CN106232349A - Coated steel plate and manufacture method thereof and cooking appliance parts - Google Patents
Coated steel plate and manufacture method thereof and cooking appliance parts Download PDFInfo
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- CN106232349A CN106232349A CN201580017735.8A CN201580017735A CN106232349A CN 106232349 A CN106232349 A CN 106232349A CN 201580017735 A CN201580017735 A CN 201580017735A CN 106232349 A CN106232349 A CN 106232349A
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- steel plate
- coated steel
- film
- coating
- coated
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Classifications
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- 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)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Food Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Cookers (AREA)
Abstract
The coated steel plate (10) of the present invention is consisted of overlapping steel plates successively (11) and upper painting film (14).Upper painting film (14) comprises polyimides (141) and curing silicone (144).The occupied area rate of the curing silicone (144) in the surface of upper painting film (14) is more than 5%.Both the thermostability of coated steel plate (10) and soil resistance are excellent, suitably as the materials'use of cooking appliance parts.
Description
Technical field
The present invention relates to thermostability and coated steel plate and the manufacture method thereof of soil resistance excellence and comprise this coated steel plate
Cooking appliance parts.
Background technology
In recent years, develop in heating chamber, supply the microwave oven of steam.Above-mentioned heating chamber is typically by having thermostability
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 such as by metallic plate, master
Primary coat film and the upper painting film to be made up of polyether sulfone overlap according to this order, and on this, painting film contains tetrafluoro second
Alkene perfluoroalkyl vinyl ether copolymer (PFA) and PFA are distributed (for example, referring to patent documentation 1) unevenly on surface.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2005-262465 publication
Summary of the invention
The problem that invention is to be solved
Both the thermostability of above-mentioned coated steel plate and soil resistance are excellent.But, in recent years, develop and to the market supply
The microwave oven can cooked with higher temperature.Therefore, to the coated steel plate for such cooking appliance, it is desirable to thermostability
Improve further.
The present invention completes in view of this, its object is to offer and has both more preferable thermostability and soil resistance
Coated steel plate.
It addition, another object of the present invention is to provide the cooking appliance parts comprising this coated steel plate.
The scheme of solution problem
The inventors discovered that by combining specific silicone in polyimides, in the surface appropriateness of the film of polyimides
Ground dispersion, expose silicone, and this film be used for the upper painting film of coated steel plate, make painting film on this show soil resistance with
And the thermostability of excellence.And study further and complete the present invention.
That is, the present invention relates to following coated steel plate.
[1] a kind of coated steel plate, has film on steel plate, and wherein, described film includes painting film, described upper painting
Film contains polyimides and curing silicone, and the occupied area rate of the described curing silicone in the surface of described upper painting film is 5%
Above.
[2] coated steel plate as described in [1], wherein, the content of the described curing silicone in described upper painting film 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 described curing silicone in the surface of described upper painting film
Occupied area rate is 5～70%.
[4] coated steel plate as described in any one in [1]～[3], wherein, in the surface of described upper painting film, described
Polyimides and described curing silicone become island structure.
[5] coated steel plate as described in [4], wherein, the island of described curing silicone substantially circular in shape, described in each
The area on the island of curing silicone is 300 μm2Below.
[6] coated steel plate as described in any one in [1]～[5], wherein, will be by based on In situ ATR-FTIR
When the surface of described upper painting film is measured by the infrared spectrum analysis of method, 1014cm-1Peak strength relative to
1375cm-1The ratio of peak strength be defined as A,
And by when described upper painting film being measured by infrared spectrum analysis based on pellet technique,
1014cm-1Peak strength relative to 1375cm-1The ratio of peak strength when being defined as B,
The described A ratio relative to described B is 1.1～100.
[7] coated steel plate as described in any one in [1]～[6], wherein, the glass transition temperature of described polyimides
Degree is 270～400 DEG C.
Moreover, it relates to the manufacture method of following coated steel plate.
[8] manufacture method of a kind of coated steel plate, including: on the application raw sheet comprise steel plate, coat coating, shape
Become the operation of the layer of coating；And it is former in described application by the layer of described coating is heated its roasting
Plate, thus form the upper operation being coated with film, described coating contains the presoma of polyimides, curable silicone, Yi Jirong
Agent, the content of the described curable silicone relative to the presoma of polyimides described in 100 mass parts in described coating
It is more than 1.0 mass parts, in the way of making the arrival temperature of described steel plate be more than 180 DEG C, to described curable silicone extremely
The layer that a few part floats to the described coating on surface heats, and forms described upper painting film.
[9] manufacture method of the coated steel plate as described in [8], wherein, is coated on described application from by described coating
Raw sheet is 5～60 seconds to the time started described heating.
[10] manufacture method of the coated steel plate as described in [8] or [9], wherein, is heated to reach described described in starting
The time till temperature that arrives is 30～240 seconds.
[11] manufacture method of the coated steel plate as described in any one in [8]～[10], wherein, the arrival of described steel plate
Temperature is more than 200 DEG C.
[12] manufacture method of the coated steel plate as described in any one in [8]～[11], wherein, so that described upper painting
The thickness of film is that the mode of 2～20 μm coats described coating.
[13] manufacture method of the coated steel plate as described in any one in [8]～[12], wherein, in described coating
The content of described curable silicone be 1～10 mass parts relative to the presoma of polyimides described in 100 mass parts.
[14] manufacture method of the coated steel plate as described in any one in [8]～[13], wherein, described steel plate is at its table
Mask has chemical conversion treatment epithelium.
Further, the present invention relates to comprise the cooking appliance parts of above-mentioned coated steel plate.
Invention effect
Compared with the existing coated steel plate exposing fluororesin, the coated steel plate of the present invention can embody higher heat-resisting
Property, on an equal basis or more excellent soil resistance.Thus, the coated steel plate of the present invention is suitable for the cooking device used at relatively high temperatures
The parts of tool.
Accompanying drawing explanation
Fig. 1 is the figure of the structure of the coated steel plate schematically showing one embodiment of the present invention.
Fig. 2 A is the figure of the trend of the composition in the layer schematically showing coating, and Fig. 2 B is to schematically show admittedly
The figure of the state in the surface of the layer that SiClx ketone is present in coating dispersedly, 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 representing embodiment, shot by scanning electron microscope
The electron micrograph of backscattered electron image, Fig. 3 B be represent curable silicone assemble after upper painting film surface,
The electron micrograph of the backscattered electron image shot by scanning electron microscope.
Fig. 4 is the figure of the island structure schematically shown in painting film and the fluid contaminants being attached to this film.
Description of reference numerals
10 coated steel plates
11 steel plates
12 chemical conversion treatment epitheliums
13 primary coat films
14, film it is coated with 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 curable silicone
514 pollutant
Detailed description of the invention
The coated steel plate of the present invention has film on steel plate.For film, as long as such as including upper painting film described later
Film as most surface.Above-mentioned film such as can also further include at steel plate surface formed primary coat film,
Or the middle painting film in the formation of the surface of primary coat film.Such as, as it is shown in figure 1, the coated steel plate 10 of the present invention is by weighing successively
Fold steel plate 11, chemical conversion treatment epithelium 12, primary coat film 13 and upper painting film 14 and constitute.Primary coat film 13 is main by resin
131 are constituted, and can comprise the additives such as various pigment 132 as described later.As described later, upper painting film 14 is main by polyamides
Imines 141 is constituted, and can comprise the additive such as alumina particles 142 or inorganic additive 143.It addition, upper painting film 14 comprises at least
The curing silicone 144 existed on its surface.
[steel plate]
Above-mentioned steel plate suitably can select from known steel plate according to the purposes of coated steel plate or desired characteristic etc.
Select.As the example of steel plate, including galvanized steel plain sheet (plating Zn, hot dip galvanizing), alloy galvanized steel plate (after hot dip galvanizing warp
Alloying Treatment alloyed hot-dip plating 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 improving 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 entering one
From the viewpoint of step improves the reflectance of corrosion resistance and microwave, preferably hot-dip Al stainless-steel sheet.
[chemical conversion treatment epithelium]
From the viewpoint of the corrosion resistance improving coated steel plate and film adhesion, steel plate can also have chemical conversion
Process epithelium.Chemical conversion treatment epithelium is the thin layer formed by the matrix process of application.Example as chemical conversion treatment
Son, including chromate process, chromium-free treatment and phosphate treated.The adhesion amount of chemical conversion treatment epithelium can be effectively
Improve and suitably determine in the range of corrosion resistance and film adhesion.Such as, the adhesion amount of chromate epithelium is for making full Cr change
Calculating adhesion amount is 5～100mg/m2Amount.It addition, the adhesion amount of Chrome-free epithelium, such as Ti-Mo composite film is for making complete Ti and Mo
Conversion adhesion amount is 10～500mg/m2Amount, the adhesion amount of fluoracid system epithelium is for making fluorine conversion adhesion amount or total metallic element
Conversion adhesion amount is 3～100mg/m2Amount.Further, the adhesion amount of phosphate coating is 0.1～5g/ for making phosphorus conversion adhesion amount
m2Amount.
