CN106634479B - Metal coiled material extra-weather-proof microspheroidal powdery paints and preparation method thereof of supercritical fluid technique preparation - Google Patents
Metal coiled material extra-weather-proof microspheroidal powdery paints and preparation method thereof of supercritical fluid technique preparation Download PDFInfo
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- 239000003973 paint Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 46
- 239000012530 fluid Substances 0.000 title claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 38
- 239000002184 metal Substances 0.000 title claims abstract description 38
- 238000000576 coating method Methods 0.000 claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 229920001225 polyester resin Polymers 0.000 claims abstract description 20
- 239000004645 polyester resin Substances 0.000 claims abstract description 20
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 14
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- -1 poly- M-phthalic acid neopentyl glycol ester Chemical class 0.000 claims abstract description 5
- 239000002033 PVDF binder Substances 0.000 claims abstract description 4
- 239000000049 pigment Substances 0.000 claims abstract description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract 2
- PYHXGXCGESYPCW-UHFFFAOYSA-N diphenylacetic acid Chemical compound C=1C=CC=CC=1C(C(=O)O)C1=CC=CC=C1 PYHXGXCGESYPCW-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims 1
- 230000003078 antioxidant effect Effects 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000013456 study Methods 0.000 description 3
- WFLOTYSKFUPZQB-UHFFFAOYSA-N 1,2-difluoroethene Chemical group FC=CF WFLOTYSKFUPZQB-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 230000002421 anti-septic effect Effects 0.000 description 2
- 239000012296 anti-solvent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- CFFZDZCDUFSOFZ-UHFFFAOYSA-N 3,4-Dihydroxy-phenylacetic acid Chemical compound OC(=O)CC1=CC=C(O)C(O)=C1 CFFZDZCDUFSOFZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 235000015511 Liquidambar orientalis Nutrition 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000004870 Styrax Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 125000005670 ethenylalkyl group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000008542 thermal sensitivity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery 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
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to powder coating technology fields, and in particular to a kind of metal coiled material extra-weather-proof microspheroidal powdery paints and preparation method thereof of supercritical fluid technique preparation.The microspheroidal powdery paints is made of the raw material of following mass percent: poly- M-phthalic acid neopentyl glycol ester type polyester resin 35~88, semicrystalline polyester resin 0.1~10, isocyanuric acid three-glycidyl ester 3.2~7, benzyltriethylammoinium chloride 0.1~1.6, polyvinylidene fluoride type fluororesin 1~10, acrylate 0.5~1.5, diphenylhydroxyethanone 0.2~1, pentaerythritol ester 0.1~0.8, pigment 0.2~26 and other auxiliary agents 0~3.The present invention uses supercritical fluid technique, has the characteristics of simple process, stable product quality.Powder coating particles are microspheroidal, and partial size is small and particle size distribution is concentrated, and carry out surfacing when metal coiled material scumbling dress, and weather resistance is good, and flexibility is good, low temperature performance well, are suitble to the ready coating of metal coiled material.
Description
Technical field
The invention belongs to powder coating technology fields, and in particular to a kind of metal coiled material use of supercritical fluid technique preparation
Extra-weather-proof microspheroidal powdery paints and preparation method thereof.
Background technique
Powdery paints is free of any solvent, is solid powdery coating very.Since powdery paints is arranged with Diamond Search
Put, be pollution-free to atmospheric environment, the landing powdery paints that does not spray to workpiece can recycle again, save the energy and resource,
It reduces labor intensity and the advantages such as film excellent combination property.In in the past few decades, in metal product and thermal sensitivity material
Rapid Popularization application has been obtained in material products.And with various countries in recent years to environmental requirement and energy saving resource requirement not
Disconnected to improve, some pollutions are strong, the waste of resource energy coating material is gradually banned, and as with obvious environment-friendly advantage
Powdery paints also gradually expands its application field.
The coating on metal coiled material surface has coating speed fast, and for linear velocity in 100m/min or so, film is thin, and thickness is 35
μm or so, surfacing, comprehensive performance is preferable, the features such as being suitble to open air use, and the intrinsic part of properties of powdery paints is difficult to
Reach these requirements.Therefore, powdery paints applies the application loaded onto metal coiled material and is constantly subjected to limit.Metal coiled material largely produces
Product still use paint spraying.But in recent years, as the continuous pressure and policy of national governments are encouraged, people are to powdery paints
Application study work in metal coiled material field also starts to be paid attention to.Find it is a kind of environmental protection, can completely replace by painting
The new material and new process of coating metal coiled material are extremely urgent.
