following table 2 is prepared.Curability silicone F~H is cured by heat progress Thermocurable silicone.The specific gravity (SG) of curability silicone F~H, viscosity (Vis), functional group equivalent (EWFG), chemical combination name and ProductName is as shown in table 2.In table 2, " BYK-377 " is Bi Ke chemical company system, and " BYK " is the registered trademark of the said firm."X22- 4039 " be Shin-Etsu Chemial Co., Ltd's system." FZ-2191 " is Dow Corning Toray Co., Ltd.'s system.
[table 2]
In plastic containers, it is taken into aftermentioned varnish A, solvent, pigment dispersing agent, coloring pigment, adds suitable glass Bead has been shaken the plastic containers 8 hours using coating shakeout machine.Later, glass beads are removed, to obtained mixed liquor Middle addition curability silicone F is stirred the mixed liquor with 1000rpm using propeller type mixer, is prepared for applying Coating (coating) a of film.The containing ratio of nonvolatile component (solid component) in coating a is 22.13 mass %. In addition, " carbon black MA100 " is Mitsubishi chemical Co., Ltd's system." DISPERBYK-130 " is Bi Ke chemical company system, " DISPERBYK " is the registered trademark of the said firm.In addition, the containing ratio of nonvolatile component is, polyimide precursor, heat cure Property silicone, coloring pigment and pigment dispersing agent in nonvolatile component total (28.56 mass parts) relative to aftermentioned material Total amount (129.05 mass parts) ratio.
Raw material shown in table 3 has been used according to amount shown in following Table 3, in addition to this, in the same manner as coating a, point It is not prepared for coating b~m.The composition of coating a~m is as shown in table 3.In table 3, " Cw " indicates the content of varnish, " PI-pre " indicates that polyimide precursor, " Cnv1 " indicate the content of the nonvolatile component in varnish, and " S-pre " indicates solidification Property silicone, " Cs " indicates the content of curability silicone, and " Csol " indicates the content of solvent, and " Cpig " indicates that coloring pigment contains Amount, " Cda " indicate the content of pigment dispersing agent, and " Ctotal " indicates the total of the content of each ingredient, apply in " Cnv2 " expression The content of nonvolatile component in material, moreover, " RS/P" curability silicon of the expression relative to 100 mass parts of polyimide precursor The mass fraction of ketone.Content other than Cnv1 is the content in upper painting film.
[table 3]
[production of coated steel plate 1~30]
The plate (plate thickness: 0.4mm) for the SUS430 that surface finish work is No.4 grinding finishing is prepared.Moreover, carrying out Alkali degreasing and chemical conversion treatment are as Coating Pretreatment.Alkali degreasing is, by the SURF of Nippon Paint Co., Ltd. CLEANER 155 (concentration: 2 mass %) cleans 10 seconds after the spraying of the surface of above-mentioned stainless-steel sheet, with 60 DEG C of hot water, then The processing washed.Chemical conversion treatment is that the NRC300 of Nippon Paint Co., Ltd. is coated on above-mentioned stainless steel steel The surface of plate is so that Cr adhesion amount is 50mg/m2, then right at a temperature of the arrival temperature of above-mentioned stainless-steel sheet is 80 DEG C The chromic acid salt treatment that coating liquid is dried.
Then, the surface of the stainless-steel sheet after Coating Pretreatment, the chemical conversion treatment skin i.e. on stainless-steel sheet On film, using bar coater coating coating a so that dry film thickness is 5 μm, form coating a's on stainless-steel sheet Layer.
Then, at a temperature of the arrival temperature of stainless-steel sheet is 350 DEG C, the layer of coating a is heated, it will Layer roasting is on stainless-steel sheet, having obtained the coated steel plate 1 with the upper painting film formed by this layer.In coated steel plate 1 Production in, after coating coating a to heating start waiting time be 15 seconds, above-mentioned arrival is reached since heating The heating time of temperature is 130 seconds.