Chemical conversion treatment epithelium can be formed by known method.Such as, chemical conversion treatment solution is passed through roller coat
The methods such as method, spin-coating method, stick coating method, spraying process are coated on the surface of steel plate, do not carry out making it be dried with washing.For dry
Dry temperature and drying time, as long as moisture can be made to evaporate, it is defined the most especially.From the viewpoint of productivity ratio, preferably
Baking temperature is 60～150 DEG C with the arrival temperature of steel plate, and preferably drying time is 2～10 seconds.
[primary coat film]
From the viewpoint of the corrosion resistance improving coated steel plate and film adhesion, coated steel plate can also be at steel plate table
There is on the surface of face or chemical conversion treatment epithelium primary coat film further.Generally, the tree based on primary coat film contains
Fat and rust resisting pigment.The resin of primary coat film can be same with the resin-phase on the basis as other films such as upper painting films, it is possible to
With difference.As the example of kind of the resin of primary coat film, including: polyester resin, epoxy resin, acrylic resin, benzene oxygen
The inorganic resin such as resin and silicate resin.As the example of the kind of above-mentioned rust resisting pigment, including magnesium phosphate, zirconium phosphate,
Zinc phosphate, aluminium triphosphate, phosphomolybdic acid zinc, barium metaborate and silicon dioxide based compound.
Primary coat film can also contain other compositions further.Such as, primary coat film can also be containing to above-mentioned organic tree
Fat carries out the cross-linking agent cross-linked.As the example of the kind of cross-linking agent, including: melmac and isocyanate resin.Separately
Outward, primary coat film can also contain coloring pigment, metallic pigments or filler pigment further.As the example of coloring pigment, bag
Include: titanium dioxide, white carbon black, chromium oxide, ferrum oxide, colcother, titan yellow, cobalt blue, cobalt green, nigrosine and phthalocyanine blue.As metal face
The example of material, including: aluminium flake (non-floating type), latten(-tin), copper sheet, stainless steel substrates and nickel sheet.As the example of filler pigment, including
Barium sulfate, silicon dioxide and calcium carbonate.
Further, primary coat film can also contain pigment dispersing agent.As the example of pigment dispersing agent, including: unsaturated carboxylic
Acid the solution (solvent e.g. alkylbenzene/ethylene glycol monobutyl ether=5/1) of polyaminoamide, polyether ester acid amine salt, with
And low molecular weight polycaprolactone ester compounds.
The thickness of primary coat film for example, 0.5～30 μm.
[above film]
Upper painting film constitutes the surface of coated steel plate.Upper painting film contains polyimides and curing silicone.
[polyimides]
Above-mentioned polyimides can be one can also be two or more.It is coated with film strength from raising thermostability and upper painting
From the point of view of viewpoint, preferably this polyimides contains aromatic group in main chain.From the viewpoint of thermostability and cementability, logical
Often, the glass transition temperature (Tg) of above-mentioned polyimides is preferably 270～400 DEG C, more preferably 300～380 DEG C, further
It is preferably 320～360 DEG C.Measurement of Dynamic Viscoelasticity device can be utilized to measure the Tg of above-mentioned polyimides.
Polyimides is by being mixed to get the product (forerunner of polyimides in a solvent by diamidogen and tetracarboxylic dianhydride
Body), and the solidification of this product is obtained.Used diamidogen and the combination of tetracarboxylic dianhydride can be passed through or containing ratio
Deng, the glass transition point (Tg) of above-mentioned polyimides is designed.Such as, it it is 270～400 DEG C as being suitable to prepare Tg
The example of the diamidogen of polyimides, including: 4, amino as 4 '-epoxide diaminobenzene (4,4 '-diamino-diphenyl ether) exists
The diamidogen of para-position or 1, as 3-double (3-amino-benzene oxygen) benzene, 4,4 '-bis-(3-amino-benzene oxygen) biphenyl, amino is in meta
Diamidogen.Especially, the most above-mentioned diamidogen includes 4,4 '-epoxide diaminobenzene (4,4 '-diamino-diphenyl ether) or 4,4 '-bis-
(3-amino-benzene oxygen) biphenyl.As being suitable to prepare the example of the tetracarboxylic dianhydride of the polyimides of above-mentioned Tg, including: all benzene four
Anhydride (1,2,4,5-benzene tertacarbonic acid's dianhydride), 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride and 3,3 ', 4,4 '-biphenyltetracarboxyacid acid
Dianhydride.Wherein, the most above-mentioned tetracarboxylic dianhydride includes 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride.
[curing silicone]
Curing silicone is heating during the roasting by upper painting film etc. and the silicone that solidifies.After curing silicone can pass through
The heat cure etc. of the curable silicone stated obtains.
If the content of the curing silicone in upper painting film is very few, be the most sometimes positioned at painting film surface curing silicone by
Relatively early scraped in reusing of coated steel plate.Therefore, sometimes it is difficult to keep long-term soil resistance.If in upper painting film
The content of curing silicone is too much, the most sometimes containing uncured silicone in curing silicone.Therefore, sometimes on the surface of upper painting film
Producing viscous, the processability of coated steel plate reduces due to this viscous.Further, if the content mistake of the curing silicone in upper painting film
Many, then different due to the linear expansion coefficient under the polyimides high temperature from curing silicone, thus the upper solidification being coated with in film sometimes
The adhesion of silicone is insufficient, and curing silicone peels off from upper painting film.Therefore, the soil resistance of coated steel plate is insufficient sometimes.From
From the viewpoint of so, the content of the preferably upper curing silicone being coated with in film is 1～10 matter relative to polyimides 100 mass parts
Amount part, more preferably 2～6 mass parts.
Being capable of in the range of the effect of the present invention, upper painting film can also contain other compositions further.As
The example of other compositions, including alumina particles, above-mentioned coloring pigment, pigment dispersing agent and inorganic additive.
In order to upper painting film give design (metal sense) and in coating aluminum mixture granule.It is not specially limited
The purity of the aluminum in alumina particles.Such as, alumina particles can be only made up of aluminum, it is also possible to is made up of acieral.As alumina particles
The example of shape, including flakey (laminar), granular, tabular and bulk.From the viewpoint that upper painting film is given metal sense
From the point of view of, preferably alumina particles be shaped as flakey.The content of the alumina particles in upper painting film is such as relative to polyimides 100 matter
Amount part is 0.1～50 mass parts.
In order to improve hardness and the wearability of upper painting film, it is also possible to mix inorganic additive in coating.As
The example of inorganic additive, including glass flake, graphite flake, synthetic mica thin slice, silicon dioxide thin slice etc., flakey is inorganic
Additive；And potassium titanate fibre, wollastonite fibre, silicon carbide fibre, alumina fibre, aluminosilicate fibre, silicon dioxide
The inorfils such as fiber, asbestos, mineral wool, glass fibre, carbon fiber.
The thickness of painting film is not specially limited, but if upper painting film is the thinnest, the thermostability of coated steel plate the most sometimes
And soil resistance is insufficient, if blocked up, although thermostability and soil resistance then can be obtained fully, but upper from manufacturing cost sometimes
Rise or from the viewpoint of other reasons such as the reduction of processability of coated steel plate, be undesirable.From this point of view, excellent
The thickness choosing painting film is 2～20 μm, more preferably 3～15 μm, more preferably 5～10 μm.
The occupied area rate of the curing silicone in the surface of upper painting film is more than 5%.If above-mentioned occupied area rate is less than
5%, anti-fouling effect as lotus-effect the most described later is insufficient.If above-mentioned occupied area rate is excessive, then as it has been described above,
Owing to the linear expansion coefficient under the polyimides high temperature from curing silicone is different, thus curing silicone is shelled from upper painting film sometimes
Falling, the soil resistance of coated steel plate is the most abundant.From this point of view, the most above-mentioned occupied area rate is 5～70%.
