CN1302317A - Fluororesin powder liquid dispersion capable of forming thick coatings - Google Patents

Fluororesin powder liquid dispersion capable of forming thick coatings Download PDF

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CN1302317A
CN1302317A CN98812484A CN98812484A CN1302317A CN 1302317 A CN1302317 A CN 1302317A CN 98812484 A CN98812484 A CN 98812484A CN 98812484 A CN98812484 A CN 98812484A CN 1302317 A CN1302317 A CN 1302317A
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fluororesin powder
liquid dispersion
colloidal particle
water
dispersion
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CN1198893C (en
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齐藤卓三
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Chemours Mitsui Fluoroproducts Co Ltd
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Du Pont Mitsui Fluorochemicals Co Ltd
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Priority claimed from JP25009598A external-priority patent/JP4159665B2/en
Priority claimed from JP27197798A external-priority patent/JP4208102B2/en
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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
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
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    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
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    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/65—Additives macromolecular

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Abstract

A fluororesin powder liquid dispersion comprising heat-flowable fluororesin powder, liquid dispersion medium having a surface tension of not more than 45 dyne/cm, and colloidal particles having an average particle size of not more than 1 [mu]m provides thick corrosion resistant coated films. Preferred colloidal particles for the dispersion are particles of polyether sulfone (PES) which are added in an aqueous dispersion containing an organic solvent and a water-miscible solvent. An aqueous dispersion of PES colloidal particles having an average particle size of not more than 1 [mu]m is preferably prepared by (1) dissolving PES in an organic solvent capable of solubilizing PES; (2) combining the dissolved PES with a water-miscible solvent which is capable of being dissolved in the organic solvent; and (3) combining water in which there is a dissolved surfactant with the dissolved PES.

Description

Can form the fluororesin powder liquid dispersion of thick coating
Invention field
The present invention relates to be applicable to the fluororesin powder liquid dispersion of coated article, specifically, relate to liquid dispersion and irreversible cohesion can not take place and can form the very fluororesin powder liquid dispersion of thick coating.
Background of invention
Have being heated of performances such as chemical resistant properties, non-viscosity, thermotolerance, low-friction coefficient and the electrical insulating property fluoro-resin that can flow and also can form the free of pinholes film, therefore be suitable for use as coating.Used the being heated fluoro-resin that can flow comprises in this class application of paints, for example, the multipolymer (ETFE) of the multipolymer (FEP) of the multipolymer of tetrafluoroethylene and perfluor (alkyl vinyl ether) (hereinafter being referred to as PFA), tetrafluoroethylene and R 1216 and tetrafluoroethylene and ethene.Water insoluble and the organic solvent of these resins is so can not be used as solution-based paint.Therefore, various other means of the electrostatic applications that this resinoid will be by comprising the powder-type coating composition just can be applied to matrix and get on, and perhaps use with the form of liquid dispersion.Liquid dispersion can be water base and with surfactant-stabilized, also can be the organic liquid base.Liquid dispersion forms film coating by heating and fusion then by being applied on the matrix such as means such as spraying, dip-coating or the showerings of curtain formula.
By the film coating that electrostatic applications obtained of powder paint compositions, thickness is generally about 50-100 μ m, and dispersion coating composition generally produces the coating that thickness is 20 μ m.But for requiring etch-proof application, such thickness is not enough, and this just requires to develop the coating composition that can form than thick coating.
Japanese patent application 57-15607 discloses a kind of fluoro-resin liquid dispersion that is applicable to thick film coating construction, and it comprises and is dispersed in that a kind of surface tension is no more than in the liquid dispersion medium of 45 dynes per centimeter, median size is that 2-300 μ m, porosity are not more than a kind of fluororesin powder that can flow that is heated of 0.74.When this dispersion physical efficiency is in level on applied surface, form the thick thick coating of 500 μ m, but when applied Surface Vertical or inclination certain angle, this fluororesin powder can fall down from being coated with the surface before baking and film forming.
In order on vertical surface, also to form thick coating, United States Patent (USP) 5,502,097 discloses a kind of fluororesin powder liquid dispersion that is applicable to the thick film coating coating, it comprises a kind of fluororesin powder that can flow that is heated, the median size of powder is 5-300 μ m, porosity be no more than 0.74 and total surface area be no more than 10m 2/ cm 3, they are dispersed in that a kind of surface tension is no more than 45 dynes per centimeter, also comprises a kind of boiling point is in 150 ℃-340 ℃ the liquid dispersion medium of organic liquid.Even this invention can make and is coated with the surface and also can form thick coating when vertical.But,, Working environment is restricted because the combustibility of organic liquid in the dispersion has the danger of blast.
Therefore, still need to form the coating composition of thick coating and energy safe construction on vertical surface, particularly in requiring etch-proof application, for example coating performance almost depends in the chemical plant of coat-thickness.
Summary of the invention
The present invention relates to following discovery: when comprising median size in the fluororesin powder liquid dispersion that can flow when being heated and being no more than the colloidal particle of 1 μ m, can form thick powder coating on vertical surface, this coating can not fall down from matrix before baking and film forming.By add a kind of fibrous heat-resistant filler in dispersion, this effect can further improve.
Therefore, the invention provides and to form the fluororesin powder coating composition that thickness is 100-1000 μ m and the thick coating with excellent corrosion resistance.With an easy spray gun or similar tool, adopt single stage method just can make this coating form a coating film, and the without explosion danger of determining.
Specifically, described fluororesin powder liquid dispersion comprises and accounts for can flow fluororesin powder, surface tension of being heated of liquid dispersion 5-50 volume % and be no more than the liquid dispersion medium of 45 dynes per centimeter and the colloidal particle that median size is no more than 1 μ m, wherein the median size of fluororesin powder be 5-300 μ m, porosity be no more than 0.74 and total surface area be no more than 10m 2/ cm 3Preferred colloidal particle is selected from one group that is made up of inorganic oxide and organic thermally stable polymer.More preferably fluororesin powder liquid dispersion also comprises length and is at least 20 μ m and length-to-diameter ratio and is at least 2 fibrous heat-resistant filler.