By changing the type of coating, waiting time, heating time shown in following table 4 and 5 and from painting be covered with painting In the same manner as coated steel plate 1, coated steel plate 2~29 has been made respectively in addition to this to the time of roasting after coating.Moreover, right In each of coated steel plate 1~29, dry film thickness, occupied area rate, the distribution of curing silicone and its shape, island have been found out Maximum area and the peak strength of FT-IR ratio.The type of coating in coated steel plate 1~29, the upper drying for applying film Film thickness (Tf), heating time (Temp-h), reaches temperature (Temp-a), the upper curing silicone applied in film at the waiting time (Tw) Occupied area rate (Rarea), distribution, distribution shape, the maximum area (Smax) on island and above-mentioned peak strength ratio (A/B) As shown in table 4, table 5.
By gravimetric method, i.e. from the weight of the steel plate after coating, subtract after mechanically eliminating film using sand-blast etc. Steel plate weight, acquire the weight of film, and divided by steel plate area and the method for applying film density, acquired dry film thickness.
In addition, (can clearly grasp distributional pattern with 100~3000 times of backscattered electron image using scanning electron microscope Multiplying power) surface of film, the photograph image of the charge pattern at shooting any 5, to obtained photograph image are applied in observation Digital processing is carried out, the area ratio of the part of the curing silicone in each photograph image is calculated, by the face of the photograph image at above-mentioned 5 The average value of product rate is set as occupied area rate.
In addition, observe the photograph image, will be observed in the continuous phase of polyimides or curing silicone curing silicone or The case where dispersed phase of polyimides, is determined as " island " of island structure.In addition, the case where not observing above-mentioned island structure It is determined as " continuous ".Also, the shape on island and the area on island are acquired.Even if in addition, will be shown to being believed that using scanning electron The 5mm that micro mirror can sufficiently and reasonably determine the presence or absence of island structure2Region arbitrary 5 at observed, The case where not observing island structure is determined as " continuous ".
For the shape on island, the flat ratio (ratio of long side and short side) of the shape on the island in the photograph image is calculated. Moreover, by flat ratio be 0.9~1.1 island number be whole islands in the photograph image number 95% or more situation Be determined as " roughly circular ", will for 80% more than and less than 95% the case where be determined as " a part of roughly circular ", will be less than 80% the case where, is determined as " unsetting ".
As an example, indicate the surface of the upper painting film in the coated steel plate 3 of embodiment, clapped by scanning electron microscope The electron micrograph for the backscattered electron image taken the photograph is as shown in Figure 3A.It is found that being made in coated steel plate 3, on its surface The upper upper painting film with the subtle island structure for being dispersed with subtle island (island is curing silicone).
In addition, the area on the maximum island in 5 above-mentioned photograph images to be set as to the maximum area on island.Shape on island is In the case where a part of roughly circular or unsetting, due to the complexity of shape, it is difficult to measure maximum area sometimes, acquires the situation Under the maximum area on island be shown in bracket as approximation, and in table 4 and table 5.
In addition, using FT-IR ATR method, with incidence angle: 45 °, measurement range: 1000~3000cm-1Condition to upper painting The surface of film is measured, and according to obtained measurement result, acquires 1014cm-1Peak strength (a1) relative to 1375cm-1 Peak strength (a2) ratio (a1/a2), and be set as " A " of the peak strength than in.It is applied in addition, peeling upper painting from coated steel plate Film, or cut using Mini-Plane (Co., Ltd.'s STJAPAN system) etc. to 4 μm of depth and obtain sample strip, by FT-IR to benefit It is measured with the sample that KBr method makes, according to obtaining as a result, acquiring 1014cm-1Peak strength (b1) relative to 1375cm-1Peak strength (b2) ratio (b1/b2), and be set as " B " of the peak strength than in.Also, it is opposite to have acquired above-mentioned A In the ratio of above-mentioned B, as above-mentioned peak strength ratio.
[table 4]
[table 5]
For coated steel plate 12, coating l does not contain Thermocurable silicone, therefore does not observe consolidating in film coated surface The distribution (island) of SiClx ketone.The A and B of peak strength ratio A/B can not be acquired as a result,.In addition, for coated steel plate 13, upper painting Coating m does not contain polyimide precursor, therefore curing silicone constitutes the entirety of film coated surface, does not observe in film coated surface The island of curing silicone.The A and B of peak strength ratio A/B can not be acquired as a result,.In addition, for coated steel plate 28, curing silicone For sea, polyimides is distributed as unsetting island.In addition, for coated steel plate 19 and coated steel plate 29, " distribution " All it is " continuous ", therefore whichever coated steel plate can not all acquire " maximum area (Smax) on island ".