Additionally, it is preferred that the surface of upper painting film comprises the island structure based on polyimides and curing silicone.Additionally, " extra large "
Referring to the continuous phase in the surface of painting film, " island " refers to the dispersion phase in the surface of painting film.Polyimides is the most permissible
Being above-mentioned island structure " extra large ", it is also possible to be " island ", curing silicone both can be above-mentioned island structure " island ", it is also possible to be
" extra large ".From the generation of the viscous preventing the content of curing silicone from too much causing and the viewpoint of the reduction etc. of the processability of coated steel plate
From the point of view of, in the most above-mentioned island structure, polyimides is " extra large ", and curing silicone is the island structure on " island ".
Further, from the point of view, the most above-mentioned island is circular, and the area on each island is 300 μm2With
Under.About the shape on island, " circular " refers to that the ratio of major diameter and minor axis is 0.9～1.1.Ratio about the island of circular
Example, as long as the shape on island represents with above-mentioned " circular ", such as, more than the 80% of whole islands meet above-mentioned substantially
Circular.
The configuration of the curing silicone in the surface of upper painting film can by as shown in Figure 3A, use scanning electron microscopy
The backscattered electron image that mirror (SEM) obtains confirms.The area on above-mentioned occupied area rate, the shape on island and island can pass through this back of the body
The image procossing of scattered electron picture is tried to achieve.
It addition, in upper painting film, the most aftermentioned A ratio (A/B) relative to aftermentioned B is 1.1～100.Here, " A " refers to,
By based on ATR method (ATR method: Attenuated Total Reflection Method, In situ ATR-FTIR method) red
When the surface of upper painting film is measured by external spectrum analysis, 1014cm-1Peak strength relative to 1375cm-1Peak value
The ratio of intensity.It addition, " B " refers to, it is coated with upper by infrared spectrum analysis based on KBr method (KBr method: pellet technique)
When film is measured, 1014cm-1Peak strength relative to 1375cm-1The ratio of peak strength.For above-mentioned A the most also
It is above-mentioned B, 1014cm-1Peak strength all derive from silicon atom (Si-O-Si), depositing of curing silicone expression being coated with in film
In amount.It addition, 1375cm-1Peak strength derive from nitrogen-atoms (C-N), the existence of polyimides expression being coated with in film
Amount.
Above-mentioned peak strength can be surveyed by the detection infrared spectroscopy of peak strength, such as FT-IR
Fixed.It addition, as it is well known, the ATR method method that is by the infrared spectrum analysis on surface.As it is well known, KBr method is
Plate holder by the tablet of the KBr of the dispersed section having upper painting film or using KBr holds the sample of above-mentioned section as sample,
The method carrying out infrared spectrum analysis.Section for the upper painting film in KBr method, it is possible to use the upper painting film that peels,
Or use the 80% or deeper part that upper painting film is coated with from the scraping of its surface coating thickness.Or, it is possible to use in system
The sample of the upper painting film additionally prepared when making painting film.
The above-mentioned ratio A/B situation less than 1.1 represents, has also been uniformly dispersed curing silicone in the inside of upper painting film.
Thus, if above-mentioned ratio A/B is less than 1.1, the amount of the curing silicone the most sometimes occurred on the surface of upper painting film is insufficient.Cause
This, can not obtain the soil resistance of coated steel plate sometimes fully.It addition, the amount of the curing silicone existed inside upper painting film is relatively
Many, the adhesion of upper painting film reduces, and the upper film that is coated with peels off sometimes.On the other hand, if above-mentioned ratio A/B is more than 100, then upper painting
The amount of the curing silicone of the near surface of film is more, sometimes produces and is expanded system by the line of polyimides under high temperature with curing silicone
Count difference causes, above-mentioned peeling and the reduction of soil resistance.
From embody above-mentioned upper painting film film part peel off prevent with both soil resistances from the viewpoint of, preferably
Above-mentioned A is 0.1～1.0.If above-mentioned A is less than 0.1, soil resistance is insufficient the most sometimes.If above-mentioned A is more than 1.0, the most sometimes produce
The part stating painting film is peeled off.For above-mentioned B, it is defined the most especially, but owing to curing silicone is generally coated with upper
Being non-uniformly distributed in its surface in film, the most above-mentioned B is usually 0.01～0.09.
[manufacture method of coated steel plate]
Above-mentioned coated steel plate can manufacture by the following method, and the method includes: the first operation, is comprising the application of steel plate
Coat coating on raw sheet, form the layer of coating；And second operation, by the layer of coating is heated,
By its roasting in application raw sheet, form above-mentioned upper painting film.It is being capable of in the range of the effect of the present invention, this manufacture method
Other operations can also be farther included.
[the first operation]
Application raw sheet can be steel plate itself, it is also possible to be the steel plate with above-mentioned chemical conversion treatment epithelium, it is also possible to
It 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 by bottom-coating
The surface of film, and carry out roasting and make.
Bottom-coating such as can be by by the resin of above-mentioned primary coat film or its material such as presoma, additive and molten
Agent carries out mixing to prepare.
Above-mentioned solvent can be one can also be two or more.As the example of solvent, including: N-methyl-2-pyrroles
Alkanone (NMP) or DMF (DMF), N,N-dimethylacetamide (DMAc), N, N-dimethyl-imidazolinone
(DMI), the aprotic polar solvent such as hexone (MIBK)；Diethylene glycol dimethyl ether (DMDG) or diethyl carbitol
(DEDG) ethers such as；The halogenated aliphatic hydrocarbons such as dichloromethane or carbon tetrachloride；The hydrocarbon such as dimethylbenzene；And alcohol.
Bottom-coating can be coated with by the known method such as rolling method, flow coat method, curtain stream method, stick coating method and spraying process
Cover.For the sintering temperature of primary coat film, the most preferably make the temperature that arrival temperature is 150～400 DEG C of steel plate, the most above-mentioned
Roasting time is 30～180 seconds.
Above-mentioned coating contains the presoma of polyimides, curable silicone and solvent.Coating can also enter one
Step is containing other compositions such as above-mentioned alumina particles.The presoma of polyimides is on consisting of the heating etc. in the second operation
It is coated with the polymer of film, e.g. becomes the polymer of above-mentioned polyimides by heat-blockage cyclization or be dissolved in coating
Polyimides etc..That is, as the example of presoma of polyimides, including polyamic acid and soluble polyimide.
Curable silicone is such as made up of silicone and the functional group constituted with siloxanes component unit.This functional group passes through
Heat, active energy beam, catalyst etc. are combined with silicone or are bonded to each other by functional group.As the example of functional group, including: second
Thiazolinyl or (methyl) acryloyl group etc. have hydroxyl silicyl, the methoxyl group such as the group of carbon-carbon double bond, monohydroxy silicyl
The alkoxysilyls such as silicyl, hydroxyl, methanol-based, phenolic group, epoxy radicals, amino, NCO.
For the molecular weight of above-mentioned curable silicone, if too small, then there is the tendency that the curable of silicone reduces, if mistake
Greatly, it is likely that viscosity improves, it is impossible to occur in fully on the surface of painting film.From this point of view, preferably go up
The quantity stating the siloxanes component unit in curable silicone is 2～5000, more preferably 10～2000.Above-mentioned component unit
Quantity can be passed through gel permeation chromatography (GPC) and measure.
It addition, from the viewpoint of reactivity, the equivalent (g/mol) of the above-mentioned functional group in preferred consolidation silicone is 2
～60000, more preferably 10～30000.The equivalent of above-mentioned functional group such as can be surveyed by nuclear magnetic resonance, NMR optical spectroscopy (NMR)
Fixed.
As the example of curable silicone, including various modified silicones, as the example of this modified silicone, including: amino
Modified silicone, carbinol-modified silicone, acrylic modified silicone, ethylene modified silicone, silanol-modified silicone, phenol-modified
Silicone, epoxy-modified silicone, NCO modified silicone, polyether modified silicone.Point from long-term resistance to food pollution
From the point of view of, particularly preferably polyether modified silicone.
Solvent can be one can also be two or more.Intermiscibility from the presoma of polyimides Yu curable silicone
Raising or the viewpoint such as the adjustment of viscosity of coating use solvent.Solvent for coating, it is possible to use with upper
State the solvent that the solvent phase of bottom-coating is same.The solvent of coating can be one can also be more than one, can be the end of with
The solvent phase of painting coating is same can also be different.Furthermore it is possible to by the method identical with the painting method of bottom-coating, by upper painting
Coating is coated on steel plate, chemical conversion treatment epithelium or the surface of primary coat film.