Colloidal particle in the preferred fluororesin powder liquid dispersion is the polyethersulfone particle, and they are to add as the aqueous dispersion that comprises a kind of organic solvent and the mixable solvent of a kind of water.Preferably prepare the aqueous dispersion that median size is no more than the PES colloidal particle of 1 μ m with the following step: (1) is dissolved in PES in the organic solvent of a kind of energy solubilization PES; (2) with dissolved PES and a kind of mixable solvent of water that can be dissolved in organic solvent; And (3) will be wherein be dissolved with the water of tensio-active agent and dissolved PES and the mixable solvent of water.
The detailed Description Of The Invention fluoro-resin that to flow that is heated
Can be used for the fluoro-resin that can flow of being heated of the present invention is the multipolymer of tetrafluoroethylene and other comonomer, their can fusing under the temperature more than the fusing point with liquefaction thereby can flow.The example of this analog copolymer comprises tetrafluoroethylene and perfluor (alkyl vinyl ether) (PFA), as perfluor (propyl vinyl ether), the multipolymer (FEP) of multipolymer, tetrafluoroethylene and R 1216 and the multipolymer (ETFE) of tetrafluoroethylene and ethene.The speech that " is heated and can flows ", as used herein, be meant that fluoro-resin is that melt is machinable, therefore, fluorinated resin particle will flow and be fused together when the melt temperature that is heated to them is above.
Can the flow median size of fluororesin powder of used being heated is preferably 5-300 μ m among the present invention.The median size of fluororesin powder of can flowing if be heated surpasses 300 μ m, and then pin hole appears in the coating of Xing Chenging easily.On the other hand, if median size less than 5 μ m, then when forming thick film, the surface of film is cracking easily.In addition, this fluororesin powder that can flow of being heated can also contain filler, but perhaps also can be that wherein particle is through the flowing powder that is heated of surface modification treatment.
The present invention is used, and be heated can the flow mean porosities of fluororesin powder is no more than 0.74, preferably in the 0.34-0.65 scope.If porosity surpasses 0.74, then the coating of Xing Chenging ftractures easily, the easy variation of the surface flatness of coating.In the present invention, " porosity " speech is meant the spatial volume in the powder bed, is expressed from the next:
Figure A9881248400071
In addition, can the flow total surface area of fluororesin powder of being heated of the present invention is no more than 10m 2/ cm 3As used herein, " total surface area " is meant the total surface area of fluororesin powder in the per unit volume resin, with m 2/ cm 3Be unit representation.This value can be obtained with following formula:
Total surface area=(total surface area of every gram powder) * (proportion of resin)
The total surface area of every gram powder is measured with the BET method.Total surface area used among the present invention is less than 10m 2/ cm 3The fluororesin powder that can flow that is heated, when stirring or being dispersed in the dispersion medium, be difficult for fragmentation with lance ejection, and, when they have been separated in dispersion medium and have precipitated, be easy to carry out redispersion by stirring.Therefore can form the slick thick coating of one deck.
Total surface area surpasses 10m 2/ cm 3The fluororesin powder that can flow that is heated, broken tendency is arranged, and broken powder can cause cracking and uneven filming when spraying with spray gun.In addition, because this powder is difficult for redispersion, thereby is difficult to obtain the uniform coat composition of fluorine of concentration, therefore can not form the uniform coating of thickness.
This median size be 5-300 μ m, porosity be no more than 0.74 and total surface area be no more than 10m 2/ cm 3The fluororesin powder that can flow that is heated, can be by the described method of for example JP-B53-11296, by copolymer powder is prepared in one air-flow spirt agglomerating chamber, the environment of agglomerating chamber maintains under the temperature that is not less than the multipolymer fusing point, condition be can not cause each particle to each other molten also.Also can be as JP-A4-202329 to be disclosed, cohesion, particulate semi-molten and efflorescence by colloidal particle prepare.Therefore, used powder can be a kind of more short grained sinter in the liquid dispersion of the present invention.
Can the flow content of fluororesin powder of being heated is the 5-50 volume % of dispersion.Resin concentration is during greater than 50 volume %, the mobile variation of dispersion, thereby in the coating application of the showering of curtain formula and dip-coating and so on, be difficult to obtain uniform coating.And, needing high injection pressure when spraying with spray gun, this is undesirable.On the other hand, when resin concentration is lower than 5 volume %, just be difficult for forming thick film coating, and the consumption of coat composition of fluorine is too many, thereby prolongs time of drying, this is disadvantageous economically.Dispersion medium
The surface tension of used dispersion medium is no more than 45 dynes per centimeter among the present invention.When using the polycomponent dispersion medium, require that surface tension compatible with each other and the blending dispersion medium is no more than 45 dynes per centimeter between dispersion medium.When the surface tension of dispersion medium surpassed 45 dynes per centimeter, powder of the present invention can not fully be soaked into, thereby can form a kind of unsettled liquid dispersion.Surface tension at room temperature (20 ℃) records.
Surface tension is less than the dispersion medium of the 45 dynes per centimeter liquid mixture of water and a kind of water-soluble organic liquid preferably.The example of this water-soluble organic liquid comprises the alcohols as methyl alcohol, ethanol, Virahol and trimethyl carbinol and so on, the ketone of acetone and methylethylketone (MEK) and so on, and their mixture.But it is undesirable containing a high proportion of water in the liquid mixture, because this can cause film forming efficiency low.Therefore, ratio of mixture is to determine according to coating application and required thickness.Colloidal particle
The median size of used colloidal particle is no more than 1 μ m among the present invention, preferably is no more than 0.5 μ m.Colloidal particle can be that spheric also can be fibrous.For increasing film-forming properties, preferably they are fibrous.
" colloid " speech is meant a kind of material that is in separate stage, it can stop up the passage of semi-permeable membranes, by the very little granulometric composition that can't differentiate with ordinary optical microscope, looks to resemble solution, and in suspension or solution, can not settle down, but can diffracted ray.The particle diameter that is applicable to colloidal particle of the present invention is little, thereby forms the colloid that a kind of water and/or organic solvent play the dispersion medium effect therein.This helps the volatilization of dispersion medium, thus can be heated can flow dry and solidify under the temperature below the fluororesin powder fusing point.If colloidal particle is heat-staple (heat-stable), then they can not cause dehydration reaction or gasification more than the fusing point of fluoro-resin being heated to flow, and dehydration and gasification are not wished to take place, because their can cause bubble in coating.In addition, high temperature also is undesirable, the decomposition of fluororesin powder of can flowing because they may promote to be heated.