Also, without above-mentioned chemical conversion treatment, in addition to this, in the same manner as coated steel plate 3, coated steel plate has been made 30.For the upper painting film of coated steel plate 30, it has been carried out similarly observation, measurement with coated steel plate 1, as a result: solidification silicon The occupied area rate of ketone is 35%, and distribution is " island ", and distribution shape is " roughly circular ", and the maximum area on island is 100 μ m2, peak strength ratio A/B is 30.
[evaluation]
For aftermentioned project, coated steel plate 1~30 is evaluated.
[film adhesion]
(1) adhesion (Ad-1) is processed
To each of coated steel plate 1~30, determines width 70mm and length is 2 times or so of part of width, inciting somebody to action After upper painting film carries out 2T bending as table side, processing department (part of bending) is acquired and is carrying out adhesive tape stripping using adhesive tape The survival rate of upper painting film from after, and evaluated by following benchmark.In addition, the both ends 10mm's for eliminating bending part In the region of 50mm, using the size of the part of scale measurement film remaining, and the area of the remnant is calculated relative to this The ratio of the area in the region of 50mm width has acquired the upper survival rate for applying film.
(evaluation criteria of film adhesion)
A: survival rate 100%
B: survival rate is 95% more than and less than 100%
C: survival rate is 90% more than and less than 95%
D: survival rate is 80% more than and less than 90%
E: survival rate is 70% more than and less than 80%
F: survival rate is 50% more than and less than 70%
G: survival rate is less than 50%
(2) water-fast secondary adhesion (Ad-2)
After coated steel plate 1~30 is impregnated in boiling water 2 hours respectively, the cross-hatching adhesive tape stripping that film is applied on implementing is acquired Film survival rate from after, and evaluated by above-mentioned evaluation criteria.
[heat resistance]
For each of coated steel plate 1~30, taken care of 24 hours with 250 DEG C, 300 DEG C and 350 DEG C of temperature respectively Afterwards, the film survival rate after acquiring the cross-hatching adhesive tape removing for applying film on implementing, and evaluated by above-mentioned evaluation criteria.
[resistance to food pollution]
(1) the resistance to food pollution (AP-1) at initial stage
Food is placed on the upper painting film of each of the coated steel plate 1~30 of not test (N.T.) state, to the painting steel loading After plate is heated 1 hour with 250 DEG C, the state of wiping when being wiped food contaminant from coated steel plate using paper handkerchief is seen It examines.Food used salad oil, butter, soy sauce and sauce these four, observe every kind of food variety wipes state.And it presses Evaluation criteria is stated to be evaluated.
(evaluation criteria of resistance to food pollution)
A: each food can easily remove and with paper handkerchief wiping
B: each food can remove (noresidue) by rubbing with paper handkerchief
C:1 kind food can be removed by being rubbed with paper handkerchief, but have residual (other 3 kinds can remove)
Even if D:1 kind food can not remove (other 3 kinds can remove) with paper handkerchief friction
Even if E:2 kind food can not be removed with paper handkerchief friction it is not possible that (other 2 kinds can remove)
Even if F:3 kind food can not be removed with paper handkerchief friction it is not possible that (other a kind can remove)
G: even if the food friction of all categories can not remove
(2) the resistance to food pollution (AP-2) after heat resistant test
Food is placed on the coated steel plate after heated 24 hours with 350 DEG C, in addition to this, has carried out above-mentioned (1) Condition test, the state of wiping of each food is observed, and is evaluated by above-mentioned evaluation criteria.
(3) the resistance to food pollution (long run test, AP-3) when being used continuously
The test for repeating the condition of 10 times above-mentioned (1) with identical coated steel plate, the wiping to the 10th each food Fall state to be observed, and is evaluated by said reference.
The results are shown in Table 6.
[table 6]
[production, the evaluation of clear-coated steel plate]
Aftermentioned raw material is stirred with 1000rmp using propeller type mixer, is prepared for applying the painting of film Expect (clear dope).That is, unmixed coloring pigment and pigment dispersing agent have been prepared as thoroughly with coating c in addition to this Bright coating.The content of the nonvolatile component of the clear dope is 16.83 mass %, relative to 100 matter of polyimide precursor (P) The amount for measuring the curability silicone (S) of part is 5.0 mass parts.