The above-mentioned curable silicone of the presoma relative to the 100 above-mentioned polyimides of mass parts in above-mentioned coating
Content is more than 1.0 mass parts.If above-mentioned content is less than 1.0 mass parts, the curing silicone in the upper surface being coated with film
Occupied area rate less than 5%.As it has been described above, from preventing by reusing the reduction of the soil resistance caused or upper painting film
From the viewpoint of partly peeling off the reduction of the soil resistance caused, the preferably content of the above-mentioned curable silicone in coating is relative
Presoma in 100 mass parts polyimides is 1～10 mass parts, more preferably 2～6 mass parts.
Preferably coating is coated on steel plate, chemical conversion treatment in the way of making the thickness of upper painting film be 2～20 μm
Reason epithelium or primary coat film.The thickness of upper painting film can be adjusted by the thickness (coated weight of this coating) of the layer of coating
Whole.The thickness of the layer of coating can be by the viscosity of coating or the painting method of this coating, the coating time of this coating
Numbers etc. adjust.
[the second operation]
In second operation, in the way of making the arrival temperature of steel plate be more than 180 DEG C, at least to curable silicone
The layer dividing the coating floated on surface heats, and formation is coated with film.Here, " at least of curable silicone
Divide the layer of the coating floated on surface " refer to, this layer that a part for curable silicone is just occurring on its surface, this
Outward, the part also including curable silicone gradually arrives its surface but and this layer of occurring on surface is (substantially it is believed that just
This layer occurred on surface).
In the case of curable silicone has Thermocurable, the forerunner of polyimides can be carried out by above-mentioned heating
The imidizate of body and the solidification of curable silicone.In the case of curable silicone does not have above-mentioned Thermocurable, above-mentioned system
The method of making can also farther include to make the operation of curable silicone cure.Such as, at curable silicone, there is photo-curable
In the case of, the most further the polyimide film formed by this heating process can be irradiated light by carrying out above-mentioned heating process
And make curable silicone cure.Further, at curable silicone, there is both Yin Re and light and in the case of the character that solidifies, on
State manufacture method to farther include the irradiation of the surface to upper painting film and make curable silicone after above-mentioned heating process
The operation of the light of solidification.In this case the curable silicone that can make the surface of painting film cures sufficiently, thus preferably.Make
The example of the light for irradiating, including ultraviolet.
If above-mentioned arrival temperature is less than 180 DEG C, even if then curable silicone has Thermocurable, the solidification of curable silicone
The most insufficient, the upper film that is coated with shows viscous sense sometimes, and the processability of coated steel plate is due to the uncured of curable silicone
Reduce.It addition, sometimes produce owing to the polyimides under high temperature causes from the different of the linear expansion coefficient of curable silicone
Peel off and the reduction of soil resistance.If above-mentioned arrival temperature is more than 200 DEG C, then from the presoma promptly carrying out polyimides
Polyimides from the viewpoint of, be preferred.
By the layer of above-mentioned coating is heated so that it arrives above-mentioned arrival temperature or by entering one behind
Step includes the suitable operation of the solidification for curable silicone, it is possible to suitably go out on the surface of upper painting film at curable silicone
Under existing state, carry out polyimides and the heat cure of curable silicone of the presoma of polyimides in this layer, formed
Above-mentioned upper painting film.Emersion amount in this layer, curable silicone can be by the heating speed after the layer of formation coating
Waiting time or above-mentioned arrival temperature before degree, heating are adjusted.I.e., both can be while the layer of coating have been heated
While making curable silicone emersion, it is also possible to make curable silicone to keep this state after the abundant emersion of layer of coating
Mode heat rapidly.From the viewpoint of the desired distribution of the curable silicone stably realized in film, excellent
Select the latter.
In the former case, from the viewpoint of the distribution of the curable silicone being coated with from controlling in the surface of film, excellent
Selecting from coating is coated on the application raw sheet temperature to steel plate reaching time (heat time heating time) of above-mentioned arrival temperature is 30
～240 seconds.If being less than above-mentioned heat time heating time 30 seconds, the amount of the curable silicone the most sometimes occurred on the surface of upper painting film is not filled
Point.If above-mentioned heat time heating time was more than 240 seconds, the amount of the curable silicone the most sometimes occurred on the surface of upper painting film is too much.From
From the viewpoint of so, the most above-mentioned heat time heating time is 30～240 seconds.
In the latter case, preferably from coating being coated on the application raw sheet time to heating beginning (during wait
Between) it is 5～60 seconds.If the above-mentioned waiting time is less than 5 seconds, curable silicone cannot be in the surface of the layer of coating the most sometimes
Occurring fully, the amount of the curable silicone of the inside of this layer is more.In this case, as it has been described above, painting on sometimes
The adhesion of film reduces, and upper painting film peels off.If the above-mentioned waiting time was more than 60 seconds, the most substantially curable silicone of full dose exists
The surface of the layer of coating occurs, sometimes produces the linear expansion coefficient due to the polyimides under high temperature and curing silicone
Peeling that difference causes and the reduction of soil resistance.The above-mentioned waiting time such as can by coating coating unit and
The transporting velocity of the steel plate between the heater of steel plate is adjusted.
It addition, heat time heating time in the latter case, i.e. after the above-mentioned waiting time terminates, temperature to steel plate reaches
Time till above-mentioned arrival temperature is 30～180 seconds, and this, from the viewpoint of identical with the former heat time heating time, is preferred
, more preferably 30～150 seconds.
Fig. 2 A is the figure of the trend of the composition in the layer schematically showing coating.As shown in Figure 2 A, it is coated with upper
Material layer 31 in, the solvent 311 represented by white triangle (△) in Fig. 2 A evaporates, in Fig. 2 A by consolidating that white circle (zero) represents
The property changed silicone 312, by the surface free energy difference with base resin (presoma of polyimides), moves to the surface of this layer.This
Time it is believed that the liquid particles of curable silicone is assembled while moving to the surface of this layer on one side the most each other.
Fig. 2 B is the figure of the state on the surface of be present in coating layer with schematically showing curable dispersion.
As shown in Figure 2 B, can by the gathering of the aforesaid liquid granule of the curable silicone of the surface appearance of the layer at coating not
When fully carrying out, this layer heated, make it solidify, be produced on its surface and there is the upper painting film of trickle island structure,
This island structure is dispersed with trickle island (island is curable silicone) (with reference to Fig. 3 A).
Fig. 2 C is the figure of the state schematically showing curable silicone after the surface aggregation of the layer of coating, Fig. 3 B
Be represent curable silicone assemble after upper painting film surface, the backscattered electron image that shot by scanning electron microscope
Electron micrograph.As shown in Figure 2 C, if making the aforesaid liquid of the curable silicone occurred on the surface of the layer of coating
Granule is fully assembled, then, as shown in the photo of Fig. 3 B, can be produced on its surface and have the island structure that there is bigger island
Upper painting film.The no matter island in which kind of island structure, its thickness is the thinnest to number 10nm degree.
The thermostability of upper painting film is mainly brought by polyimides, and the soil resistance on the surface of upper painting film is mainly by solidification silicon
Ketone brings.Thus, in the upper painting film formed by the layer of the coating as shown in Fig. 2 B or Fig. 2 C, owing to there is solidification silicon
The island of ketone, so higher soil resistance can be embodied.
Fig. 4 is the figure of the island structure schematically shown in painting film and the fluid contaminants being attached to this film.
The trickle island structure that the dispersion phase that upper painting film 51 has the continuous phase by polyimides 513 and curing silicone 512 is constituted.
As shown in Figure 4, the pollutant 514 of liquid are attached to the surface of painting film 51.Drop phase with pollutant 514
Ratio, the island of the curing silicone 512 in island structure is the least.It addition, the island of the curing silicone 512 in the surface of upper painting film 51
Density the highest.Therefore, the drop of pollutant 514 crosses over multiple islands, is attached to the surface of painting film 51.
Compared with the polyimides 513 as sea, the surface tension as the curing silicone 512 on island is less, therefore pollutes
The drop of thing 514 is at the work being subject on the direction big with the change of the contact angle of this contact surface with the contact surface on island structure Zhong Ge island
With.Accordingly, it is believed that excellent liquid repellency is embodied on the surface of upper painting film 51, it is easy to remove the drop of pollutant 514, separately
Outward, heating time be difficult to pollutant cooked-on.
So, from the viewpoint of the contact of the drop relative to attachment, it is believed that the anti-fouling effect being above coated with film 51 is
(in concavo-convex trickle asperities, multiple gaps that liquid cannot penetrate into are produced, with the apparent contact angle of liquid by with lotus-effect
Becoming big phenomenon) identical effect brings.
Understand according to the above description, by making curing silicone stably be distributed in the upper painting of resin based on polyimides
The surface of film, it is possible to formed and there is the thermostability of excellence and hydrophilic and oil loving liquid component are all had excellence
The upper painting film of soil resistance.Particularly from the viewpoint of the durability improving soil resistance and uniformity, at the table of upper painting film
It is more effective that face builds the trickle island structure with curing silicone as island.
