CN102267267A - Fluororesin covering materials and method of preparing the same - Google Patents
Fluororesin covering materials and method of preparing the same Download PDFInfo
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- CN102267267A CN102267267A CN2011101072200A CN201110107220A CN102267267A CN 102267267 A CN102267267 A CN 102267267A CN 2011101072200 A CN2011101072200 A CN 2011101072200A CN 201110107220 A CN201110107220 A CN 201110107220A CN 102267267 A CN102267267 A CN 102267267A
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin 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
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- 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
- A47J27/00—Cooking-vessels
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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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
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0008—Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
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- 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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/536—Hardness
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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
- B32B2371/00—Polyethers, e.g. PEEK, i.e. polyether-etherketone; PEK, i.e. polyetherketone
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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
- B32B2509/00—Household appliances
Abstract
The invention provides a fluororesin covering material and a method of preparing the same, which is characterized by comprising a base material, an engineering plastic layer coated on the surface of the base material and a fluorine-containing resin layer coated on the surface of the engineering plastic layer. The engineering plastic layer has the pencil hardness of over 4H. The fluorine-containing resin layer contains crosslinked fluorine-containing resin subject to the irradiation of ionizing radiation.
Description
Technical field
The present invention relates to employed fluorine resin lining material and manufacture methods thereof such as cooking-vessels such as pot for cooking rice, frying pan or flatiron.
Background technology
The fluorine resin lining material is meant that the surface at the base material of being made by metal etc. is provided with the material of fluorine resin coating.Fluorine resin is chemically highly stable and low adhesion is good.Therefore, the fluorine resin coating is set, can gives low adhesion, thereby Jiao that can prevent food materials in gastronomical process sticks with paste etc., therefore is widely used in cooking-vessel etc. by surface at base material.
On the other hand, thus there is the low problem of peeling off easily of adhesive tension with the base material of being made by metal etc. in the fluorine resin coating.Therefore, in order to improve the adhesive tension between fluorine resin and base material, the whole bag of tricks has been proposed up to now.
For example, thus having proposed that substrate surface is implemented roughening handles the method that improves the adhesive tension between substrate surface and the fluoropolymer resin layer by so-called anchoring effect.Particularly, following method is disclosed in patent documentation 1: use aluminium and stainless steel sandwich material (bimetal), this aluminium superficial layer is removed substantially, carrying out roughening by electrochemistry or chemical etching then handles, and then on this matsurface, be coated with the fluorine resin dispersion liquid and carry out drying, baking, thereby form fluoropolymer resin layer.
In addition, the also known method that priming coat is set between base material and fluoropolymer resin layer.Particularly, be coating silane coupling agent and form fluoropolymer resin layer thereon on the surface of base materials such as aluminium, thereby by silane coupling agent with method firmly gluing between base material and the fluoropolymer resin layer etc.
In addition,, be extensive use of and comprise fluorine resin, sneak into the engineering plastics of about 10 weight %～about 40 weight % and the silane coupling agent that disperses with the form on the island of so-called island structure therein as the fluoropolymer resin layer silane coupling agent.In this silane coupling agent, give adhesive tension between priming coat and the base material by the existence of engineering plastics, and, give the adhesive tension between the fluoropolymer resin layer on priming coat and surface by the fluorine resin in the silane coupling agent.For example, at patent documentation 2 method of the composition of fluorine resins such as using engineering plastics such as containing polyether sulfone, polyamidoimide with 15: 85～35: 65 weight ratio and polytetrafluoroethylene (PTFE) as silane coupling agent disclosed.
In addition, the manufacture method of the resin-coated material of a kind of modified fluoride-containing is disclosed in patent documentation 3, it is characterized in that, form fluoropolymer resin layer with the surface of fluorine resin covering substrates, then to the surface irradiation ionizing ray of fluoropolymer resin layer, the cross-linking reaction of fluorine resin and the chemical reaction between fluorine resin and the substrate surface are taken place simultaneously, realize the firmly gluing of the two thus.
The prior art document
Patent documentation
Patent documentation 1: No. 2792044 communique of Japan Patent
Patent documentation 2: Japanese kokai publication hei 11-349887 communique
Patent documentation 3: TOHKEMY 2002-225024 communique
Summary of the invention
According to above-mentioned known method, the adhesive tension between base material such as metal and the fluoropolymer resin layer is improved.In addition, according to the method for in fluoropolymer resin layer, implementing cross-linking reaction disclosed methods such as () patent documentations 3, can significantly improve the mar proof of fluoropolymer resin layer, and can significantly improve the character (corrosion resistance) that prevents because of the corrosion due to cooking material (liquid that for example, ODEN (ぉ In ん) soup etc. contains salt).