100 mass parts of varnish C
1.25 mass parts of curability silicone F
25 mass parts of n,N-dimethylacetamide
Using above-mentioned clear dope, in addition to this, in the same manner as coated steel plate 1, coated steel plate 31 has been made.For coating The upper painting transparent coating of steel plate 31 has been carried out similarly observation, measurement with coated steel plate 1, as a result: curing silicone occupies The area ratio is 35%, and distribution is " island ", and distribution shape is " roughly circular ", and the maximum area on island is 100 μm2, peak value is strong Degree is 30 than A/B.
In addition, being carried out respectively for above-mentioned film adhesion, heat resistance and resistance to food pollution for coated steel plate 31 Evaluation, has obtained result identical with the coated steel plate 3 in table 6.
[production of coated steel plate 32,33]
Hot-dip Al-9%Si steel plate (plate thickness: 0.4mm, single-face plating adhesion amount 40g/m is prepared2) it is used as steel plate.Into Above-mentioned alkali degreasing gone as Coating Pretreatment, has carried out Ti system chromium-free treatment as chemical conversion treatment.Fluotitanic acid is used (H2TiF6: 0.1mol/L) it is used as chemical conversion treatment solution, which is coated on to the surface of above-mentioned clad steel sheet So that the adhesion amount of Ti is 10mg/m2, and make it dry.
On the other hand, 30 mass parts of aluminium dihydrogen tripolyphosphate magnesium are added in the polyimide precursor B of 100 mass parts As rust resisting pigment, it is prepared for primary coat film coating.The primary coat film is coated on to the chemistry of above-mentioned clad steel sheet with coating Conversion processing epithelium is that 280 DEG C of temperature is heated with the arrivals temperature of clad steel sheet so that dry film thickness is 5 μm, production The primary coat film that is made of polyimides.
On the surface of room temperature, made primary coat film, by coating c with condition identical with coated steel plate 3 into Row coating, heating, have made upper painting film.In this way, having made coated steel plate 32.In addition, do not make primary coat film, except this with Outside, in the same manner as coated steel plate 32, coated steel plate 33 has been made.
[evaluation]
It is directed to above-mentioned film adhesion, heat resistance and resistance to food pollution respectively, coated steel plate 32,33 is commented Valence.Also, coated steel plate 32,33 is evaluated for aftermentioned corrosion resistance.
[corrosion resistance]
In flat part (part other than the section of end) mark signature lattice of coated steel plate 32 and 33,35 DEG C of ring is being kept It is implemented in border and carries out spraying salt spraytest with film of 5% salt water to coated steel plate (according to SST, JIS Z2371) 240 hours.After experiment, the maximum swelling width in crossed grid portion is observed, and presses and states evaluation criteria and commented Valence.The results are shown in Table 7.
(evaluation criteria of corrosion resistance)
A: maximum swelling width is less than 1mm
B: maximum swelling width is 1mm more than and less than 2mm
C: maximum swelling width is 2mm more than and less than 3mm
D: maximum swelling width is 3mm more than and less than 4mm
E: maximum swelling width is 4mm or more
[table 7]
Coated steel plate 1~5,7~11 and 14~33 all in film adhesion, heat resistance, resistance to food pollution, is demonstrated by At least as the cooking appliance component performance that there is no problem in actual use.Coated steel plate 32 and 33 in corrosion resistance, It is further demonstrated by least as the cooking appliance component performance that there is no problem in actual use.
In this regard, the resistance to food pollution of coated steel plate 6 is insufficient in actual use.This is believed that since upper painting applies The occupied area rate of curing silicone in the surface of film is 4%, so insufficient.In addition, the resistance to food pollution of coated steel plate 12 Property is also insufficient in actual use.This may be considered since the upper substrate for applying film is only that polyimides (above applies film not Contain curing silicone).Also, film adhesion, heat resistance and the resistance to food pollution of coated steel plate 13 are all in actual use It is insufficient.This may be considered since the upper substrate for applying film is only curing silicone (above applying film without containing polyimides).