As it has been described above, both the thermostability of the coated steel plate of the present invention and soil resistance are excellent.Thus, especially for antifouling
Property, by using above-mentioned trickle island structure, thus the soil resistance more excellent relative to the dirty embodiment of liquid.Thus, suitable
In as can with the utensils for cooking such as steam-heated microwave oven, for being constituted as the heating chamber of this microwave oven 350
The parts or its pre-coated steel plate that use and produce the part of drop attachment at a temperature of about DEG C use.
Hereinafter, with reference to embodiment, the present invention is described in detail, but the invention is not restricted to these embodiments.
[embodiment]
[preparation of polyimide precursor A～E]
In the delivery flask of 300mL, it is taken into DMAc (N,N-dimethylacetamide) 120.3g as solvent and conduct
The 1 of diamidogen, double (3-amino-benzene oxygen) benzene (Mitsui Chemicals, Inc's system) 23.0g (78.7mmol) of 3-also makes it dissolve.?
Wherein add the pyromellitic dianhydride (1,2,4,5-benzene tertacarbonic acid's dianhydride) (Co., Ltd.'s Daicel system) as tetracarboxylic dianhydride
17.1g (78.3mmol), has obtained the varnish A containing polyimide precursor (polyamic acid) A.
Employ DMAc138.3g, and employ 4,4 '-bis-(3-amino-benzene oxygen) biphenyl (Mitsui Chemicals of 78.7mmol
Co., Ltd.'s system) as diamidogen, in addition, with the method identical with varnish A obtained containing polyimide precursor B clear
Paint B.
Employ DMAc103.1g, employ 4 according to mol ratio 9:1, and 4 '-epoxide diaminobenzene (4,4 '-diaminourea hexichol
Base ether) (Nippon Seika K.K.'s system) and (1,3-double (3-amino-benzene oxygen) benzene amount to 78.7mmol as diamidogen, and according to
Mol ratio 9:1 employs pyromellitic dianhydride (1,2,4,5-benzene tertacarbonic acid's dianhydride) and 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride
(Co., Ltd.'s Daicel system) 78.3mmol altogether, as tetracarboxylic dianhydride, in addition, obtains with the method identical with varnish A
Varnish C containing polyimide precursor C.
Employ DMAc101.0g, employ the 4 of 78.7mmol, and 4 '-epoxide diaminobenzene (4,4 '-diamino-diphenyl
Ether) as diamidogen, employ pyromellitic dianhydride (1,2,4,5-benzene tertacarbonic acid's dianhydride) and 3 according to mol ratio 9:1,3 ', 4,4 '-two
Benzophenonetetracarboxylic dianhydride (Co., Ltd.'s Daicel system) amount to 78.3mmol as tetracarboxylic dianhydride, in addition, with clearly
Method identical for paint A has obtained the varnish D containing polyimide precursor D.
Employing DMAc98.7g, employ the 4 of 78.7mmol, 4 '-epoxide diaminobenzene is as diamidogen, in addition, with
The method identical with varnish A has obtained the varnish E containing polyimide precursor E.
Obtained by the raw material i.e. diamidogen (DA) of polyimide precursor (PIpre) A～E and tetracarboxylic dianhydride (TD) and
The glass transition temperature Tg of this presoma is as described in Table 1.The content of polyimide precursor A～E in varnish A～E
It is 25.0 mass %.
[table 1]
[preparation of coating]
Prepare curable silicone F～H shown in table 2 below.Curable silicone F～H is solidified by heat
Thermocurable silicone.The proportion (SG) of curable silicone F～H, viscosity (Vis), the equivalent (EW of functional groupFG), 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 trade mark of the said firm.“X22-
4039 " it is 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 varnish A described later, solvent, pigment dispersing agent, coloring pigment, adds appropriate glass
Beadlet, utilizes coating shakeout machine that these plastic containers have been shaken 8 hours.Afterwards, glass beads is removed, to obtained mixed liquor
Middle interpolation curable silicone F, uses propeller type mixer to be stirred this mixed liquor with 1000rpm, is prepared for being coated with
Coating (coating) a of film.The containing ratio of the nonvolatile component (solid constituent) in coating a is 22.13 mass %.
Additionally, " white carbon black MA100 " is Mitsubishi chemical Co., Ltd's system." DISPERBYK-130 " is Bi Ke chemical company system,
" DISPERBYK " is the registered trade mark of the said firm.It addition, the containing ratio of nonvolatile component is, polyimide precursor, heat cure
The total (28.56 mass parts) of the nonvolatile component in property silicone, coloring pigment and pigment dispersing agent is relative to aftermentioned material
The ratio of total amount (129.05 mass parts).
The raw material shown in table 3 is employed according to the amount shown in Table 3 below, in addition, 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 " represents the content of varnish,
" PI-pre " represents polyimide precursor, and " Cnv1 " represents the content of the nonvolatile component in varnish, and " S-pre " represents solidification
Property silicone, " Cs " represents the content of curable silicone, and " Csol " represents the content of solvent, and " Cpig " represents the containing of coloring pigment
Amount, " Cda " represents the content of pigment dispersing agent, and " Ctotal " represents the total of the content of each composition, and " Cnv2 " represents painting
The content of the nonvolatile component in material, and, " RS/P" represent the curable silicon relative to polyimide precursor 100 mass parts
The mass fraction of ketone.Content beyond Cnv1 is the content in upper painting film.
[table 3]
[making of coated steel plate 1～30]
Having prepared Surface Finishing is the plate (thickness of slab: 0.4mm) that No.4 grinds the SUS430 of polish.And, carry 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 %) is after the surface spraying of above-mentioned stainless-steel sheet, with 60 DEG C of hot water cleanings 10 seconds, then
Carry out the process washed.Chemical conversion treatment is, the NRC300 of Nippon Paint Co., Ltd. is coated on above-mentioned rustless steel steel
The surface of plate is so that Cr adhesion amount is 50mg/m2, then the arrival temperature at above-mentioned stainless-steel sheet is right at a temperature of 80 DEG C
The chromate that coating liquid is dried processes.
Then, the chemical conversion treatment skin on the surface of the stainless-steel sheet after Coating Pretreatment, i.e. stainless-steel sheet
On film, utilize bar coater coating coating a so that dry film thickness is 5 μm, stainless-steel sheet defines coating a's
Layer.
Then, the arrival temperature at stainless-steel sheet is at a temperature of 350 DEG C, heats the layer of coating a, will
This layer of roasting, on stainless-steel sheet, has obtained the coated steel plate 1 with the upper painting film formed by this layer.At coated steel plate 1
Making in, from coating coating a after to heating start waiting time be 15 seconds, start to reach above-mentioned arrival from heating
The heat time heating time of temperature is 130 seconds.
As shown in table 4 below and 5, change the kind of coating, waiting time, heat time heating time and be covered with painting from painting
To the time of roasting after coating, in addition, in the same manner as coated steel plate 1, make coated steel plate 2～29 respectively.And, right
In each of coated steel plate 1～29, dry film thickness, occupied area rate, the distribution of curing silicone and shape thereof, island are obtained
The peak strength ratio of maximum area and FT-IR.The kind of the coating in coated steel plate 1～29, upper painting film be dried
Curing silicone in thickness (Tf), waiting time (Tw), heat time heating time (Temp-h), arrival temperature (Temp-a), upper painting film
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 the weight of gravimetric method, i.e. steel plate after application, deduct after utilizing sand-blast etc. mechanically to eliminate film
The weight of steel plate, try to achieve the weight of film, and divided by steel plate area and the method that is coated with film density, tried to achieve dry film thickness.
It addition, use scanning electron microscope, (can clearly grasp distributional pattern with backscattered electron image 100～3000 times
Multiplying power) be coated with the surface of film in observation, shoot the photograph image of this charge pattern at any 5, to obtained photograph image
Carry out digital processing, calculate the area occupation ratio of the part of curing silicone in each photograph image, by the face of the photograph image at above-mentioned 5
The meansigma methods of long-pending rate is set to occupied area rate.
It addition, observe this photograph image, by observe in the continuous phase of polyimides or curing silicone curing silicone or
The situation of the dispersion phase of polyimides is judged to " island " of island structure.It addition, the situation that above-mentioned island structure will not observed
It is judged to " continuously ".Further, the shape on island and the area on island have been tried to achieve.Even if additionally, will be to it is believed that utilize scanning electron to show
The 5mm that the presence or absence of island structure can sufficiently and reasonably be judged by micro mirror2Region arbitrary 5 at observe, also
Do not observe that the situation of island structure is judged to " continuously ".