The example of available colloidal particle comprises the colloidal particle of the colloidal particle of inorganic oxide such as silicon oxide, aluminum oxide, zinc oxide, stannic oxide etc. and organic heat stable resin such as aromatic polyimide (comprising polyamidoimide), aromatic poly, aromatic polyester, polyethylene terephthalate, polyphenylene sulfide, polyether-ether-ketone, polysulfones, polyetherimide, polyethersulfone etc.Consider water-repellancy and chemical resistant properties, preferably select the type of colloidal particle according to the requirement of coating application.
Organic heat stable resin comprise a kind of be heated to when fusing can film forming polymkeric substance, it is heat-staple, ability is at least about 140 ℃ life-time service temperature.Heat stable resin is being used for that fluoropolymer is bonded to matrix, film forming and is giving rub resistance and the non-adhering surfaces coating of wear resistant is well-known.This resinoid is generally fluorine-containing but can bond with fluoropolymer yet.The example of this base polymer comprise following one or more: (1) polysulfones: this is that a class second-order transition temperature is about 185 ℃ amorphous thermoplastic polymers, the life-time service temperature that ability is 140 ℃-160 ℃; (2) polyethersulfone: this is that a class second-order transition temperature is about 230 ℃ amorphous thermoplastic polymers, the life-time service temperature that ability is 170 ℃-190 ℃; (3) polyphenylene sulfide: this is that a class fusing point is about 280 ℃ partially crystalline polymer, the life-time service temperature that ability is about 200 ℃-240 ℃; (4) polyimide and/or polyamidoimide or their polyamic acid presoma (for example polyamic acid salt): they take place crosslinked when coating is heated to fusing, the life-time service temperature of ability more than 250 ℃; (5) polyarylene ether ketone such as polyether-ether-ketone and PEKK: the life-time service temperature of their abilities more than at least 250 ℃; Wherein, the glass transition temperature of amorphous ketone polymer should be at least about 145 ℃, and the fusing point of crystallization ketone polymer should be at least about 290 ℃.All these base polymers in their life-time service temperature range or following all be thermally-stabilised and dimensional stabilizing, and be attrition resistant.This base polymer can also be bonded on the metallic surface of cleaning well.Have found that polyimide and/or polyamidoimide particularly suitable are because they can make composition have good wear resistance and thermotolerance.
Before but liquid dispersion is baked to be heated fusion of stir-in resin powder particle and film forming, the colloidal particle that is dispersed in the fluororesin powder plays linking agent and promotion and bond matrix simultaneously, thereby stops the fluororesin powder that can flow of being heated to be fallen down from being coated with matrix.So can form a thick coating.
Preferred colloidal particle content is no more than the 6.0 weight % of fluororesin powder of can flowing that are heated.Preferred can stop to apply the content of expecting the colloidal particle that falls down low as far as possible.6.0 the above colloidal particle content of weight % tends to make institute's applied layer to fade and bubble.When this content was very high, the plasticity of coating reduced, and form the defective of pin hole and so in coating, and the intensity of coating was not high.
Preferred colloidal particle is a kind of organic heat stable resin with self-forming coating ability.The especially preferred colloidal particle of being made by polyethersulfone (below be referred to as PES), this colloidal particle has high thermotolerance and high chemical resistant properties.The PES colloidal particle
In the preferred version of the present invention that adopts the PES colloidal particle, the present invention adopts median size to be no more than 1 μ m, preferably is no more than the PES colloidal particle of 0.5 μ m.Preferably with colloidal particle with comprise the PES colloidal particle, a kind of can solubilization the organic solvent of PES, be under 20-25 ℃ and the form of the aqueous dispersion of the mixable solvent of a kind of water adds preferably in room temperature.
Median size is unfavorable greater than the commodity PES of 1 μ m.Because the particle diameter according to the used PES colloidal particle of the present invention is little, water or organic solvent are made dispersion medium can form colloidal solution.This form is relatively good because it helps the evaporation of dispersion medium, thereby can be lower than be heated can flow dry and solidify under the temperature of fluororesin powder fusing point.
PES is a kind of polymer compound that contains repeating unit shown in the following formula at least.PES polymkeric substance or multipolymer can be used.Structure 1
Figure A9881248400101
The example of PES comprises following polymkeric substance, promptly only contains the polymkeric substance (" the VICTREX PES " that ICI company makes, " the ULTRASON E " that BASF AG makes) of above-mentioned repeating unit; The polymkeric substance (" UDEL " that Amoco company makes, " ULTRASONS " that BASF AG makes) that contains following repeating unit.Structure 2
Figure A9881248400102
Median size is no more than the aqueous dispersion of the PES colloidal particle of 1 μ m, preferably preparation through the following steps: (1) is dissolved in PES in the organic solvent of a kind of energy solubilization PES, is to carry out under 20-25 ℃ in room temperature preferably; (2) with the described PES of dissolved and a kind of mixable solvent of water that can be dissolved in described organic solvent; And (3) wherein have been dissolved with tensio-active agent to produce the dispersive colloidal particle with water and dissolved PES and the mixable solvent of water in the water.The present invention relates to a kind of method that is used for preparing the aqueous dispersion that has good dispersion and particulate footpath polyethersulfone colloidal particle concurrently.
The preferred organic solvent of dissolving PES is the mixture of N-N-methyl-2-2-pyrrolidone N-(below be referred to as NMP) or N,N-DIMETHYLACETAMIDE (below be referred to as DMA) or NMP and DMA.If can disperse PES and the solvent of not solubilization PES, then can obtain dispersed bad big particle diameter PES with a kind of.