In summary, it is known that following coated steel plates as cooking appliance component coated steel plate in heat resistance and antifouling Excellent in property the two, which is made up of successively overlapping steel plates and film, and above-mentioned film includes upper painting film, on Stating and applying film includes polyimides and curing silicone and the surface for constituting coated steel plate, in the above-mentioned upper surface for applying film The occupied area rate of curing silicone is 5% or more.
In addition, coated steel plate 3,7 is all more excellent in resistance to food pollution for example compared with coated steel plate 6.In addition, example Such as compared with coated steel plate 9, coated steel plate 3,8 is more excellent in the resistance to food pollution all after heat resistant test.In conclusion can Know that the content of the curing silicone in upper painting film relative to 100 mass parts of polyimides is 1~10 mass parts, this is from soil resistance It is relatively effective from the viewpoint of durability.
In addition, coated steel plate 3,7,14 is all more excellent in resistance to food pollution for example compared with coated steel plate 6.In addition, Such as compared with coated steel plate 9, coated steel plate 3,8,17 is more excellent in the resistance to food pollution all after heat resistant test.To sum up institute It states, it is known that the occupied area rate for above applying the curing silicone in the surface of film is 5~70%, this sight from the durability of soil resistance It is relatively effective from the point of view of point.
In addition, resistance to food of the coated steel plate 3 after heat resistant test and in long run test is dirty for example compared with coated steel plate 29 It is more excellent in metachromia.In summary, it is known that the surface for above applying film is the island structure of polyimides and curing silicone, this is from anti- It is relatively effective from the viewpoint of the durability of dirt.In addition, coated steel plate 27 is heat-resisting for example compared with coated steel plate 28 It is more excellent in resistance to food pollution after test.In summary, it is known that above apply film surface be based on polyimides sea and The island structure on the island of curing silicone is relatively effective from the viewpoint of this durability from soil resistance.
In addition, compared with coated steel plate 18, coated steel plate 15~17 is after heat resistant test in coated steel plate 15~18 It is more excellent in resistance to food pollution.In addition, the resistance to food after film adhesion, heat resistant test is dirty in coated steel plate 20~22 Sequence in resistance to food pollution in metachromia and long run test according to coated steel plate 20,21,22 is gradually more excellent.To sum up It is described, it is known that the area for above applying the island of each curing silicone in the surface of film is 300 μm2Below or it is upper apply film table The island of curing silicone in face it is substantially circular in shape, this is from the viewpoint of the durability of soil resistance or from the sight of film adhesion It is relatively effective from the point of view of point.
In addition, in coated steel plate 15~18, coated steel plate 15,16 is more resistance to after heat resistant test than coated steel plate 17,18 It is more excellent in food pollution.In addition, coated steel plate 25,26 is than coated steel plate 24 in resistance to food in coated steel plate 24~27 It is more excellent in pollution, it is more more excellent than in resistance to food pollution of the coated steel plate 27 after heat resistant test and in long run test.It is comprehensive It is upper described, it is known that when by being measured by the infrared spectrum analysis based on ATR method to the upper surface for applying film, 1014cm-1Peak strength relative to 1375cm-1The ratio of peak strength be defined as A, and will be by based on the infrared of KBr method When spectrum analysis is measured upper painting film, 1014cm-1Peak strength relative to 1375cm-1Peak strength ratio When being defined as B, A is 1.1~100 relative to the ratio A/B of B, is relatively effective from the viewpoint of this durability from soil resistance.
In addition, for the heat resistance at 250 DEG C, coated steel plate 2~5 is more excellent than coated steel plate 1 in coated steel plate 1~5 Different, for the heat resistance at 300 DEG C, compared with coated steel plate 1, coated steel plate 2,5 is more excellent, and coated steel plate 3,4 is more excellent, right Heat resistance at 350 DEG C, compared with coated steel plate 1, coated steel plate 2 and 5 is more excellent, and coated steel plate 4 is more excellent, coated steel plate 3 is more excellent.In addition, the resistance to food pollution for initial stage, compared with coated steel plate 1, coated steel plate 2~5 is more excellent, for Resistance to food pollution after heat resistant test or in long run test, compared with coated steel plate 1, coated steel plate 2~5 is more excellent, with painting Cartridge plate 2 is compared, and coated steel plate 3~5 is more excellent.As can be observed from the foregoing, the Tg of polyimides is 270~400 DEG C, this is from heat-resisting Property and soil resistance durability from the viewpoint of, be relatively effective.