Since people were still in infancy the research of this project in recent years, these correlative studys are related separately to below
The different function prepared to metal coiled material powdery paints, supercritical fluid powdery paints preparation facilities, supercritical fluid technique
Powdery paints, powdery paints raw material and water paint.
Chinese patent CN105038525A discloses a kind of pre-coated metal coiled material powdery paints and its preparation method and application.
The powdery paints of the invention is that curing agent is added using carboxyl end group saturated polyester resin and end carboxyl super branched polyester resin as base-material
Isocyanuric acid three-glycidyl ester and curing accelerator solidification are made, and have the characteristics that formula is simple, flow leveling is excellent.China
Patent CN105885648A discloses a kind of automatically cleaning polymolecularity coiled material powdery paints and preparation method thereof.The powder of the invention
Coating is by low temperature weather polyester resin, TGIC or HAA, bisphenol A type epoxy resin, PVDF thermoplastic fluorocarbon resin, nano oxygen
Change aluminium, nanometer calcium carbonate, acrylate leveling agent, quaternary ammonium salt accelerator, pigment, filler, other auxiliary agents to be prepared.The present invention
Powdery paints have it is scattered, not easy to knot groups and easily storage, film have stain resistance it is strong, easy to clean, adhesive force is good, surface
Smooth characteristic.Above-mentioned two patent and some other patent all study metal coiled material with powdery paints, but this
A little patents are all the preparation processes of the traditional powder coating used.Compared with supercritical fluid technique, traditional handicraft process is more, work
Skill is complicated, uncontrollable preparation parameter is more, and influences on the powder coating product performance of preparation very big.
Chinese patent CN103055728A discloses a kind of Supercritical fluid device of powdery paints.It includes raw material tank, adds
Hopper, stirring power, processing kettle, classification kettle and packing device, device structure is simple, and dissolubility is strong, and diffusion is good and is easy to
Control.Chinese patent CN101519545 discloses a kind of supercritical CO2Antisolvent precipitation prepares the device and its production work of powdery paints
Skill.Its process unit includes supercritical CO2Antisolvent precipitation kettle, supercritical CO2Export fluid and solid separation system, multi-stage compression
Machine, the supercritical CO dissolved with toluene2Storage tank, tubular heat exchanger, supercritical CO2With the separator of toluene.The invention overcomes tradition
The defects of powdery paints working system, reduces production cost and energy consumption.Above-mentioned two patent is only prepared supercritical fluid
The equipment of powdery paints is updated, and provides development foundation for the innovation preparation process of powdery paints.
Chinese patent CN104109453A discloses a kind of Composite functional form agricultural machinery clear top powder coatings and its production
Technique.The powdery paints includes the component of following mass parts: 2-8 parts of polyester/acrylic resin compound, polyester resin 30-50
Part, 12-22 parts of epoxy modified acrylic resin, 20-35 parts of nanometer glass powder, 1-5 parts of crosslinking agent, 1-2.5 parts of auxiliary agent；It is made
Preparation Method uses supercritical carbon dioxide fluid method.The powdery paints can it is antiseptic and rustproof, again have excellent weatherability, life
Production. art energy consumption is small, high-efficient, reduces production and processing temperature.Chinese patent CN104140746A discloses a kind of compound function
Change infrared external reflection engineering machinery powdery paints and its production technology.The powdery paints includes the component of following mass parts: polyester/the third
2-8 parts of olefin(e) acid resin complexes, 30-50 parts of polyester resin, 10-20 parts of epoxy modified acrylic resin, infrared reflecting paint 15-
35 parts, 1-5 parts of crosslinking agent, 8-18 parts of filler, 1-2.5 parts of auxiliary agent；Its production technology uses supercritical carbon dioxide fluid method.It should
Powdery paints i.e. have it is antiseptic and rustproof, again have excellent weatherability, energy consumption in production process is small, high-efficient, reduce production add
Work temperature.Chinese patent CN105885499A discloses a kind of thermosetting property scratch resistance open air low brightness paint powder and its preparation process.It should
Powdery paints mainly includes at least one resin containing epoxy group such as epoxy group acrylic resin, epoxy resin, isocyanuric acid three
Ethylene oxidic ester and at least one carboxylic resin such as carboxyl polyester resin, carboxyl acrylic resin composition.The family of the invention
Outer low brightness paint powder is to make coating various composition fluidisation by the supercritical carbon dioxide and prepare, and has scratch resistance
Well, the features such as gloss can drop to 5%.Chinese patent CN104559694A discloses a kind of thermosetting property ultrafine powder paint and its preparation
Method.Powdery paints uses supercritical CO by the raw material of following parts by weight2Fluids process is made: 30-70 parts of resin；Curing agent
2-25 parts；0.2-0.7 parts of styrax；0.05-0.75 parts of levelling agent；0.1-0.4 parts of degasser；2.5-22.5 parts of pigments and fillers and anti-
0-5 parts of oxygen agent.Coating partial size is at 10-20 μm, and particle diameter distribution is uniform, geometric configuration is uniform, suitable for there is the automobile of scumbling requirement
The fields such as finishing coat or acrylic acid powder coatings.Preparation method simple process of the invention is easily achieved.Aforementioned four patent is all
The powdery paints of different function is prepared using supercritical fluid technique.