In being dissolved with the organic solution of PES (preferred NMP or DMA or their mixture), the content of preferred PES is 20 weight % or littler.If the content of PES surpasses 20 weight %, then when adding or infiltrating the mixable solvent of water that is dissolved among NMP or the DMA, wherein being dissolved with the nmp solution of PES or DMA solution or their mixture will condense, and perhaps can condense when it mixes with purified water.This cohesion is not wished to take place.And, in NMP or N,N-DIMETHYLACETAMIDE the weight of molten water-soluble solvent big more, then the median size of PES colloidal particle is just more little in the PES aqueous dispersion.
The mixable solvent of water of any solvent as PES solution can be dissolved in the mixable solvent of water of organic solvent (preferred NMP or DMA or their mixture), all can be used as to add the solvent that contains PES organic solution.The mixable solvent of preferably water is at least a following one group organic solvent that is selected from: alcohol, glycol, ketone or ester.Specific examples comprises ethanol, Virahol, tetrahydrofurfuryl alcohol, 1,2 ethylene glycol, propylene glycol, acetone, methyl acetate etc.Do not use other solvent but do not get rid of.
When the above-mentioned weight that is dissolved in the mixable solvent of water of organic solvent increased, the median size of the PES colloidal particle in the PES aqueous dispersion trended towards diminishing.
If the amount of the mixable solvent of water that adds is too much, then in the solution molten PES will condense and precipitate.If the amount of the mixable solvent of water that adds is very few, then PES will condense in this subsequent step that the solution of moisture mixable solvent is added while stirring distilled water and precipitate.The amount of the mixable solvent of water that is added depends on the type of the mixable solvent of water.But, wish to adopt the consumption that can not cause the problems referred to above.
When the solution adding that wherein contains dissolved PES that will prepare as mentioned above wherein contains the purified water of having dissolved tensio-active agent and mixes, may obtain a kind of colloidal solution of forming by the PES colloidal particle.Preferably be dissolved in tensio-active agent in the purified water and comprise the negatively charged ion or the nonionogenic tenside that can guarantee the PES aqueous dispersion stable emulsion that constitutes by the PES colloidal particle.Particularly preferably be octylphenoxy polyethoxy ethanol.
The median size of contained PES is measured with particle-size analyzer in moisture PES dispersion, and the median size that obtains is 1 μ m or littler.The moisture PES dispersion for preparing among the present invention contains particulate footpath PES colloidal particle.This moisture PES dispersion can be used separately, perhaps also can make up with other resin such as fluoro-resin, obtaining a kind of blended aqueous dispersion, and makes heat resisting coating or coating polymer is used.Bat wool
Fluororesin powder liquid dispersion of the present invention preferably includes a kind of length and is at least 20 μ m and length-to-diameter ratio and is at least 2 fibrous heat-resistant filler.Fibrous heat-resistant filler helps to stop the be heated fluororesin powder that can flow to be fallen down from being coated with the surface between the coating dry epoch.Thought already, length is at least 20 μ m and length-to-diameter ratio and is at least 2 fibrous heat-resistant filler, can by and big particle diameter be heated can flow that fluororesin powder takes place to tangle and by during alleviating film and forming because of matrix and the distortion that the difference of thermal expansion and thermal contraction causes between the fluororesin powder of can flowing of being heated reduce coming off of coating.Length is relatively poor in effect aspect the prevention coating shedding less than 2 bat wool less than 20 μ m and length-to-diameter ratio.
Useful fiber shape heat-resistant filler, be at least the example that 20 μ m and length-to-diameter ratio are at least those fibrous heat-resistant fillers of 2 as length, the inorganic fibre that glass fibre, carbon fiber, rock wool, ceramic fiber and potassium titanate crystal whisker and so on are arranged, the organic fibre of aromatic poly and so on and their mixture.
The content of bat wool is less than that comprising is heated and can flows 65 volume % of the solid amount of fluororesin powder and bat wool.The content that surpasses 65 volume % can cause too many cavity, is difficult to obtain uniform coating.Other filler
The coating composition of fluororesin powder liquid dispersion of the present invention can contain other filler except that above-mentioned bat wool.The example of this class filler comprises inorganic materials such as metal powder, metal oxide, granulated glass sphere, pottery, silicon carbide, Calcium Fluoride (Fluorspan), carbon black, graphite, cullet and mica and other inorganic substance, PPS (polyphenylene sulfide), PEEK (polyether-ether-ketone), aromatic poly, " Econol " (registered trademark of a kind of aromatic polyester) and other heat resistant plastice.These fillers can add with above-mentioned fibrous heat-resistant filler.But they should have anti-at least 200 ℃, or the thermotolerance of preferred anti-300 ℃ or higher temperature, and their pyrolysis of fluoro-resin of can flowing that should not promote to be heated.The fluororesin powder weight that can flow to be heated is benchmark, adds the PPS that 0.05-5 weight % median size is no more than 20 μ m, has at fluororesin powder under the situation of decomposition, can suppress effectively to film to bubble or foaming.
If with spraying method fluorine resin coating powder liquid dispersion, then the viscosity of preferred dispersions is 8-14 second, crosses rare fluid drips that causes because of liquid when preventing to spray and drop down; Or causing coating inhomogeneous because of liquid is feeding-up, viscosity is measured with No. 4 cup viscometers of Zahn (manufacturing of Toyo Seiki company).
Fluororesin powder liquid dispersion of the present invention can be coated directly onto on the matrix, and dispersion perhaps of the present invention also can be coated with behind the priming paint that coating first road is made by PTFE or PFA colloidal solution on the base material earlier again.
By selecting filler type and consumption thereof, or be coated with by cover and contain filler coating, the fluororesin powder liquid dispersion that is obtained by the present invention is applicable to the construction that is intended to protection against corrosion, not sticking, wear-resisting or purposes such as electric or conduction.The example of protection against corrosion purposes comprises the coating of reactor, agitator paddle, plate washer or heat exchanger tube.The example of abrasionproof purposes comprises the coating of hopper, chute, compressor rotor, papermaking roller, peel of mould and sliding members.The example of electric insulation purposes comprises the coating of electrode.