In addition, in coated steel plate 20~23, for film adhesion, according to the sequence of coated steel plate 20,21,22,23 Gradually more excellent, for heat resistance, each coated steel plate is substantially good, for the resistance to food after heat resistant test and in long run test Product pollution, compared with coated steel plate 20, coated steel plate 21~23 is more excellent, compared with coated steel plate 21, coated steel plate 22,23 It is more excellent.In summary, it is known that the manufacturing method of following coated steel plate includes: to be covered with painting in the coating raw sheet painting comprising steel plate to apply Material, the process for forming the layer of coating；And heated by the layer to coating, it is roasted in coating raw sheet shape At the upper process for applying film, coating contains the presoma of polyimides, curability silicone and solvent, so that steel plate The mode that temperature is 180 DEG C or more is reached, the layer of the coating on surface is floated to at least part of curability silicone It is heated, film in formation, this method is capable of providing the excellent coated steel plate of both heat resistance and soil resistance, as cooking Adjust the coated steel plate of utensil component.
In addition, coated steel plate 25,26 is more excellent in resistance to food pollution than coated steel plate 24 in coated steel plate 24~27 It is different, it is more more excellent than in resistance to food pollution of the coated steel plate 27 after heat resistant test and in long run test.In summary, it is known that from By coating be coated on coating raw sheet to time (waiting time) for beginning to warm up be 5~60 seconds, this is from offer soil resistance It is relatively effective from the viewpoint of the coated steel plate of excellent in te pins of durability.
In addition, coated steel plate 25 is more excellent than coated steel plate 24 in resistance to food pollution in coated steel plate 24,25.Separately Outside, in coated steel plate 27,29, coated steel plate 27 is more excellent than coated steel plate 29 in the resistance to food pollution after heat resistant test. In summary, it is known that from begin to warm up reach reach temperature time (calcining time) be 30~240 seconds, this from provide it is antifouling Property excellent in te pins of durability coated steel plate from the viewpoint of, be relatively effective.
In addition, in coated steel plate 21,22, coated steel plate 22 is after film adhesion and heat resistant test and long run test In resistance to food pollution on it is more excellent than coated steel plate 21.In summary, it is known that the arrival temperature of steel plate is 200 DEG C or more, this It is relatively effective from the viewpoint of the coated steel plate of excellent in te pins of durability that film adhesion and soil resistance are provided.
In addition, coated steel plate 15 is in the resistance to food pollution in long run test than applying steel loading in coated steel plate 14,15 Plate 14 is excellent.In addition, coated steel plate 16 compares coating in the resistance to food pollution after heat resistant test in coated steel plate 16,17 Steel plate 17 is excellent.In summary, it is known that from the viewpoint of the coated steel plate of excellent in te pins of durability for providing soil resistance, painting is covered with painting Coating is so that it is relatively effective that the upper film thickness for applying film, which is 2~20 μm,.
In addition, for example coated steel plate 3,7 is more more excellent in resistance to food pollution than coated steel plate 6.In addition, such as coating Steel plate 3,8 is more excellent in the resistance to food pollution than coated steel plate 9 after heat resistant test.In summary, it is known that coating In curability silicone content relative to 100 mass parts polyimides presoma be 1~10 mass parts, this from provide it is antifouling Property excellent in te pins of durability coated steel plate from the viewpoint of, be relatively effective.
In addition, for example coated steel plate 3 is more more excellent in film adhesion than coated steel plate 30.In summary, it is known that from mentioning From the viewpoint of the excellent coated steel plate of film adhesion, having chemical conversion treatment epithelium on the surface of steel plate is relatively effectively 's.
The application is willing to 2014-072302 claims priority based on the Japanese patent application laid proposed on March 31st, 2014 Power.The content recorded in the specification and attached drawing of this application all refers in present specification.