But in the use of cooking-vessel etc., spoon, fork or other cooking appliance etc. can produce scraping, thereby expose base material because of scraping makes the surface of fluorine resin lining material produce damage sometimes.Therefore, also wish to suppress this problem (raising scratch resistance), but the fluorine resin lining material that obtains by above-mentioned known method can not satisfy this requirement.That is, even carried out crosslinkedly, the scratch resistance of fluoropolymer resin layer can not improve yet, and, can not give described silane coupling agent good scratch resistance.
The invention is characterized in to provide and have fluoropolymer resin layer and also good fluorine resin lining material and the manufacture method thereof of scratch resistance that is difficult for peeling off.
Found that of inventor's research:
By to by the engineering plastics layer that only forms or form by material with cover the fluoropolymer resin layer irradiation ionizing ray on the surface of this project plastic layer based on engineering plastics by engineering plastics, make fluorine resin crosslinked, can obtain the good adhesive tension between engineering plastics layer and the fluoropolymer resin layer;
And the engineering plastics of layer that can be formed in the pencil hardness that has under 30 ℃ more than the 4H by use can obtain to have the fluorine resin lining material of good scratch resistance, thereby finish the present invention as described engineering plastics.
Promptly, the invention provides a kind of fluorine resin lining material (first aspect), it is characterized in that, have: base material, the engineering plastics layer that on described base material, is provided with and cover the surface of described engineering plastics layer and as the fluoropolymer resin layer on top layer, described engineering plastics layer has the pencil hardness more than the 4H under 30 ℃, described fluoropolymer resin layer comprise by the irradiation ionizing ray carried out crosslinked fluorine resin.
Fluorine resin lining material of the present invention is characterised in that, the engineering plastics layer is set between base material and fluoropolymer resin layer, and the material of formation this project plastic layer is only for engineering plastics or based on engineering plastics.And its feature also is, this fluoropolymer resin layer comprises by the irradiation ionizing ray and carried out crosslinked fluorine resin.By this feature, can obtain the good adhesive tension between engineering plastics layer and the fluoropolymer resin layer.
As previously mentioned, between base material and fluoropolymer resin layer the priming coat that contains engineering plastics being set is technique known (patent documentation 2).But the containing ratio of the engineering plastics of this priming coat is about 10 weight %～about 40 weight %, based on other resins such as fluorine resins.This is because thought in the past, and engineering plastics and the adhesive tension that comprises between the coating of fluorine resin are low, and when the content of engineering plastics increased, fluoropolymer resin layer was peeled off easily.
But, the inventor finds, if to fluoropolymer resin layer irradiation ionizing ray and make fluorine resin crosslinked,, between this layer and its surperficial fluoropolymer resin layer of covering, also has good adhesive tension even then only constitute or based on the layer of engineering plastics by engineering plastics.And the adhesive tension between engineering plastics layer and the base material is better than the silane coupling agent of the low prior art of the content of engineering plastics and the adhesive tension between the base material.Therefore, constitute engineering plastics layer of the present invention and base material and fluoropolymer resin layer and all have good adhesive tension, thereby can between base material and fluoropolymer resin layer, obtain good gluing.
In addition, fluoropolymer resin layer is the layer that covers the surface of engineering plastics layer." covering surfaces " is meant that the mode to contact with the surface forms." as the fluoropolymer resin layer on top layer " is meant that fluoropolymer resin layer is the outermost layer of fluorine resin lining material." base material is provided with the engineering plastics layer " be meant the engineering plastics layer with situation about forming with the mode that directly contacts of surface of base material and engineering plastics layer by in the gluing situation of priming coat and base material any one.According to the kind of employed engineering plastics, difficult sometimes gluing with base material, can be provided with the stronger priming coat of adhesive tension this moment.
Feature of the present invention is that also described engineering plastics layer has the pencil hardness more than the 4H under 30 ℃.The engineering plastics layer becomes the good layer of scratch resistance by having described rerum natura.Promptly, exist on the surface of fluorine resin lining material under the situation of the scraping that cooking appliance etc. causes, though the fluoropolymer resin layer on top layer peels off, but non-easy damaged owing to engineering plastics layer scratch-resistant with above-mentioned rerum natura, therefore scraping can not connect to base material, thereby can prevent exposing of base material.If thereby base material exposes the corrosion that then can produce base material and causes coating to peel off, but, can prevent exposing of base material, thereby prevent the peeling off of burn into coating of base material according to the present invention.
In addition, engineering plastics are in a ratio of low adhesion (release property is good) with the metals such as aluminium that constitute base material.And the area of the fluoropolymer resin layer that peels off because of scraping is limited.Therefore,, can the low adhesion of fluorine resin lining material not impacted substantially yet, we can say not influence of practical application even scraping causes the fluoropolymer resin layer on top layer to peel off.