Embodiment
The present invention is illustrated with the following example.Narrate parent material such as resin, dispersion medium and other starting material below one by one and the evaluation method that forms the test method and the physicals of filming of filming etc.(1) parent material (a) fluororesin powder that to flow that is heated
The PFA powder Poly-fluorine chemistry company of Mitsui Du Pont product (median size 28 μ m, porosity 0.64, total surface area 0.6m 2/cm 3)
The PEP powder Poly-fluorine chemistry company of Mitsui Du Pont product (median size 45 μ m, porosity 0.47, total surface area 0.4m 2/cm 3)
The ETFE powder Poly-fluorine chemistry company of Mitsui Du Pont product (median size 22 μ m, porosity 0.46, total surface area 0.7m 2/cm 3)
The performance of fluororesin powder is measured with following method
(ⅰ) median size
Little footpath method: use Leeds ﹠amp; Little footpath particle-size analyzer 7991-01 type that Northrup company makes is measured.
(ⅱ) porosity:
Figure A9881248400131
(ⅲ) total surface area
Total surface area=(total surface area of every gram powder) * (proportion of resin)
The total surface area of every gram powder is measured with the BET method.(b) colloidal particle (b-i) PES colloidal particle
Make by while stirring PES (" polyethersulfone 5003P ", Sumitomo chemical company product) being dissolved in NMP that PES content is the solution of 5.0 weight % among the NMP.
While stirring 10g ethanol is added in the above-mentioned solution of 40g, to form clear solution.Then, this solution is added to 37.5g wherein has been dissolved with in the purified water of octylphenoxy polyethoxy ethanol solution that 2.5g concentration is 10 weight %, and mix, forming PES colloidal particle concentration is the creamy white colloidal solution of 2 weight %.For the PES colloidal particle in the colloidal solution, measure its median size with particle-size analyzer (" Microtrack " UPA 150 particle-size analyzers that Nikkiso K.K. Corp. makes), the result is 0.16 μ m.
As mentioned above, the used mixable solvent of water is an ethanol among the embodiment.Be applicable to that colloidal particle of the present invention is to produce with 10g Virahol, tetrahydrofurfuryl alcohol, acetone or methyl acetate respectively, the particle diameter of formed PES is respectively 0.16 μ m, 0.16 μ m, 0.20 μ m, 0.18 μ m and 0.18 μ m.Similarly, change the add-on of the mixable etoh solvent of water and the consumption of tensio-active agent, prepare 6.0 weight % and the solution of 20 weight %PES in NMP and NMP/DMA, forming particle diameter is the particle of 0.17-0.20 μ m.
And observed, in PES solution, adding entry or contain before the water of tensio-active agent if do not add the mixable solvent of water earlier, solution will condense, and what obtain is the creamy white precipitation, rather than colloidal particle of the present invention.(b-ⅱ) other colloidal particle
SO 2 The Snowtex UP (the minority particle diameter is 5-30 μ m, and most particle diameters are 40-300 μ m) that Nissan chemical industrial company makes
Al 2O 3 The aluminum oxide Sol-100 (the minority particle diameter is 10 μ m, and most particle diameters are 100 μ m) that Nissan chemical industrial company makes
SiO 2/LiO 2 (Nissan chemical industrial company makes lithium silicate 75, SiO 2/LiO 2The mol ratio be 7.5)
(c) fibrous heat-resistant filler
Carbon fiber The carbon fiber M2007S (the minority diameter is 14.5 μ m, and most diameters are 100 μ m) that Kureha chemical company makes
Glass fibre The glass fibre EPG140M (the minority diameter is that 9.0 μ m and most diameter are 140 μ m) that Nippon Denki Glass K.K. Corp. makes
(d) suds suppressor
PPS The Ryton that Toso Susteel K K company makes V-1 milling product (median size 14 μ m)
(e) organic liquid composition in the dispersion medium
Ethanol 78.3 ℃ of boiling points, surface tension 24.0 dynes per centimeter
The trimethyl carbinol 82.5 ℃ of boiling points, surface tension 22.2 dynes per centimeter
(f) other filler
Tetrafluoroethylene molding powder The 70-J (median size 35 μ m) that fluorine chemistry company of Mitsui Du Pont makes
Polyether-ether-ketone The 150PF/PB134 (median size 35 μ m) that Mitsui chemical company makes
(2) coating forms the coating of test method (a) prime treatment
By PTFE: PFA resin ratio is 3: 1, and with the liquid dispersion that emulsion polymerization PTFE dispersion and emulsion polymerization PFA liquid mixing are made, it is thick to be applied to 3-5 μ m on the SUS plate of a thick 1mm, wide 50mm and long 100mm.Spraying is gone up a kind of fluororesin powder dispersion to form the coating of specific thicknesses then.Is that 45 ° mode places in the warm air convection oven with this plate with coating surface, carries out drying and sintering according to the temperature program(me) shown in table I and the table II, with the formation film.(b) directly coating
On the SUS plate of a thick 1mm, wide 50mm and long 100mm, spray fluororesin powder liquid dispersion, have the coating of specific thicknesses with formation.Is that 45 ° mode places in the warm air convection oven with this plate with coating surface, carries out drying and sintering by the temperature program(me) shown in table I and the table II, with the formation film.