For the shape on island, calculate the flat ratio ratio of minor face (the long limit with) of the shape on island in this photograph image.
And, by the situation of more than the 95% of number that the number on the island that flat ratio is 0.9～1.1 is whole islands in this photograph image
Be judged to " circular ", by for 80% less than 95% situation be judged to " a part of circular ", will be less than
The situation of 80% is judged to " unsetting ".
As an example, represent the upper painting film in the coated steel plate 3 of embodiment surface, clapped by scanning electron microscope
The electron micrograph of the backscattered electron image taken the photograph is as shown in Figure 3A.Understand, make in coated steel plate 3, on its surface
On there is the upper painting film of the trickle island structure being dispersed with trickle island (island is curing silicone).
It addition, the area on the maximum island in 5 above-mentioned photograph images to be set to the maximum area on island.Being shaped as on island
A part of circular or atypic in the case of, due to the complexity of shape, sometimes be difficult to measure maximum area, try to achieve this situation
Under the maximum area on island as approximation, and be shown in bracket in table 4 and table 5.
It addition, utilize FT-IR ATR method, with angle of incidence: 45 °, measurement range: 1000～3000cm-1Condition to upper painting
The surface of film is measured, and according to the measurement result obtained, tries to achieve 1014cm-1Peak strength (a1) relative to 1375cm-1
The ratio (a1/a2) of peak strength (a2), and be set to " A " in peak strength ratio.It addition, peel upper painting from coated steel plate
Film, or utilize Mini-Plane (Co., Ltd.'s STJAPAN system) etc. to cut to the degree of depth 4 μm to obtain sample strip, by FT-IR to profit
The sample made by KBr method is measured, and according to the result obtained, tries to achieve 1014cm-1Peak strength (b1) relative to
1375cm-1The ratio (b1/b2) of peak strength (b2), and be set to " B " in peak strength ratio.Further, above-mentioned A has been tried to achieve relative
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 contains Thermocurable silicone, does not therefore observe consolidating in film coated surface
The distribution (island) of SiClx ketone.Thus, peak strength all cannot be tried to achieve than A and B of A/B.It addition, for coated steel plate 13, upper painting
Coating m does not contains polyimide precursor, and therefore curing silicone constitutes the entirety of film coated surface, does not observes in film coated surface
The island of curing silicone.Thus, peak strength all cannot be tried to achieve than A and B of A/B.It addition, for coated steel plate 28, curing silicone
For sea, polyimides is distributed as atypic island.It addition, for coated steel plate 19 and coated steel plate 29, " distribution "
Being all " continuously ", therefore whichever coated steel plate all cannot try to achieve " maximum area (Smax) on island ".
Further, do not carry out above-mentioned chemical conversion treatment, in addition, in the same manner as coated steel plate 3, made coated steel plate
30.For the upper painting film of coated steel plate 30, having carried out observing, measuring in the same manner as coated steel plate 1, its result is: solidification silicon
The occupied area rate of ketone is 35%, and distribution is " island ", and distribution shape is " circular ", and the maximum area on island is 100 μ
m2, peak strength is 30 than A/B.
[evaluation]
For project described later, coated steel plate 1～30 is evaluated.
[film adhesion]
(1) processing adhesion (Ad-1)
To each of coated steel plate 1～30, determine the part of about 2 times of width 70mm and a length of width, will
After upper painting film carries out 2T bending as table side, processing department (part of bending) is tried to achieve and is utilizing adhesive tape to carry out adhesive tape stripping
The survival rate of the upper painting film after from, and evaluated by following benchmark.Additionally, eliminating the two ends 10mm of bending part
In the region of 50mm, utilize scale to measure the size of the remaining part of film, and calculate the area of this remnant relative to this
The ratio of the area in the region of 50mm width, has tried to achieve the survival rate of upper painting film.
(metewand of film adhesion)
A: survival rate is 100%
B: survival rate is 95% less than 100%
C: survival rate is 90% less than 95%
D: survival rate is 80% less than 90%
E: survival rate is 70% less than 80%
F: survival rate is 50% less than 70%
G: survival rate is less than 50%
(2) water-fast secondary adhesion (Ad-2)
After coated steel plate 1～30 be impregnated in boiling water 2 hours respectively, try to achieve and implement the upper cross-hatching adhesive tape stripping being coated with film
Film survival rate after from, and evaluated by above-mentioned metewand.
[thermostability]
For each of coated steel plate 1～30, respectively with the temperature keeping 24 hours of 250 DEG C, 300 DEG C and 350 DEG C
After, try to achieve and implement the film survival rate after the upper cross-hatching adhesive tape being coated with film is peeled off, and evaluated by above-mentioned metewand.
[resistance to food pollution]
(1) the resistance to food pollution (AP-1) at initial stage
The upper painting film of each of the coated steel plate 1～30 of not test (N.T.) state is placed food, to this painting steel loading
After plate was with 250 DEG C of heating 1 hour, seen utilizing napkin that when coated steel plate is wiped, food contaminant is wiped state
Examine.Food employs salad oil, butter, soy sauce and dip these four, and observe every kind of food variety wipes state.And press
State metewand to be evaluated.
(metewand of resistance to food pollution)
A: each food can be by easily removing with napkin wiping
B: each food can be by removing (noresidue) with napkin friction
C:1 kind food by removing with napkin friction, but can have residual (other 3 kinds can remove)
Even if D:1 kind food can not remove (other 3 kinds can remove) with napkin friction
Can not (other 2 kinds can remove) even if E:2 kind food can not remove with napkin friction
Can not (other a kind can remove) even if F:3 kind food can not remove with napkin friction
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, has carried out above-mentioned (1)
The test of condition, each food is wiped state and is observed, and evaluated by above-mentioned metewand.
(3) the resistance to food pollution (long run test, AP-3) when using continuously
The test of the condition of 10 times above-mentioned (1) is repeated, the wiping to each food of the 10th time with identical coated steel plate
Fall state to be observed, and evaluated by said reference.
Result is as shown in table 6.
[table 6]
[making of clear-coated steel plate, evaluation]
Use propeller type mixer with 1000rmp, raw material described later to be stirred, be prepared for the painting of painting film
Material (clear dope).That is, unmixed coloring pigment and pigment dispersing agent, in addition, be prepared as with coating c thoroughly
Bright coating.The content of the nonvolatile component of this clear dope is 16.83 mass %, relative to polyimide precursor (P) 100 matter
The amount of the curable silicone (S) of amount part is 5.0 mass parts.
Varnish C 100 mass parts
Curable silicone F 1.25 mass parts
N,N-dimethylacetamide 25 mass parts
Use above-mentioned clear dope, in addition, in the same manner as coated steel plate 1, make coated steel plate 31.For application
The upper painting transparent coating of steel plate 31, has carried out observing, measuring in the same manner as coated steel plate 1, and its result is: occupying of curing silicone
Area occupation ratio is 35%, and distribution is " island ", and distribution shape is " circular ", and the maximum area on island is 100 μm2, peak value is strong
Degree is 30 than A/B.
It addition, for coated steel plate 31, be respectively directed to above-mentioned film adhesion, thermostability and resistance to food pollution and carry out
Evaluate, obtained the result identical with the coated steel plate 3 in table 6.
[making of coated steel plate 32,33]
Hot-dip Al-9%Si steel plate (thickness of slab: 0.4mm, single-face plating adhesion amount 40g/m are prepared2) as steel plate.Enter
Go above-mentioned alkali degreasing as Coating Pretreatment, carry out Ti system chromium-free treatment as chemical conversion treatment.Employ fluotitanic acid
(H2TiF6: 0.1mol/L) as chemical conversion treatment solution, this chemical conversion treatment solution is coated on the surface of above-mentioned clad steel sheet
So that the adhesion amount of Ti is 10mg/m2, and make it be dried.
On the other hand, the polyimide precursor B of 100 mass parts adds aluminium dihydrogen tripolyphosphate magnesium 30 mass parts
As rust resisting pigment, it is prepared for primary coat film coating.This primary coat film coating is coated on the chemistry of above-mentioned clad steel sheet
Conversion processing epithelium, so that dry film thickness is 5 μm, heats with the temperature that arrival temperature is 280 DEG C of clad steel sheet, makes
The primary coat film that is made up of polyimides.
On the surface of room temperature, made primary coat film, coating c is entered with the condition identical with coated steel plate 3
Row coating, heating, made upper painting film.So, coated steel plate 32 has been made.It addition, do not make primary coat film, except this with
Outward, in the same manner as coated steel plate 32, make coated steel plate 33.