" based on engineering plastics " are meant with engineering plastics is main component, this means to have above-mentioned specific rerum natura (pencil hardness more than the 4H) and can obtain at the engineering plastics layer can contain other resin in the scope that target effect of the present invention is good scratch resistance.The content range that is used to obtain the engineering plastics of good scratch resistance changes according to the kind of engineering plastics etc., but need contain the above engineering plastics of 50 weight % usually at least, is preferably and contains the above scope of 80 weight %.
The fluoropolymer resin layer that constitutes fluorine resin lining material of the present invention comprises by the crosslinked fluorine resin of ionizing ray irradiation having carried out.Therefore because it is crosslinked that fluorine resin has carried out, can form and have the good mar proof and the fluoropolymer resin layer of corrosion resistance.
A second aspect of the present invention is as the described fluorine resin lining material of first aspect, it is characterized in that, the thickness of fluoropolymer resin layer is 10 μ m～60 μ m, and the thickness of engineering plastics layer is 10 μ m～200 μ m.
Constitute the fluoropolymer resin layer of fluorine resin lining material of the present invention, owing to improved mar proof and corrosion resistance by ionizing ray irradiation as previously mentioned, therefore can must be thinner with thickness setting.If with thickness setting is more than the 10 μ m, then can obtain to be enough to be used in the mar proof and the corrosion resistance of purposes such as common cooking appliance or flatiron.If increase the thickness of fluoropolymer resin layer, then mar proof and corrosion resistance improve.But manufacturing cost also rises.In addition, the problem that becomes eye-catching easily in the time of also can occurring producing scraping.Usually, even thickness surpasses 60 μ m, the raising of mar proof and corrosion resistance is also less, and problem such as manufacturing cost rising becomes remarkable on the other hand.Therefore, preferred thickness is more than the 10 μ m and below the 60 μ m usually.
By the thickness setting with the engineering plastics layer is that it is better that scratch resistance becomes more than the 10 μ m.Consider that from the viewpoint of scratch resistance the engineering plastics layer is preferably thicker, more preferably more than the 30 μ m, is preferably especially more than the 50 μ m.But when the thickness of engineering plastics layer surpassed 200 μ m, the raising that thickness increases the scratch resistance that brings diminished, and on the other hand, manufacturing cost rises, and therefore considers from this viewpoint, below the preferred 200 μ m.
A third aspect of the present invention is as the described fluorine resin lining material of first aspect, it is characterized in that, described engineering plastics layer is formed by more than one the resin that is selected from the group of being made up of polyether-ether-ketone, polyether sulfone, polyamidoimide and polyimides.As engineering plastics with the pencil hardness more than the 4H, can enumerate polyether-ether-ketone (PEEK), polyether sulfone (PES) or polyamidoimide so-called super engineering plastics such as (PAI), the preferred a kind of resin that is selected from these resins or the mixture of two or more resins of using separately.
A fourth aspect of the present invention is as the described fluorine resin lining material of first aspect, it is characterized in that the fluorine resin that constitutes described fluoropolymer resin layer comprises more than one the resin that is selected from the group of being made up of polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer and tetrafluoraoethylene-hexafluoropropylene copolymer.
As the fluorine resin that constitutes described fluoropolymer resin layer, the preferred a kind of resin that is selected from polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) and the tetrafluoraoethylene-hexafluoropropylene copolymer (FEP) or the mixture of two or more resins of using separately.Crosslinked by using these resins and carrying out ionizing ray irradiation, can obtain better mechanical strength, particularly better mar proof, corrosion resistance.
A fifth aspect of the present invention is as the described fluorine resin lining material of either side in first to fourth aspect, it is characterized in that base material comprises the material that is selected from polyimide resin, metal material, pottery and glass.
As the base material that constitutes fluorine resin lining material of the present invention, can enumerate polyimide resin, metal material, pottery, glass etc., also can use the composite that comprises these materials, the present invention is preferably applied to use metal material or ceramic occasion as base material especially.Under the situation of using pottery as base material, corrosion resistance is low when utilizing prior art when general silane coupling agent (use existing), for example, can not tolerate so-called ODEN corrosion test.But, even fluorine resin lining material of the present invention also can fully tolerate above-mentioned corrosion test under the situation of using pottery as base material.In addition, the metal material that uses as base material can be enumerated iron, aluminium, stainless steel (SUS) etc.
Fluorine resin lining material of the present invention can be made by the method that comprises following operation: the operation that forms the engineering plastics layer with the hardness more than the 4H on the surface of base material; Cover described engineering plastics layer with fluorine resin and form the operation of fluoropolymer resin layer; With to the surface irradiation ionizing ray of described fluoropolymer resin layer and make the crosslinked operation of fluorine resin.A sixth aspect of the present invention is equivalent to this manufacture method.
A seventh aspect of the present invention is the manufacture method as the described fluorine resin lining material in the 6th aspect, it is characterized in that the operation that forms the engineering plastics layer comprises: heating varnish or dispersion after the varnish of the surface of base material coating engineering plastics or dispersion and make the engineering plastics of its dry operation or applying solid shape and make the operation of its fusion.