Industrial applicibility
5% or more in surface that coated steel plate of the invention applies film on the upper surface for applying film is with this occupies face Product rate contains curing silicone.Therefore, with compared with the upper surface for applying film has the coated steel plate of fluororesin, have it is same or While superior soil resistance, there is higher heat resistance.Coated steel plate of the invention is suitable in higher temperature as a result, The material of the equipment of soil resistance is needed under environment.Coated steel plate according to the present invention as a result, it can be expected that it helps to pass through The more special heating such as the heating of higher temperatures or steam heating is come the further development for the heating and cooking appliance cooked.

Claims (12)

1. a kind of coated steel plate has film on the steel plate, wherein
The film includes upper painting film,
The upper painting film contains polyimides and curing silicone,
The content of the curing silicone is 1~10 mass parts relative to polyimides described in 100 mass parts,
The occupied area rate of the curing silicone in the upper surface for applying film is 5% or more,
The upper surface for applying film is the island phase island structure of marine facies and the curing silicone based on the polyimides.
2. coated steel plate as described in claim 1, wherein
The occupied area rate of the curing silicone in the upper surface for applying film is 5~70%.
3. coated steel plate as described in claim 1, wherein
The shape on the island of the curing silicone is the circle that the ratio of major diameter and minor axis is 0.9~1.1, each curing silicone The area on island is 300 μm2Below.
4. the coated steel plate as described in any one of claims 1 to 3, wherein
The glass transition temperature of the polyimides is 270~400 DEG C.
5. a kind of coated steel plate has film on the steel plate, wherein
The film includes upper painting film,
The upper painting film contains polyimides and curing silicone,
The content of the curing silicone is 1~10 mass parts relative to polyimides described in 100 mass parts,
The occupied area rate of the curing silicone in the upper surface for applying film is 5% or more,
When by being measured by the infrared spectrum analysis based on In situ ATR-FTIR method to the upper surface for applying film , 1014cm-1Peak strength relative to 1375cm-1The ratio of peak strength be defined as A,
And by by the infrared spectrum analysis based on pellet technique to it is described it is upper apply film be measured when, 1014cm-1 Peak strength relative to 1375cm-1The ratio of peak strength when being defined as B,
The A is 1.1~100 relative to the ratio of the B.
6. coated steel plate as claimed in claim 5, wherein
The glass transition temperature of the polyimides is 270~400 DEG C.
7. a kind of manufacturing method of coated steel plate, comprising:
Coating is coated on the coating raw sheet comprising steel plate, the process for forming the layer of coating；And
It is heated, is roasted in the coating raw sheet by the layer to the coating, to apply film on being formed Process,
The coating contains the presoma of polyimides, curability silicone and solvent,
The content of the curability silicone of the presoma relative to polyimides described in 100 mass parts in the coating More than 1.0 mass parts,
Since by the coating be coated on time of the coating raw sheet to ing until the heating be 5~70 seconds,
So that the arrival temperature of the steel plate is 180 DEG C or more and reaches the arrival temperature from the heating is started and be The mode that time only is 30~240 seconds, the upper painting on surface is floated to at least part of the curability silicone The layer of coating is heated, and the upper painting film is formed.
8. the manufacturing method of coated steel plate as claimed in claim 7, wherein
The arrival temperature of the steel plate is 200 DEG C or more.
9. the manufacturing method of coated steel plate as claimed in claim 7, wherein
The coating is coated in a manner of making upper 2~20 μm of film thickness for applying film.
10. the manufacturing method of coated steel plate as claimed in claim 7, wherein
The content of the curability silicone in the coating is relative to the presoma of polyimides described in 100 mass parts 1~10 mass parts.
11. the manufacturing method of coated steel plate as claimed in claim 7, wherein
The steel plate has chemical conversion treatment epithelium on its surface.
12. a kind of cooking appliance component, wherein
Include coated steel plate described in any one of claim 1~6.
CN201580017735.8A 2014-03-31 2015-03-31 Coated steel plate and its manufacturing method and cooking appliance component Active CN106232349B (en)

Applications Claiming Priority (3)

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JP2014072302A JP6163128B2 (en) 2014-03-31 2014-03-31 Painted steel sheet, method for producing the same, and cooking utensil member
PCT/JP2015/001850 WO2015151509A1 (en) 2014-03-31 2015-03-31 Coated steel sheet, method for producing same and member for cooking utensils

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