Chinese patent CN101338105 discloses a kind of preparation method of fluor-containing powder resin fro coating.The invention is related to one
Kind carries out radical copolymerization preparation in supercritical carbon dioxide fluid with Fluorine containing olefine and vinyl alkyl ethers/ester monomer and contains
The method of fluorine powdex.The invented technology is simple, eliminate other methods prepare a large amount of energy consumption of fluorine resin and complexity
Last handling process.The invention is only related to the preparation of fluorine resin.Fluorine resin is one in powder coating formulation design
Kind raw material are not directed to the formula design of powdery paints.
Chinese patent CN106010104A discloses a kind of particulate coating material composition preparation process.Compared with prior art, should
The aqueous epoxide resin paint of the supercritical fluid technique preparation of invention, energy rapid curing film forming, coating have outstanding attachment
Power, resistant abrasion, price are low, good leveling property, it is environment-protecting and non-poisonous the advantages that.The invention equally applies supercritical fluid technique, still
Its product belongs to the preparation field of water paint.
Since metal coiled material powdery paints needs some characteristic properties, traditional powdery paints preparation process is used
It is extremely difficult to its requirement, finds a kind of powdery paints preparation process of innovation, and performance according to needed for it is formulated progress to it
Adequately design is very important.
Summary of the invention
The object of the present invention is to provide a kind of extra-weather-proof microspheroidal powder of metal coiled material of supercritical fluid technique preparation
Coating, partial size is small, and size distribution concentration degree is high, and weather resistance is good；Present invention simultaneously provides preparation methods.
The extra-weather-proof microspheroidal powdery paints of metal coiled material of supercritical fluid technique preparation of the present invention, by following
The raw material of mass percent is made:
Wherein:
Poly- M-phthalic acid neopentyl glycol ester type polyester resin is Qing Te company CC2244-0 type polyester resin.
Semicrystalline polyester resin is day pine new material company's T S2100 type polyester resin.
Gross mass percentage composition≤0.4% of organochlorine and inorganic chlorine in isocyanuric acid three-glycidyl ester.
The shape of powder coating particles is microspheroidal, and partial size is between 10~24 μm.
The metal coiled material preparation method of extra-weather-proof microspheroidal powdery paints of the described supercritical fluid technique preparation is
Raw material is put into supercritical reaction kettle to be uniformly mixed, controls CO in reaction kettle2Content is 35~55wt%, and temperature is 48~68
DEG C, pressure is 70~110Kg/cm2, ejiction opening temperature is 56~70 DEG C.
In the present invention:
Firstly, powder coating particles of the invention are the microspheroidal of rule, and size distribution concentration degree is high, and raw material are resistance to
It is good to wait performance.It is irregular shape, and size distribution model that it, which is solved by the powder coating particles of conventional preparation techniques preparation,
Enclose the surface irregularity of coiled material scumbling film caused by width, the non-uniform problem of spraying.
Secondly, powdery paints of the present invention is prepared by supercritical fluid technique, it is able to solve following two problem:
One, it since this technology is when preparing powdery paints, more evenly to the mixing of its raw material, therefore solves and is added in powdery paints
The bad problem of appearance of film caused by extra-weather-proof fluororesin and other raw material poor compatibilities.Pass through supercritical fluid technique
The powdery paints of preparation can add further amounts of extra-weather-proof fluororesin, therefore also substantially increase its outdoor weathe resistance energy.Two,
Product is prepared since this technology belongs to one-step shaping when preparing powdery paints, is different from traditional raw material by high temperature
Multiple processes such as melting extrusion, cooling tabletting is broken, high-speed impact crushes, cyclonic separation sieve powder.Therefore in supercritical fluid skill
Art preparation powdery paints raw material in can add part semicrystalline polyester resin, without because high-temperature fusion, repeatedly
It is crushed and crushes and influence its recrystallization state, it is possible to be obviously improved flatness, flexibility, weatherability and the low temperature of film
Curing performance.