As the method that forms the engineering plastics layer, can be set forth in the organic solvent dissolving engineering plastics and make varnish or in decentralized media such as water, disperse engineering plastics and make dispersion, heat the method that the organic solvent in varnish or the dispersion or decentralized medium are removed behind the surface of base material thereby this varnish or dispersion are coated.In addition, can also enumerate the engineering plastics of powder shaped (solid shape) are coated the surface of base material after, heating makes its fusion and cambial method.
A eighth aspect of the present invention is the manufacture method as the described fluorine resin lining material in the 6th or the 7th aspect, it is characterized in that, to the surface irradiation ionizing ray of fluoropolymer resin layer the crosslinked operation of fluorine resin is carried out in the following way: to use electron ray as ionizing ray, under oxygen-free atmosphere, in than high 0～30 ℃ temperature range of the fusing point of fluorine resin, carry out.
The ionizing ray that uses during as fluorine resin crosslinked can be enumerated high energy electromagnetic waves such as charged particle ray, gamma rays, X ray such as electron ray, preferably uses electron ray.The electron ray generating means is relatively cheap and can obtain the electron ray of big power output and be easy to control the degree of cross linking.For the good adhesivity between the good mar proof, corrosion resistance and engineering plastics layer and the fluoropolymer resin layer that obtain fluoropolymer resin layer, preferably at oxygen-free atmosphere, particularly be below the oxygen concentration 100ppm, more preferably under the atmosphere below the 5ppm, under the temperature more than the fusing point of fluorine resin, particularly for the fusing point than fluorine resin high 0 ℃～carry out in 30 ℃ the temperature range crosslinked.
Fluorine resin lining material of the present invention has: therefore features such as the low and fluoropolymer resin layer of the cohesive of fluoropolymer resin layer etc. is difficult for peeling off, scratch resistance is good are suitable for utensil for cooking such as flatiron, particularly pot for cooking rice, frying pan etc.Therefore a ninth aspect of the present invention provides a kind of utensil for cooking, it is characterized in that, comprise: base material, cover described base material the surface the engineering plastics layer and cover the fluoropolymer resin layer on the surface of described engineering plastics layer, described engineering plastics layer has the pencil hardness more than the 4H under 30 ℃, described fluoropolymer resin layer comprise by the irradiation ionizing ray carried out crosslinked fluorine resin.
The invention effect
Fluorine resin lining material of the present invention has the fluoropolymer resin layer that is difficult for peeling off, and scratch resistance is also good.Fluorine resin lining material of the present invention can easily be made by manufacture method of the present invention.
Description of drawings
Fig. 1 is the profile of an example of fluorine resin lining material of the present invention.
Fig. 2 is the key diagram of the method for the expression rotation wear test of carrying out among the embodiment.
Fig. 3 is the result's of the expression rotation wear test of carrying out among the embodiment a chart.
Label declaration
1. base material
2. engineering plastics layer
3. fluoropolymer resin layer
10. fixed part
11. rotating part
12. sample
Wipe away bright (ス コ Star チ Block ラ イ ト) rag 13. think height
14. weight
The specific embodiment
Below, describe being used to implement mode of the present invention.In addition, the invention is not restricted to this mode or embodiment, in the scope of not damaging aim of the present invention, can change to alternate manner.
Fig. 1 is the profile of an example of fluorine resin lining material of the present invention.Among the figure, 1 is base material, and 2 is the engineering plastics layer, and 3 is fluoropolymer resin layer, gluing powerfully between base material 1, engineering plastics layer 2, the fluoropolymer resin layer 3.
Below, the manufacturing process of fluorine resin lining material of the present invention is described.
At first, engineering plastics are dissolved in the organic solvent and the varnish that makes or engineering plastics are scattered in the decentralized medium such as water and the dispersion that makes (engineering plastic powder is dispersed in the decentralized medium and the liquid that obtains) in the coating of the surface of base material.About the method for coating, can for example roller coat, spraying wait and carry out by the known method used in the coating of varnish or dispersion in the past.After the coating, the base material that the surface is formed with the layer of varnish or dispersion blows to wait by heating furnace or hot blast and heats, and organic solvent or decentralized medium is evaporated remove and carries out drying.Under the situation of varnish,, can obtain the engineering plastics layer by this drying.Under the situation of dispersion, the fusing point that usually further is heated to engineering plastics is above and calcine, and between the powder of engineering plastics heat bonding takes place and obtains the engineering plastics layer thereby make.
In addition, explanation when above-mentioned explanation is the relevant engineering plastics layer that forms directly contact on the surface of base material, in order further to improve the adhesive tension of base material and engineering plastics interlayer, also can form priming coat on the surface of base material, form the engineering plastics layer with above-mentioned method thereon again by elder generations such as known method.