Temperature program(me)
Table I-used temperature program(me) of embodiment 1-7
Table I A
PFA (the about 1200 μ m of the about 600 μ m-of thickness)
In 60 minutes, be heated to 110 ℃ from 80 ℃
In 30 minutes, be heated to 180 ℃ from 110 ℃
In 60 minutes, be heated to 210 ℃ from 180 ℃
In 60 minutes, be heated to 310 ℃ from 210 ℃
In 80 minutes, be heated to 350 ℃ from 310 ℃
350 ℃ of sintering 30 minutes
Table I B
ETFE (the about 1200 μ m of the about 600 μ m-of thickness)
In 60 minutes, be heated to 110 ℃ from 80 ℃
In 30 minutes, be heated to 180 ℃ from 110 ℃
In 60 minutes, be heated to 210 ℃ from 180 ℃
In 90 minutes, be heated to 300 ℃ from 210 ℃
300 ℃ of sintering 30 minutes
The used temperature program(me) table II A of table II-embodiment 8-16
PFA and FEP (the about 500 μ m of the about 300 μ m-of thickness)
110 ℃ of dryings 40 minutes, then at 20 minutes internal heating to 210 ℃
210 ℃ of dryings 40 minutes, then at 20 minutes internal heating to 310 ℃
310 ℃ of dryings 40 minutes, then at 20 minutes internal heating to 340 ℃
340 ℃ of sintering 20 minutes
Table II B
ETFE (the about 500 μ m of the about 300 μ m-of thickness)
110 ℃ of dryings 40 minutes, then at 20 minutes internal heating to 200 ℃
200 ℃ of dryings 40 minutes, then at 20 minutes internal heating to 280 ℃
280 ℃ of dryings 40 minutes, then at 20 minutes internal heating to 310 ℃
310 ℃ of sintering 20 minutes
(3) method of assess performance (a) film forming and the state that comes off:
Zero: the coating that has formed institute's required thickness
*: toner falls down between dry epoch, thereby does not form coating.(b) thickness:
Measure with micrometer
Embodiment 1 and 2
Can flow being heated fluororesin powder PFA, liquid dispersion medium, bat wool carbon fiber and 2 weight %PPS suds suppressors mix by the consumption of table shown in the III, described liquid dispersion medium is the liquid mixture of ethanol, the trimethyl carbinol and ethylene glycol, and its surface tension is 45 dynes per centimeter or lower.
Then, the PES colloidal solution of water and 2 weight % is added in the mixture that is obtained to form fluoride resin powder liquid dispersion.
With coating method (2-a) this fluororesin powder liquid dispersion is coated on the SUS plate, carries out sintering by the temperature program(me) shown in the table I A then.Estimate the performance of coating, the results are shown in the table III.
Embodiment 3
By with embodiment 2 in identical method prepare fluororesin powder liquid dispersion, but replace carbon fiber among the embodiment 2 as bat wool, and change the consumption of PFA powder into 19.4g with glass fibre.Form and list in the table III.
By with embodiment 2 in identical method, fluororesin powder liquid dispersion is coated on the SUS plate and the sintering film forming.Estimate the performance of coating, the results are shown in the table III.
Embodiment 4
By with embodiment 2 in identical method prepare fluororesin powder liquid dispersion, but in embodiment 2, the used glass fibre, also add the PEEK of 10 weight %, and change the consumption of PFA powder into 16.4g by the consumption shown in the table III.
By with embodiment 2 in identical method, fluororesin powder liquid dispersion is coated on the SUS plate and the sintering film forming.Estimate the performance of coating, the results are shown in the table III.
Embodiment 5
By with embodiment 4 in identical method prepare fluororesin powder liquid dispersion, but by the listed amount of table III with the PEEK that uses as another kind of filler among the tetrafluoroethylene molding powder replacement embodiment 4.
By with embodiment 4 in identical method, fluororesin powder liquid dispersion is coated on the SUS plate and the sintering film forming.Estimate the performance of coating, the results are shown in the table III.
Embodiment 6
By with embodiment 4 in identical method prepare fluororesin powder liquid dispersion, but replace that being used as among the embodiment 2 is heated and can flow the PFA of fluororesin powder, and change the consumption of carbon fiber into 2.0g with the 18.0gETFE powder.
By with embodiment 2 in identical method, fluororesin powder liquid dispersion is coated on the SUS plate, and by the temperature program(me) sintering film forming shown in the table I B.Estimate the performance of coating, the results are shown in the table III.
Embodiment 7
By with embodiment 6 in identical method prepare fluororesin powder liquid dispersion, but change the consumption of consumption from embodiment 6 of the colloidal solution of 2 weight %PES into 20.0g.
By with embodiment 6 in identical method, fluororesin powder liquid dispersion is coated on the SUS plate and the sintering film forming.Estimate the performance of coating, the results are shown in the table III.Comparative example 1
By with embodiment 1 in identical method prepare fluororesin powder liquid dispersion, but do not add PES colloidal solution used among the embodiment 1.
By with embodiment 1 in identical method, fluororesin powder liquid dispersion is coated on the SUS plate and the sintering film forming.Estimate the performance of coating, the results are shown in the table III.
The table III
Embodiment 1 Embodiment 2 Embodiment Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Comparative example 1
Dispersion is formed (g)
PFA ?????9.5 ?????18.2 ????19.4 ?????16.4 ????16.4 ?????- ??????- ?????9.5
ETFE ?????- ???????- ??????- ???????- ??????- ????18.0 ????18.0 ?????-
Ethanol ?????3.0 ??????6.0 ?????6.0 ??????6.0 ?????6.0 ?????6.0 ?????6.0 ?????3.0
The trimethyl carbinol ?????3.0 ??????6.0 ?????6.0 ??????6.0 ?????6.0 ?????6.0 ?????6.0 ?????3.0
1,2 ethylene glycol ?????2.5 ??????5.0 ?????5.0 ??????5.0 ?????6.0 ?????5.0 ?????5.0 ?????2.5
Purified water ?????2.5 ??????5.0 ?????5.0 ??????5.0 ?????5.0 ?????5.0 ??????- ?????2.5
2%PES solution ?????2.5 ??????5.0 ?????5.0 ??????5.0 ?????6.0 ?????5.0 ?????20.0 ??????-
Carbon fiber ?????0.5 ??????1.8 ??????- ??????1.8 ?????1.8 ?????2.0 ?????2.0 ?????0.5
Glass fibre ??????- ??????- ?????3.0 ???????- ??????- ??????- ??????- ??????-
Polyether-ether-ketone ??????- ??????- ??????- ??????1.8 ??????- ??????- ??????- ??????-
Tetrafluoroethylene ??????- ??????- ??????- ???????- ?????1.8 ??????- ??????- ??????-
PPS ?????0.2 ?????0.4 ?????0.4 ??????0.4 ?????0.4 ??????- ??????- ?????0.2
Drop priming Have Have Have Have Have Do not have Do not have Do not have
Coating performance
Film-forming properties ?????○ ?????○ ?????○ ?????○ ?????○ ?????○ ?????○ ?????×
Thickness (μ m) ?????600 ?????1200 ????1200 ?????1200 ????1200 ????1200 ????1200 ?????600
Slickness ?????○ ?????○ ?????○ ?????○ ?????○ ?????○ ?????○ ?????×
Embodiment 8-11
Fluororesin powder PFA, liquid dispersion medium, the colloidal particle SiO of can flowing will be heated 2, bat wool carbon fiber and suds suppressor PPS mix by the amount shown in the table IV, make fluororesin powder liquid dispersion, wherein said liquid dispersion medium is the liquid mixture of a kind of ethanol, the trimethyl carbinol and ethylene glycol, and its surface tension is 45 dynes per centimeter or lower.