[evaluation]
It is respectively directed to above-mentioned film adhesion, thermostability and resistance to food pollution, coated steel plate 32,33 is commented
Valency.Further, coated steel plate 32,33 is evaluated for corrosion resistance described later.
[corrosion resistance]
At par (part beyond the section of end) the mark signature lattice of coated steel plate 32 and 33, at the ring keeping 35 DEG C
Border implements the salt spraytest (according to SST, JIS Z2371) sprayed the film of coated steel plate with 5% saline
240 hours.After experiment, the maximum swelling width in crossed grid portion is observed, and press and state metewand and commented
Valency.Result is as shown in table 7.
(metewand of corrosion resistance)
A: maximum swelling width is less than 1mm
B: maximum swelling width is that 1mm is less than 2mm
C: maximum swelling width is that 2mm is less than 3mm
D: maximum swelling width is that 3mm is less than 4mm
E: maximum swelling width is more than 4mm
[table 7]
Coated steel plate 1～5,7～11 and 14～33, all in film adhesion, thermostability, resistance to food pollution, is demonstrated by
At least as the performance that cooking appliance parts are the most no problem.Coated steel plate 32 and 33 in corrosion resistance,
It is demonstrated by least the most no problem as cooking appliance parts performance further.
To this, the resistance to food pollution of coated steel plate 6 is the most insufficient.This is it is believed that be coated with due to upper
The occupied area rate of the curing silicone in the surface of film is 4%, thus insufficient.It addition, the resistance to food pollution of coated steel plate 12
Property is the most insufficient.This may be considered and (is above coated with film not owing to, the base material of upper painting film is only polyimides
Containing curing silicone).Further, the film adhesion of coated steel plate 13, thermostability and resistance to food pollution are the most in actual use
Insufficient.This may be considered owing to, the base material of upper painting film is only curing silicone (be above coated with film and do not contain polyimides).
In sum, it is known that following coated steel plate as the coated steel plate of cooking appliance parts at thermostability and antifouling
Upper excellence both property, this coated steel plate is consisted of overlapping steel plates successively and film, and above-mentioned film includes painting film, on
State painting film comprise polyimides and curing silicone and constitute the surface of coated steel plate, in the surface of above-mentioned upper painting film
The occupied area rate of curing silicone is more than 5%.
It addition, such as compared with coated steel plate 6, coated steel plate 3,7 is all more excellent in resistance to food pollution.It addition, example
As compared with coated steel plate 9, more excellent in coated steel plate 3,8 all resistance to food pollutions after heat resistant test.In sum, may be used
The content knowing the curing silicone in upper painting film is 1～10 mass parts relative to polyimides 100 mass parts, and this is from soil resistance
It is more effective from the viewpoint of durability.
It addition, such as compared with coated steel plate 6, coated steel plate 3,7,14 is all more excellent in resistance to food pollution.It addition,
Such as compared with coated steel plate 9, more excellent in coated steel plate 3,8,17 all resistance to food pollutions after heat resistant test.To sum up institute
State, it is known that above the occupied area rate of the curing silicone in the surface of film is 5～70%, and this is from the sight of the durability of soil resistance
From the point of view of Dian, it is more effective.
It addition, such as compared with coated steel plate 29, the coated steel plate 3 resistance to food after heat resistant test and in long run test is dirty
In metachromia more excellent.In sum, it is known that above the surface of film is the island structure of polyimides and curing silicone, this is from anti-
From the viewpoint of the durability of dirt, it is more effective.It addition, such as compared with coated steel plate 28, coated steel plate 27 is heat-resisting
In resistance to food pollution after test more excellent.In sum, it is known that above the surface of film be sea based on polyimides and
The island structure on the island of curing silicone, this is from the viewpoint of the durability of soil resistance, is more effective.
It addition, in coated steel plate 15～18, compared with coated steel plate 18, coated steel plate 15～17 is after heat resistant test
In resistance to food pollution more excellent.It addition, in coated steel plate 20～22, the resistance to food after film adhesion, heat resistant test is dirty
In resistance to food pollution in metachromia and long run test the most excellent according to the order of coated steel plate 20,21,22.To sum up
Described, it is known that above the area on the island of each curing silicone in the surface of film is 300 μm2Below or the table of upper painting film
The island of the curing silicone in face substantially circular in shape, this viewpoint from the durability of soil resistance or the sight from film adhesion
From the point of view of Dian, it is more effective.
It addition, in coated steel plate 15～18, coated steel plate 15,16 is than resistance to after heat resistant test of coated steel plate 17,18
In food pollution more excellent.It addition, in coated steel plate 24～27, coated steel plate 25,26 than coated steel plate 24 at resistance to food
In contaminative more excellent, more excellent than in the coated steel plate 27 resistance to food pollution after heat resistant test and in long run test.Combine
Upper described, it is known that by by infrared spectrum analysis based on ATR method on the surface of film be measured time,
1014cm-1Peak strength relative to 1375cm-1The ratio of peak strength be defined as A, and by by based on KBr method infrared
When upper painting film is measured by spectrum analysis, 1014cm-1Peak strength relative to 1375cm-1The ratio of peak strength
When being defined as B, the A ratio A/B relative to B is 1.1～100, and this is from the viewpoint of the durability of soil resistance, is more effective.
It addition, in coated steel plate 1～5, for the thermostability at 250 DEG C, coated steel plate 2～5 is more excellent than coated steel plate 1
Different, for the thermostability 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
Thermostability 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.It addition, for the resistance to food pollution at 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, and this is from heat-resisting
From the viewpoint of the durability of property and soil resistance, it is more effective.
It addition, in coated steel plate 20～23, for film adhesion, according to the order of coated steel plate 20,21,22,23
The most excellent, for thermostability, each coated steel plate is substantially good, for the resistance to food after heat resistant test and in long run test
Product contaminative, 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
More excellent.In sum, it is known that the manufacture method of following coated steel plate includes: be coated with at the application raw sheet comprising steel plate and be covered with painting painting
Material, forms the operation of the layer of coating；And by the layer of coating is heated, by its roasting in application raw sheet shape
Being coated with the operation of film on one-tenth, coating contains the presoma of polyimides, curable silicone and solvent, so that steel plate
Arrive the mode that temperature is more than 180 DEG C, the layer to the coating floated at least partially on surface of curable silicone
Heating, film in formation, the method can provide the coated steel plate that both thermostability and soil resistance are excellent, as cooking
Adjust the coated steel plate of utensil parts.
It addition, in coated steel plate 24～27, coated steel plate 25,26 than coated steel plate 24 in resistance to food pollution more excellent
Different, more excellent than in the coated steel plate 27 resistance to food pollution after heat resistant test and in long run test.In sum, it is known that from
Coating being coated on application raw sheet to the time (waiting time) begun to warm up is 5～60 seconds, and this is from providing soil resistance
From the viewpoint of the coated steel plate of excellent in te pins of durability, it is more effective.
It addition, in coated steel plate 24,25, coated steel plate 25 is more excellent than coated steel plate 24 in resistance to food pollution.Separately
Outward, in coated steel plate 27,29, more excellent than coated steel plate 29 in the coated steel plate 27 resistance to food pollution after heat resistant test.
In sum, it is known that from begin to warm up reach arrive temperature time (roasting time) be 30～240 seconds, this from provide antifouling
From the viewpoint of the coated steel plate of the excellent in te pins of durability of property, it is more effective.
It 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 more excellent than coated steel plate 21.In sum, it is known that the arrival temperature of steel plate is more than 200 DEG C, this
From the viewpoint of the coated steel plate of excellent in te pins of durability that film adhesion and soil resistance are provided, it is more effective.
It addition, in coated steel plate 14,15, than being coated with steel loading in the coated steel plate 15 resistance to food pollution in long run test
Plate 14 is excellent.It addition, in coated steel plate 16,17, coated steel plate 16 compares application in the resistance to food pollution after heat resistant test
Steel plate 17 is excellent.In sum, it is known that from the viewpoint of the coated steel plate of excellent in te pins of durability that soil resistance is provided, be coated with and be covered with painting
Coating is so that the thickness of upper painting film is 2～20 μm is more effective.
It addition, such as coated steel plate 3,7 all than coated steel plate 6 in resistance to food pollution more excellent.It addition, such as application
Steel plate 3,8 is all more excellent than in the coated steel plate 9 resistance to food pollution after heat resistant test.In sum, it is known that coating
In the content of curable silicone be 1～10 mass parts relative to the presoma of 100 mass parts polyimides, this is from providing antifouling
From the viewpoint of the coated steel plate of the excellent in te pins of durability of property, it is more effective.