The shape that can use base material of the present invention is not particularly limited.For example, can use flat base material to make fluorine resin lining material of the present invention, be configured as the shape of cooking appliance etc. then, also can use the base material of the shape that is configured as cooking appliance etc., form engineering plastics layer and fluoropolymer resin layer thereon, thereby obtain fluorine resin lining material of the present invention.
As the PEEK that is used to form the engineering plastics layer, PES, PAI, can use the material of making by known method.In addition, can use commercially available product.As the example of commercially available PEEK, can enumerate the PEEK 7964-M6 of オ キ Star モ company manufacturing etc.As the example of commercially available PES, can enumerate " PES5003P " that sumitomo chemical company makes, " P1700 " that ソ Le ベ Application ア De バ Application ス ト Port リ マ one ズ company makes, " P3500 " etc.As the example of commercially available PAI, can enumerate the trade name AE2 of for example ridge, field chemical industrial company manufacturing etc.
As the organic solvent that in described varnish, dissolves PEEK, PES, PAI etc., can enumerate aromatic hydrocarbons, N such as carbitol class, toluene, dimethylbenzene such as acetate esters, cellosolve, BC such as ketones such as acetone, MEK, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol methyl ether acetate, carbitol acetic acid esters, dinethylformamide, N, N-dimethylacetylamide, N-methyl pyrrolidone etc.Organic solvent can be used in combination.
As the decentralized medium that in dispersion, disperses PEEK, PES, PAI etc., can enumerate water etc., can be used in combination.
After forming the engineering plastics layer as previously mentioned, cover its surface and form fluoropolymer resin layer with fluorine resin.As carrying out the method that fluorine resin covers, can enumerate: the method for example method of electrostatic spraying fluorine resin powder or method or the coating fluorine resin dispersion (in decentralized medium, evenly being dispersed with the liquid of fluorine resin powder) and the dry method of removing decentralized medium etc. of spraying fluorine resin powder that cover method, the powder body coating of the film of fluorine resin.Wherein, consider that preferable methods is the method for coating fluorine resin dispersion from the viewpoint that can easily form the uniform fluoropolymer resin layer of thickness.
In order to make described fluorine resin dispersion, be decentralized medium as the liquid of efficient dispersion fluorine resin powder, can make the mixed solvent of water and emulsifying agent, water and alcohol, water and acetone or water, pure and mild acetone etc.After the coating fluorine resin dispersion, the decentralized medium drying is removed by air-dry or heated-air drying.Drying by decentralized medium, remove and form the film that comprises the fluorine resin powder, the fusing point that is heated to fluorine resin then is above and calcine, and heat bonding takes place between the fluorine resin powder forms fluoropolymer resin layer thereby make.
Calcining is preferably carried out 250～400 ℃ temperature range.Can especially drying process be set yet and in calcination process, decentralized medium be removed.By calcining,, heat bonding forms fluoropolymer resin layer thereby taking place between the powder of fluorine resin.
Then, the surface irradiation ionizing ray to the fluoropolymer resin layer of such formation carries out the crosslinked of fluorine resin.Crosslinked by this, fluoropolymer resin layer and engineering plastics interlayer are gluing securely.Think and between fluorine resin and engineering plastics, reaction has taken place.
Implement when crosslinked, under oxygen-free atmosphere, particularly for placing under the atmosphere below the oxygen concentration 100ppm, below the preferred 5ppm, and remain on than in high 0～30 ℃ temperature range of the fusing point of fluorine resin, simultaneously to the surface irradiation ionizing ray of fluorine resin film.The scope of illuminated line amount is generally 1～1000kGy, preferred 100～500kGy.
At this moment, can implement the irradiation of above-mentioned calcining and ionizing ray simultaneously.When environment temperature is lower than the fusing point of fluorine resin, be difficult to take place the cross-linking reaction of fluorine resin, when environment temperature surpasses the high 30 ℃ temperature of fusing point than fluorine resin, thereby can promote the thermal decomposition of fluorine resin that material behavior is descended, therefore not preferred.In addition, the illuminated line amount is during less than 1kGy, and cross-linking reaction is insufficient, can not expect the raising of characteristic, when surpassing 1000kGy, is easy to generate the decomposition of fluorine resin, and is therefore not preferred.
Embodiment
Test the evaluation of routine 1[scratch resistance]
Inner surface at the base material of the shape of making and form inner container of electric cooker by the material shown in the table 1, spray coating shown below, heat down at 380 ℃ then and calcined in 20 minutes, form the intermediate layer and (be meant the layer that is arranged between base material and the fluoropolymer resin layer in an embodiment; Engineering plastics layer etc.).On the engineering plastics layer that forms like this,, heat down at 380 ℃ then and calcined in 20 minutes, form PFA layer (fluoropolymer resin layer) by powder body coating coating PFA (E.I.Du Pont Company's system, MP102).