With coating method (2-a) this fluororesin powder liquid dispersion is coated on the SUS plate, carries out sintering by the temperature program(me) shown in the table II A then.Estimate the performance of coating, the results are shown in the table IV.Embodiment 12-14
To can flow as being heated the mixture of the PFA powder of fluororesin powder, ethanol, the trimethyl carbinol and water as liquid dispersion medium, as the Al of colloidal particle 2O 3, mix by the amount shown in the table IV as the carbon fiber of bat wool with as the PPS of suds suppressor, make fluororesin powder liquid dispersion.Use then with Application Example 8-11 in the identical coating that adopts form the performance that forms coating with test method and estimate them, the results are shown in the table IV.
Embodiment 15
By with embodiment 8-11 in identical method prepare fluororesin powder liquid dispersion, but, use SiO with the FEP powder PFA that fluororesin powder uses that replaces among the embodiment 8-11 can flowing as being heated 2/ LiO 2Replace used SiO among the embodiment 8-10 2With with Application Example 8-11 in the identical coating that adopts form the performance that forms coating with test method and estimate them, the results are shown in the table V.
Embodiment 16
By with embodiment 8-11 in identical method prepare fluororesin powder liquid dispersion, but with the ETFE powder PFA that fluororesin powder uses that replaces among the embodiment 8-11 can flowing as being heated, and by listed amount in the table V each identical component is mixed, to form fluororesin powder liquid dispersion.With with example 8-11 in the identical coating that adopts form with test method and form coating, carry out sintering by the temperature program(me) shown in the table II B then, to form no primer coating.Estimate the performance of coating then, the results are shown in the table V.Comparative example 2
By with embodiment 8 in identical method, prepare fluororesin powder liquid dispersion by the consumption of table shown in the V, but do not add SiO 2Colloidal particle.With with embodiment 8 in the identical coating that adopts form and test method, be coated with and sintering.Estimate the performance of coating, the results are shown in the table V.Comparative example 3
By with embodiment 8 in identical method prepare fluororesin powder liquid dispersion, but do not add SiO 2Colloidal particle and carbon fiber.Use then with embodiment 8 in identical coating form and test method, be coated with and sintering.Estimate the performance of coating, the results are shown in the table V.
In the embodiment 1-7 that has added PES colloidal solution and added among the embodiment 8-16 of mineral colloid solution, formed high-quality coating.Shown in the result of table in III-V, coating has formed, and does not have and come off and separate.By contrast, shown in comparative example 1-2, when not adding colloidal particle, though coating does not come off, in 50% coating sample separation has appearred.In both not adding the comparative example 3 that colloidal particle do not add bat wool yet, coating comes off, and does not stay any coating on matrix.The table IV
Embodiment 8 Embodiment 9 Embodiment 10 Embodiment 11 Embodiment 12 Embodiment 13 Embodiment 14
Dispersion is formed (g)
PFA ?????7.2 ?????7.2 ??????7.2 ?????7.2 ??????7.2 ??????7.2 ??????7.2
FEP ??????- ??????- ???????- ??????- ???????- ???????- ???????-
ETFE ??????- ??????- ???????- ??????- ???????- ???????- ???????-
Ethanol ?????2.25 ????2.25 ?????2.25 ????3.00 ?????2.25 ?????2.25 ?????2.25
The trimethyl carbinol ?????2.25 ????2.25 ?????2.25 ????3.00 ?????2.25 ?????2.25 ?????2.25
Purified water ?????3.00 ????3.00 ?????3.00 ????4.00 ?????3.00 ?????3.00 ?????3.00
SiO 2 ?????0.025 ????0.100 ?????0.400 ????0.400
Al 2O 3 ?????0.01 ?????0.?033 ?????0.100
SiO 2/Li0 2 ???????- ??????- ???????- ??????- ??????- ???????- ???????-
Carbon fiber ?????1.3 ?????1.3 ?????1.3 ?????1.6 ?????1.3 ?????1.3 ??????1.3
Glass fibre ???????- ??????- ???????- ??????- ??????- ???????- ???????-
PPS ?????0.15 ????0.15 ?????0.15 ????0.20 ?????0.15 ?????0.15 ?????0.15
Drop priming Have Have Have Have Have Have Have
Coating performance
Film-forming properties ?????○ ?????○ ?????○ ?????○ ?????○ ?????○ ?????○
Thickness (μ m) ?????500 ????500 ?????500 ????700 ?????500 ?????500 ?????500
Slickness ??????○ ??????○ ??????○ ??????○ ??????○ ??????○ ??????○
The table V
Embodiment 15 Embodiment 16 Comparative example 2 Comparative example 3
Dispersion is formed (g)
PFA ????????- ??????- ??????7.2 ??????7.5
FEP ???????7.2 ??????- ???????- ???????-
ETFE ????????- ?????7.2 ???????- ???????-
Ethanol ???????2.25 ?????2.50 ??????2.25 ??????2.25
The trimethyl carbinol ???????2.25 ?????2.50 ??????2.25 ??????2.25
Purified water ???????3.00 ?????4.00 ??????3.00 ??????3.00
SiO 2 ????????- ????0.020 ??????- ???????-
Al 2O 3 ????????- ??????- ??????- ???????-
SiO 2/LiO 2 ??????0.0375 ??????- ??????- ???????-
Carbon fiber ????????1.3 ??????- ??????1.3 ???????-
Glass fibre ????????- ?????1.3 ??????- ???????-
?PPS ??????0.15 ??????- ??????0.15 ??????0.15
Drop priming Have Do not have Do not have Have
Coating performance
Film-forming properties ??????○ ??????○ ??????× ??????×
Thickness (μ m) ??????500 ??????550 ??????- ???????-
Slickness ??????○ ??????○ ??????× ??????×
Therefore, the colloidal particle fluororesin powder liquid dispersion that contains of the present invention can prevent that coating from splitting away off from matrix, so can form thicker coating in dry and sintering circuit.When containing length, fluororesin powder liquid dispersion is at least 20 μ m and length-to-diameter ratio when being at least 2 bat wool, above-mentioned effect even more obvious.When being applied to this dispersion on the matrix, can form well behaved base materials such as solidity to corrosion, non-viscosity, chemical resistant properties, wear resistance, electrical insulating property, these performances are of great use to chemical plant and mechanical industry.