The characteristics of present invention combination supercritical fluid technique, controls supercritical fluid technique technological parameter, complexed metal volume
Material performance needed for powdery paints, which is formulated it, to be rationally designed, and the metal coiled material for obtaining supercritical fluid technique preparation, which is used, to be surpassed
Weather-proof microspheroidal powdery paints.The present invention provides new approaches for the preparation of metal coiled material powdery paints, also provides higher
The product of performance carries out coating by powdery paints completely for metal coiled material and provides guarantee.
The technical principle of the extra-weather-proof microspheroidal powdery paints of metal coiled material of supercritical fluid technique preparation of the invention
It is as follows:
(1) present invention prepares powdery paints using supercritical fluid technique, is different from traditional preparation process completely, can
Microspheroidal is prepared, partial size granularity is small and is distributed the high powder coating particles of concentration degree.The spherical shape and partial size point of this rule
The high powder particle of cloth concentration degree can be realized planarization when film scumbling.And since powder particle is starting melting stream
Levelling is easier in flat process, so being all improved to some extent to compactness, suppleness and the hardness after curing of coating.
(2) process characteristic is designed and prepared according to formula in powdery paints of the present invention, is added to and thermoplastic gathers inclined difluoro
Ethylene type fluororesin.Since supercritical fluid technique is when preparing powdery paints, more evenly to the mixing of its raw material, therefore it is poly- inclined
Difluoroethylene type fluororesin and other raw material compatibilities are more preferable.It can be added by powdery paints prepared by supercritical fluid technique
Add further amounts of extra-weather-proof polyvinylidene fluoride type fluororesin, therefore in the case where not influencing appearance of film, can sufficiently send out
The weather resistance of fluororesin is waved, while also substantially increasing the outdoor weathe resistance energy of powdery paints.
(3) powdery paints of the present invention belongs to one-step shaping product is prepared, and is different from traditional raw material by high temperature
Multiple processes such as melting extrusion, cooling tabletting is broken, high-speed impact crushes, cyclonic separation sieve powder.Because semicrystalline resin exists
A period of time is needed to carry out ordered arrangement to molecule again in powdery paints preparation process after the mixing with other raw material,
Again reach hemicrystalline state, and traditional preparation process needs to carry out repeatedly broken crushing, affects semi-crystalline resins
It recrystallizes, so its due performance can not be played.Part half hitch is added in powder coating formulation raw material of the present invention
Crystalline polyester resin, product preparation is that a step obtains, without because high-temperature fusion, repeatedly broken and crush and to influence its heavy
Crystalline state, semicrystalline polyester resin can give full play to its advantage function, can be obviously improved the flat of powdery paints film
Whole degree, flexibility, weatherability and low-temperature fast-curing performance.
Beneficial effects of the present invention are as follows:
(1) powder coating particles of the present invention are microspheroidal, and partial size is small and particle size distribution is concentrated, and it is thin to carry out metal coiled material
Surfacing when coating, function admirable.
(2) weathering resistance performance powder paint of the present invention is good, can reach the grade of outdoor extra-weather-proof 15-25.
(3) powdery paints flexibility of the present invention is good, low-temperature fast-curing performance is good.Be suitble to metal coiled material ready coating and
Bending Processing of the later period to pre-coated coil.
(4) powdery paints step of preparation process of the present invention is few, simple process, stable product quality.
Specific embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
The extra-weather-proof microspheroidal powdery paints of metal coiled material of the supercritical fluid technique preparation of the present embodiment, by following matter
The raw material of amount percentage are made:
Isocyanuric acid three-glycidyl ester curing agent described in formula for raw stock requires its total chlorine (organochlorine and inorganic
Chlorine) content≤0.4%.
Raw material is put into supercritical reaction kettle to be uniformly mixed, controls CO in reaction kettle2Content is 55wt%, temperature 55
DEG C, pressure 90Kg/cm2, ejiction opening temperature is 70 DEG C.The metal coiled material that grain diameter D50 is 18 μm is prepared with super resistance to
Wait microspheroidal powdery paints.