＜be used to form the coating in intermediate layer 〉
The big system EK-1208M8L (general silane coupling agent is expressed as " EK1 " in the following table) of King Company
オ キ Star モ corporate system PEEK 7964-M6 (polyether-ether-ketone is expressed as " PEEK " in the following table)
After forming the PFA layer,, use the electron ray of day サ ガ ト ロ Application (accelerating potential is 1.13MeV) of new motor company manufacturing to irradiation 300kGy on the PFA layer under the atmosphere of oxygen concentration 5ppm, under 310 ℃ temperature.Behind the irradiation electron ray, pencil hardness and scratch resistance are estimated by following method.Its result is as shown in table 1.
Pencil hardness: with under 30 ℃ of temperature with pencil when the PFA layer is swiped, generation can see that the hardness of pencil of the scraping of base material represents.
Scratch resistance (scraping experiment): the state when expression is swiped the PFA layer with fork.
Table 1
Base material material " aluminium " expression metallic aluminium (Korea S DAIHO corporate system, 3003) in the table.In addition, the general ceramic tile of " pottery " expression TOTO company manufacturing.Employed pottery also is same in the corrosion resistance evaluation.
Shown in the result of table 1, the electron ray irradiation is also carried out and the fluorine resin lining material (specimen coding 2 and the specimen coding 4: embodiment) that obtain in the intermediate layer (engineering plastics layer) that setting is formed by 100% engineering plastics PEEK, pencil hardness is more than the 6H, promptly use fork to swipe also not produce quite powerfully and be deep to peeling off of base material, thereby have good scratch resistance.All can obtain under the situation of any one base material of this effect in aluminium, pottery.On the other hand, form the intermediate layer and do not carry out in the fluorine resin lining material (specimen coding 1 and specimen coding 3) of electron ray irradiation with existing general silane coupling agent, can not obtain good scratch resistance, can shell easily by the scraping of fork and expose base material to the bottom.
Test the evaluation of routine 2[corrosion resistance]
Spraying coating shown below on the surface of the tabular base material of being made by pottery is being estimated formation intermediate layer and PFA layer (fluoropolymer resin layer) under the identical condition with scratch resistance.Then, under the condition identical, shine electron ray, obtain the corrosion resistance test sample with the scratch resistance evaluation.Behind the irradiation electron ray, carry out the evaluation of corrosion resistance by following corrosion resistance test method.Its result is as shown in table 1.
＜be used to form the coating in intermediate layer 〉
The big system EK-1283SIL (general silane coupling agent is expressed as " EK2 " in the following table) of King Company
オ キ Star モ corporate system PEEK 7964-M6 (is expressed as " PEEK " in the following table.)
＜corrosion resistance test method 〉
With S﹠amp; The plain 20g of B corporate system ODEN is dissolved in the 1L water, makes experimental liquid.Under the insulation pattern (about 90 ℃) of pot for cooking rice, the above-mentioned corrosion resistance test that obtains be impregnated in the experimental liquid with sample.Behind the dip time through regulation, by gridiron pattern test the carrying out evaluation of adaptation of JIS-K-5400 (version in 1998) defined.Its result is as shown in table 2.
Table 2
| Specimen coding | Base material | Coating | The electron ray irradiation | Gridiron pattern test after 200 |
| 5 | Pottery | EK2 | Do not have | 0/100 (between intermediate layer and base material, peeling off) |
| 6 | Pottery | EK2 | Have | 0/100 (between intermediate layer and base material, peeling off) |
| 7 | Pottery | PEEK | Do not have | 14/100 (between top layer and intermediate layer, peeling off) |
| 8 | Pottery | PEEK | Have | 100/100 |
Shown in the result of table 2, base material is the fluorine resin lining material of pottery, forming under the situation in intermediate layer with existing general silane coupling agent, even carried out electron ray irradiation (specimen coding 6), corrosion resistance is also low, the gridiron pattern test of flooding after 200 hours is 0/100, and whole gridiron patterns is all peeled off between intermediate layer and base material.In addition, even the intermediate layer (engineering plastics layer) that is formed by 100% PEEK is set, under the situation of not carrying out the electron ray irradiation, flooding that gridiron pattern after 200 hours tests is 14/100, can not obtain superior corrosion resistance.But, the intermediate layer (engineering plastics layer) that setting is formed by 100% PEEK and carry out the electron ray irradiation and the fluorine resin lining material (specimen coding 8: embodiment) that obtains, in the gridiron pattern test of dipping after 200 hours, do not observe and peel off (100/100), obtained superior corrosion resistance.