Claims (28)

1. fluororesin powder liquid dispersion, it comprises fluororesin powder, liquid dispersion medium and the colloidal particle of can flowing that be heated that accounts for this liquid dispersion 5-50 volume %, the median size of described fluororesin powder is 5-300 μ m, porosity be not more than 0.74 and total surface area be not more than 10m 2/ cm 3, the surface tension of described liquid dispersion medium is no more than 45 dynes per centimeter, and the median size of described colloidal particle is no more than 1 μ m.
2. the fluororesin powder liquid dispersion of claim 1, wherein the median size of colloidal particle is no more than 0.5 μ m.
3. the fluororesin powder liquid dispersion of claim 1, wherein the content of colloidal particle is no more than the 6.0 weight % of fluororesin powder of can flowing that are heated in the dispersion.
4. the fluororesin powder liquid dispersion of claim 1, wherein colloidal particle is selected from one group that is made up of the colloidal particle of inorganic oxide and organic heat stable resin.
5. the fluororesin powder liquid dispersion of claim 4, wherein colloidal particle is selected from following one group of organic heat stable resin: aromatic polyimide, many virtue nuclear polyamidoimides, aromatic poly, aromatic polyester, polyethylene terephthalate, polyphenylene sulfide, polyether-ether-ketone, polysulfones, polyetherimide and polyethersulfone.
6. the fluororesin powder liquid dispersion of claim 5, wherein colloidal particle is a polyethersulfone.
7. the fluororesin powder liquid dispersion of claim 4, wherein colloidal particle is selected from one group of inorganic oxide being made up of silicon oxide, aluminum oxide, zinc oxide and stannic oxide.
8. the fluororesin powder liquid dispersion of claim 1, can the flow porosity of fluororesin powder of wherein being heated is 0.34-0.65.
9. the fluororesin powder liquid dispersion of claim 1 wherein also comprises the fibrous heat-resistant filler that is no more than total solids 65 volume %, and the length of bat wool is at least 20 μ m and length-to-diameter ratio is at least 2.
10. the fluororesin powder liquid dispersion of claim 1, wherein liquid dispersion medium is the mixture of water and a kind of water-soluble organic liquid.
11. the fluororesin powder liquid dispersion of claim 1 wherein also comprises its amount and is the 0.05-5% (weight) of fluororesin powder, the polyphenylene sulfide that median size is no more than 20 μ m of can flowing that be heated.
12. the fluororesin powder liquid dispersion of claim 1, described dispersion are used for forming the thick coating of 100-1000 μ m in an one-step film forming method.
13. the fluororesin powder liquid dispersion of claim 1, wherein said fluoro-resin are a kind of multipolymers of tetrafluoroethylene.
14. the fluororesin powder liquid dispersion of claim 13, wherein said tetrafluoroethylene and perfluor (alkyl vinyl ether) copolymerization.
15. the fluororesin powder liquid dispersion of claim 13, wherein said tetrafluoroethylene and R 1216 copolymerization.
16. the fluororesin powder liquid dispersion of claim 13, wherein said tetrafluoroethylene and ethylene copolymer.
17. a method of producing the aqueous dispersion of PES colloidal particle, this method comprises the following step:
(1) polyethersulfone is dissolved in a kind of can solubilization the organic solvent of polyethersulfone;
(2) with the described polyethersulfone of dissolved and a kind of mixable solvent of water that can be dissolved in described organic solvent; And
(3), be dissolved with tensio-active agent in the wherein said water to generate colloidal particle with water and described polyethersulfone of dissolved and the mixable solvent of described water.
18. the method for claim 17, the median size of wherein said colloidal particle are no more than 1 μ m.
19. the method for claim 17, the median size of wherein said colloidal particle are no more than 0.5 μ m.
20. the method for claim 17, wherein said organic solvent are selected from one group that is made up of the mixture of N-N-methyl-2-2-pyrrolidone N-or N,N-DIMETHYLACETAMIDE or N-N-methyl-2-2-pyrrolidone N-and N,N-DIMETHYLACETAMIDE.
21. the method for claim 17, the mixable solvent of wherein said water are selected from one group that is made up of at least a alcohol, glycol, ketone and ester.
22. the method for claim 17, wherein said tensio-active agent are non-ionic or anionic.
23. the method for claim 17 wherein, contains the polyethersulfone that is no more than 20 weight % by the formed solution of dissolving polyethersulfone in step (1).
24. one kind comprises polyethersulfone colloidal particle, a kind of organic solvent of energy solubilization polyethersulfone and the water dispersion of the mixable solvent of a kind of water.
25. the water dispersion of claim 24, the median size of wherein said colloidal particle are no more than 1 μ m.
26. the water dispersion of claim 24, the median size of wherein said colloidal particle are no more than 0.5 μ m.
27. the water dispersion of claim 24, wherein said organic solvent are selected from one group that is made up of the mixture of N-N-methyl-2-2-pyrrolidone N-or N,N-DIMETHYLACETAMIDE or N-N-methyl-2-2-pyrrolidone N-and N,N-DIMETHYLACETAMIDE.
28. the water dispersion of claim 24, the mixable solvent of wherein said water are selected from one group that is made up of at least a alcohol, glycol, ketone and ester.
CNB98812484XA 1997-12-22 1998-12-18 Fluororesin powder liquid dispersion capable of forming thick coatings Expired - Fee Related CN1198893C (en)

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