It addition, such as coated steel plate 3 than coated steel plate 30 in film adhesion more excellent.In sum, it is known that from carrying
For from the viewpoint of the coated steel plate that film adhesion is excellent, it is more effective for having chemical conversion treatment epithelium on the surface of steel plate
's.
The application is willing to 2014-072302 claims priority based on the Japanese patent application laid proposed on March 31st, 2014
Power.Content described in the description of this application and accompanying drawing all refers in present specification.
Industrial applicibility
The coated steel plate of the present invention the surface of upper painting film with this on film surface in more than 5% occupy face
Long-pending rate contains curing silicone.Therefore, compared with the coated steel plate that the surface at upper painting film has fluororesin, have equal or
While more excellent soil resistance, there is higher thermostability.Thus, the coated steel plate of the present invention is applicable at higher temperature
The material of the equipment of soil resistance is needed under environment.Thus, according to the coated steel plate of the present invention, can expect that it contributes to passing through
The more special heating such as the heating of higher temperatures or steam heating carry out the further development of the heating and cooking appliance cooked.
Claims (15)
1. a coated steel plate, has film on steel plate, wherein,
Described film includes painting film,
Described upper painting film contains polyimides and curing silicone,
The occupied area rate of the described curing silicone in the surface of described upper painting film is more than 5%.
2. coated steel plate as claimed in claim 1, wherein,
The content of the described curing silicone in described upper painting film is 1～10 mass relative to polyimides described in 100 mass parts
Part.
3. coated steel plate as claimed in claim 1 or 2, wherein,
The occupied area rate of the described curing silicone in the surface of described upper painting film is 5～70%.
4. the coated steel plate as described in any one in claims 1 to 3, wherein,
In the surface of described upper painting film, described polyimides and described curing silicone are formed as island structure.
5. coated steel plate as claimed in claim 4, wherein,
The island of described curing silicone substantially circular in shape, the area on the island of each described curing silicone is 300 μm2Below.
6. the coated steel plate as described in any one in Claims 1 to 5, wherein,
By by infrared spectrum analysis based on In situ ATR-FTIR method to when the surface of film is measured on described
, 1014cm-1Peak strength relative to 1375cm-1The ratio of peak strength be defined as A,
And by when described upper painting film being measured by infrared spectrum analysis based on pellet technique, 1014cm-1
Peak strength relative to 1375cm-1The ratio of peak strength when being defined as B,
The described A ratio relative to described B is 1.1～100.
7. the coated steel plate as described in any one in claim 1～6, wherein,
The glass transition temperature of described polyimides is 270～400 DEG C.
8. a manufacture method for coated steel plate, including:
The application raw sheet comprise steel plate coats coating, forms the operation of the layer of coating；And
By the layer of described coating is heated, by its roasting in described application raw sheet, thus form upper painting film
Operation,
Described coating contains the presoma of polyimides, curable silicone and solvent,
The content of the described curable silicone relative to the presoma of polyimides described in 100 mass parts in described coating
It is more than 1.0 mass parts,
At least some of floating in the way of making the arrival temperature of described steel plate be more than 180 DEG C, to described curable silicone
The layer of the described coating on surface heats, and forms described upper painting film.
9. the manufacture method of coated steel plate as claimed in claim 8, wherein,
It it is 5～60 seconds from described coating being coated on described application raw sheet to the time started described heating.
10. the manufacture method of coated steel plate as claimed in claim 8 or 9, wherein,
It it is 30～240 seconds from being heated to the time till reaching described arrival temperature described in beginning.
The manufacture method of 11. coated steel plates as described in any one in claim 8～10, wherein,
The arrival temperature of described steel plate is more than 200 DEG C.
The manufacture method of 12. coated steel plates as described in any one in claim 8～11, wherein,
Described coating is coated in the way of making the thickness of described upper painting film be 2～20 μm.
The manufacture method of 13. coated steel plates as described in any one in claim 8～12, wherein,
The content of the described curable silicone in described coating relative to the presoma of polyimides described in 100 mass parts is
1～10 mass parts.
The manufacture method of 14. coated steel plates as described in any one in claim 8～13, wherein,
Described steel plate has chemical conversion treatment epithelium on its surface.
15. 1 kinds of cooking appliance parts, wherein,
Comprise the coated steel plate described in any one in claim 1～7.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-072302 | 2014-03-31 | ||
| 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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106232349A true CN106232349A (en) | 2016-12-14 |
| CN106232349B CN106232349B (en) | 2018-12-21 |
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| CN201580017735.8A Active CN106232349B (en) | 2014-03-31 | 2015-03-31 | Coated steel plate and its manufacturing method and cooking appliance component |
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| Country | Link |
|---|---|
| JP (1) | JP6163128B2 (en) |
| KR (1) | KR102372936B1 (en) |
| CN (1) | CN106232349B (en) |
| MY (1) | MY181183A (en) |
| PH (1) | PH12016501929B1 (en) |
| TW (1) | TWI642539B (en) |
| WO (1) | WO2015151509A1 (en) |
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|---|---|---|---|---|
| WO2023144709A1 (en) | 2022-01-25 | 2023-08-03 | Tata Steel Limited | Preparation and application of polyimide intermediates for anti-corrosion coating on metal surfaces |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62110298A (en) * | 1985-11-08 | 1987-05-21 | 松下電器産業株式会社 | Radio frequency heater |
| JPH07116056A (en) * | 1993-10-26 | 1995-05-09 | Matsushita Electric Ind Co Ltd | Hydrophilic coating film and manufacture thereof and cooling appliance having hydrophilic coating film |
| CN101724309A (en) * | 2008-10-31 | 2010-06-09 | 道康宁（上海）有限公司 | Additive for non-stick coating composite and cooking utensil with solidifying coating containing additive |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52104586A (en) * | 1976-03-01 | 1977-09-02 | Kuboko Paint Co | Protective film structure of alminium material |
| JP2807486B2 (en) * | 1989-04-19 | 1998-10-08 | 藤井金属化工株式会社 | Temperature controllable pot |
| JPH1087988A (en) * | 1996-09-12 | 1998-04-07 | Nitto Denko Corp | Heat-bonding polyimide resin film, semiconductor device using the same, its production, and tape carrier for semiconductor device using the same |
| JP4335716B2 (en) | 2004-03-16 | 2009-09-30 | 日新製鋼株式会社 | Heat-resistant non-adhesive pre-coated metal plate |
| JP4622584B2 (en) * | 2005-03-01 | 2011-02-02 | 東海ゴム工業株式会社 | Endless belt for electrophotographic equipment and method for producing the same |
| KR20130031143A (en) * | 2011-09-20 | 2013-03-28 | 고려대학교 산학협력단 | Toaster |
-
2014
- 2014-03-31 JP JP2014072302A patent/JP6163128B2/en active Active
-
2015
- 2015-03-31 WO PCT/JP2015/001850 patent/WO2015151509A1/en active Application Filing
- 2015-03-31 TW TW104110490A patent/TWI642539B/en active
- 2015-03-31 MY MYPI2016703568A patent/MY181183A/en unknown
- 2015-03-31 KR KR1020167027046A patent/KR102372936B1/en active IP Right Grant
- 2015-03-31 CN CN201580017735.8A patent/CN106232349B/en active Active
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2016
- 2016-09-29 PH PH12016501929A patent/PH12016501929B1/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62110298A (en) * | 1985-11-08 | 1987-05-21 | 松下電器産業株式会社 | Radio frequency heater |
| JPH07116056A (en) * | 1993-10-26 | 1995-05-09 | Matsushita Electric Ind Co Ltd | Hydrophilic coating film and manufacture thereof and cooling appliance having hydrophilic coating film |
| CN101724309A (en) * | 2008-10-31 | 2010-06-09 | 道康宁（上海）有限公司 | Additive for non-stick coating composite and cooking utensil with solidifying coating containing additive |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106232349B (en) | 2018-12-21 |
| TW201538311A (en) | 2015-10-16 |
| KR20160138978A (en) | 2016-12-06 |
| TWI642539B (en) | 2018-12-01 |
| PH12016501929A1 (en) | 2016-12-19 |
| PH12016501929B1 (en) | 2016-12-19 |
| MY181183A (en) | 2020-12-21 |
| JP2015193136A (en) | 2015-11-05 |
| WO2015151509A1 (en) | 2015-10-08 |
| KR102372936B1 (en) | 2022-03-08 |
| JP6163128B2 (en) | 2017-07-12 |
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