Test routine 3[abrasiveness and estimate (crosslinked effect)]
According to estimating identical condition, in proper order, on the surface of base material made of aluminum, form PEEK layer (engineering plastics layer), and form PFA layer (fluoropolymer resin layer) thereon with scratch resistance.Then, for sample (being expressed as " having crosslinked " among Fig. 3) that obtains and the sample (being expressed as " no crosslinked " among Fig. 3) that does not carry out the electron ray irradiation are rotated wear test by following method estimating irradiation electron ray under the identical condition with scratch resistance.Its result as shown in Figure 3.Can be clear and definite by result shown in Figure 3, crosslinked by the enforcement of irradiation electron ray, wearing and tearing reach the degree that does not observe, and mar proof significantly improves.
＜rotation wear test 〉
As shown in Figure 2, the think of height that mounting Sumitomo 3M company makes on sample 12 is wiped away bright rag (#3000) 13, and the weight 14 of mounting 2kg thereon, and it is rotated with 200rpm, measures the thickness reduction due to the wearing and tearing of rotation back sample 12.
Industrial applicability
Fluorine resin lining material of the present invention has the fluoropolymer resin layer that is difficult for peeling off, and scratch resistance is also good, and the material that therefore is suitable as cooking-vessels such as constituting pot for cooking rice, pot, frying pan or flatiron etc. uses.
Claims (9)
1. a fluorine resin lining material is characterized in that,
Have: base material, the engineering plastics layer that on described base material, is provided with and cover the surface of described engineering plastics layer and as the fluoropolymer resin layer on top layer,
Described engineering plastics layer has the pencil hardness more than the 4H under 30 ℃,
Described fluoropolymer resin layer comprise by the irradiation ionizing ray carried out crosslinked fluorine resin.
2. fluorine resin lining material as claimed in claim 1 is characterized in that, the thickness of fluoropolymer resin layer is 10 μ m～60 μ m, and the thickness of engineering plastics layer is 10 μ m～200 μ m.
3. fluorine resin lining material as claimed in claim 1 is characterized in that, described engineering plastics layer is formed by more than one the resin that is selected from the group of being made up of polyether-ether-ketone, polyether sulfone, polyamidoimide and polyimides.
4. fluorine resin lining material as claimed in claim 1, it is characterized in that the fluorine resin that constitutes described fluoropolymer resin layer comprises more than one the resin that is selected from the group of being made up of polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer and tetrafluoraoethylene-hexafluoropropylene copolymer.
5. as each described fluorine resin lining material in the claim 1 to 4, it is characterized in that base material comprises the material that is selected from polyimide resin, metal material, pottery and glass.
6. the manufacture method of a fluorine resin lining material is characterized in that, comprising:
Form the operation of engineering plastics layer with the hardness more than the 4H on the surface of base material;
Cover described engineering plastics layer with fluorine resin and form the operation of fluoropolymer resin layer; With
To the surface irradiation ionizing ray of described fluoropolymer resin layer and make the crosslinked operation of fluorine resin.
7. the manufacture method of fluorine resin lining material as claimed in claim 6, it is characterized in that the operation that forms the engineering plastics layer comprises: heating varnish or dispersion after the varnish of the surface of base material coating engineering plastics or dispersion and make the engineering plastics of its dry operation or applying solid shape and make the operation of its fusion.
8. as the manufacture method of claim 6 or 7 described fluorine resin lining materials, it is characterized in that, to the surface irradiation ionizing ray of fluoropolymer resin layer the crosslinked operation of fluorine resin is carried out in the following way: to use electron ray as ionizing ray, under oxygen-free atmosphere, in than high 0～30 ℃ temperature range of the fusing point of fluorine resin, carry out.
9. a utensil for cooking is characterized in that,
Comprise: base material, cover described base material the surface the engineering plastics layer and cover the fluoropolymer resin layer on the surface of described engineering plastics layer,
Described engineering plastics layer has the pencil hardness more than the 4H under 30 ℃,
Described fluoropolymer resin layer comprise by the irradiation ionizing ray carried out crosslinked fluorine resin.