The present embodiment product specific performance is shown in Table 1.
Embodiment 2
The extra-weather-proof microspheroidal powdery paints of metal coiled material of the supercritical fluid technique preparation of the present embodiment, by following matter
The raw material of amount percentage are made:
Isocyanuric acid three-glycidyl ester curing agent described in formula for raw stock requires its total chlorine (organochlorine and inorganic
Chlorine) content≤0.4%.
Raw material is put into supercritical reaction kettle to be uniformly mixed, controls CO in reaction kettle2Content is 35wt%, temperature 48
DEG C, pressure 110Kg/cm2, ejiction opening temperature is 56 DEG C.The metal coiled material that grain diameter D50 is 22 μm is prepared with super resistance to
Wait microspheroidal powdery paints.
The present embodiment product specific performance is shown in Table 1.
Embodiment 3
The extra-weather-proof microspheroidal powdery paints of metal coiled material of the supercritical fluid technique preparation of the present embodiment, by following matter
The raw material of amount percentage are made:
Isocyanuric acid three-glycidyl ester curing agent described in formula for raw stock requires its total chlorine (organochlorine and inorganic
Chlorine) content≤0.4%.
Raw material is put into supercritical reaction kettle to be uniformly mixed, controls CO in reaction kettle2Content is 42wt%, temperature 68
DEG C, pressure 70Kg/cm2, ejiction opening temperature is 64 DEG C.The metal coiled material that grain diameter D50 is 14 μm is prepared with super resistance to
Wait microspheroidal powdery paints.
The present embodiment product specific performance is shown in Table 1.
1 embodiment product correlated performance test result of table
As shown in Table 1, it is microballoon that the metal coiled material that embodiment 1-3 is obtained, which has particle with extra-weather-proof microspheroidal powdery paints,
Shape, partial size is small and particle size distribution is concentrated, outdoor weathe resistance can good, low temperature performance well, solidification rapidly, film flexibility is good,
The characteristics such as surfacing, hardness height, comprehensive performance meet or better than national standards.
Claims (4)
1. a kind of preparation method of metal coiled material of supercritical fluid technique preparation with extra-weather-proof microspheroidal powdery paints, feature
It is: raw material is put into supercritical reaction kettle and is uniformly mixed, controls CO in reaction kettle2Content be 35~55wt%, temperature be 48~
68 DEG C, pressure is 70~110Kg/cm2, ejiction opening temperature is 56~70 DEG C；
The extra-weather-proof microspheroidal powdery paints of metal coiled material of the supercritical fluid technique preparation, by following mass percent
Raw material be made:
Poly- M-phthalic acid neopentyl glycol ester type polyester resin 35~88
Semicrystalline polyester resin 0.1~10
Isocyanuric acid three-glycidyl ester 3.2~7
Benzyltriethylammoinium chloride 0.1~1.6
Polyvinylidene fluoride type fluororesin 1~10
Acrylate 0.5~1.5
Diphenylhydroxyethanone 0.2~1
Pentaerythritol ester antioxidant 0.1~0.8
Pigment 0.2~26
Other auxiliary agents 0~3.
2. the extra-weather-proof microspheroidal powdery paints of metal coiled material of supercritical fluid technique preparation according to claim 1
Preparation method, it is characterised in that: semicrystalline polyester resin is TS2100 type polyester resin.
3. the extra-weather-proof microspheroidal powdery paints of metal coiled material of supercritical fluid technique preparation according to claim 1
Preparation method, it is characterised in that: the gross mass percentage composition of organochlorine and inorganic chlorine in isocyanuric acid three-glycidyl ester≤
0.4%。
4. the extra-weather-proof microspheroidal powdery paints of metal coiled material of supercritical fluid technique preparation according to claim 1
Preparation method, it is characterised in that: the shape of powder coating particles is microspheroidal, and partial size is between 10~24 μm.
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| CN107746466A (en) * | 2017-11-07 | 2018-03-02 | 成都新柯力化工科技有限公司 | A kind of environment-friendly type preparation method of plastic color master grain |
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| KR20020079879A (en) * | 2000-12-21 | 2002-10-19 | 유씨비 소시에떼아노님 | Powdered thermosetting composition for coatings |
| DE102006057838A1 (en) * | 2006-12-08 | 2008-06-12 | Evonik Degussa Gmbh | Storage-stable PU powder coating compositions and their use for low-turbidity and flexible polyurethane coatings |
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