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| JP2010-099028 | 2010-04-22 | ||
| JP2010099028A JP5601013B2 (en) | 2010-04-22 | 2010-04-22 | Fluororesin coating material and method for producing the same |
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| CN102267267A true CN102267267A (en) | 2011-12-07 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103742954A (en) * | 2014-01-22 | 2014-04-23 | 苏州新区特氟龙塑料制品厂 | Novel Teflon microwave oven pad |
| CN104507371A (en) * | 2012-08-01 | 2015-04-08 | 大金工业株式会社 | Cooking utensil |
| CN107969123A (en) * | 2015-05-14 | 2018-04-27 | 住友电工超效能高分子股份有限公司 | The manufacture method of gluing reinforcing sheet, sliding component and gluing reinforcing sheet |
| CN108928118A (en) * | 2017-05-26 | 2018-12-04 | 精工爱普生株式会社 | The manufacturing method of nozzle plate, liquid ejecting head, liquid injection apparatus and nozzle plate |
| CN111565922A (en) * | 2018-01-11 | 2020-08-21 | 住友电气工业株式会社 | Method for producing oil-repellent sheet, and gas sensor |
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| EP2832518A4 (en) * | 2012-03-30 | 2015-08-05 | Sumitomo Elec Fine Polymer Inc | Resin-releasing jig |
| CN103213357B (en) * | 2013-01-05 | 2015-07-08 | 浙江鹏孚隆科技有限公司 | Non-stick coating layer with characteristics of high hardness, scratch resistance and corrosion resistance, and coating method thereof |
| KR102216263B1 (en) * | 2018-04-25 | 2021-02-17 | 이상선 | Butterfly valve and method of manufacturing the same |
| WO2019208910A1 (en) * | 2018-04-25 | 2019-10-31 | Lee Sang Seon | Butterfly valve and method for manufacturing same |
| JP2020103573A (en) * | 2018-12-27 | 2020-07-09 | 京セラ株式会社 | Cooking tool |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002225204A (en) * | 2001-01-30 | 2002-08-14 | Reitekku:Kk | Modified fluororesin coated material and method for producing the same |
| CN1153632C (en) * | 1999-03-16 | 2004-06-16 | Seb公司 | Antiadhesive coating with improved scratch resistance |
| JP2008194886A (en) * | 2007-02-09 | 2008-08-28 | Nippon Shokubai Co Ltd | Surface protective film |
| WO2008156016A1 (en) * | 2007-06-20 | 2008-12-24 | Sumitomo Electric Fine Polymer, Inc. | Fluororesin composite material, cooking utensil, cooker, roller for oa apparatus, belt for oa apparatus, and processes for producing these |
| CN101555384A (en) * | 2008-04-10 | 2009-10-14 | 慧智科技（中国）有限公司 | Nonstick coating composition with high heat-oil resisting property |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2791065A1 (en) * | 1999-03-16 | 2000-09-22 | Seb Sa | NON-STICK COATING HAVING IMPROVED SCRATCH RESISTANCE |
| JP4335716B2 (en) * | 2004-03-16 | 2009-09-30 | 日新製鋼株式会社 | Heat-resistant non-adhesive pre-coated metal plate |
| JP2008162027A (en) * | 2006-12-27 | 2008-07-17 | Toyo Ink Mfg Co Ltd | Hard coat film |
-
2010
- 2010-04-22 JP JP2010099028A patent/JP5601013B2/en active Active
-
2011
- 2011-04-15 KR KR1020110035259A patent/KR101749350B1/en active IP Right Grant
- 2011-04-22 CN CN2011101072200A patent/CN102267267A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1153632C (en) * | 1999-03-16 | 2004-06-16 | Seb公司 | Antiadhesive coating with improved scratch resistance |
| JP2002225204A (en) * | 2001-01-30 | 2002-08-14 | Reitekku:Kk | Modified fluororesin coated material and method for producing the same |
| JP2008194886A (en) * | 2007-02-09 | 2008-08-28 | Nippon Shokubai Co Ltd | Surface protective film |
| WO2008156016A1 (en) * | 2007-06-20 | 2008-12-24 | Sumitomo Electric Fine Polymer, Inc. | Fluororesin composite material, cooking utensil, cooker, roller for oa apparatus, belt for oa apparatus, and processes for producing these |
| CN101555384A (en) * | 2008-04-10 | 2009-10-14 | 慧智科技（中国）有限公司 | Nonstick coating composition with high heat-oil resisting property |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104507371A (en) * | 2012-08-01 | 2015-04-08 | 大金工业株式会社 | Cooking utensil |
| CN104507371B (en) * | 2012-08-01 | 2016-08-10 | 大金工业株式会社 | Cooking appliance |
| CN103742954A (en) * | 2014-01-22 | 2014-04-23 | 苏州新区特氟龙塑料制品厂 | Novel Teflon microwave oven pad |
| CN107969123A (en) * | 2015-05-14 | 2018-04-27 | 住友电工超效能高分子股份有限公司 | The manufacture method of gluing reinforcing sheet, sliding component and gluing reinforcing sheet |
| CN108928118A (en) * | 2017-05-26 | 2018-12-04 | 精工爱普生株式会社 | The manufacturing method of nozzle plate, liquid ejecting head, liquid injection apparatus and nozzle plate |
| CN111565922A (en) * | 2018-01-11 | 2020-08-21 | 住友电气工业株式会社 | Method for producing oil-repellent sheet, and gas sensor |
| CN111565922B (en) * | 2018-01-11 | 2022-08-12 | 住友电气工业株式会社 | Method for producing oil-repellent sheet, and gas sensor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5601013B2 (en) | 2014-10-08 |
| JP2011224928A (en) | 2011-11-10 |
| KR101749350B1 (en) | 2017-06-20 |
| KR20110118081A (en) | 2011-10-28 |
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Application publication date: 20111207 |