CN101824251A - Polyvinylidene fluoride type fluorocarbon resin super weather-resistant coating and production method thereof - Google Patents
Polyvinylidene fluoride type fluorocarbon resin super weather-resistant coating and production method thereof Download PDFInfo
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Abstract
The invention relates to a polyvinylidene fluoride type fluorocarbon resin super weather-resistant coating which is prepared by the following raw materials in parts by weight: 20-25 parts of PVDF resin, 8-11 parts of acrylic resin, 12-16 parts of paints, 50-60 parts of mixed solvent, 0.2-0.4 part of leveling agent, 0.1-0.3 part of defoamer, 0.3-0.5 part of dispersant and 0.4-0.6 part of anti-settling agent. The production method of the coating comprises the three steps of preparing raw materials, preparing PVDF resin dispersion liquid and preparing the PVDF type fluorocarbon super weather-resistant coating. The coating can be extensively applied in coating of wall surfaces of buildings, top surfaces, metal plates and surfaces of metal parts, has super strong weather resistance and does not need the maintenance during the outdoor long-term use, and a coating film has the advantages of very high impact resistance, great color-preserving performance, no fading above 10 years, resistance to ultraviolet and nuclear radiation, resistance to chemical corrosion, resistance to water seepage, great high temperature resistance and the like.
Description
Technical field
The present invention relates to the coating of a kind of buildings, ground and coating metal surfaces, specifically is to be super weather-resistant coating and the production method thereof that main raw material is mixed with polyvinylidene fluoride resin and acrylic resin.
Background technology
Polyvinylidene difluoride (PVDF) (hereinafter to be referred as PVDF) fluorocarbon resin is because of factors such as acquisition raw material difficulties, domestic research and development to the PVDF fluorocarbon coating lags, this coating has excellent weathering resistance, anti-pollution, performance such as corrosion-resistant and uses the characteristics of face width, be subjected to the attention of scientific and technical personnel in the industry and user's expectation day by day, in recent years the source problem that comes of some critical materialses is resolved, and new achievement in research and corresponding coating development occur in succession.Successively disclose a kind of single-component fluorine-carbon-aluminum powder baking varnish and fluorine-carbon-aluminum powder baking varnish and their preparation method as CN200810067887.0 and CN200810067922.9, made good exploration and useful technical contribution.
Summary of the invention
The present invention is directed to the PVDF resin and have the characteristics of superpower weathering resistance, use the important component that this resin is made coating, design a kind of PVDF type fluorocarbon resin super weather-resistant coating and production method thereof, to satisfy the demand of application industry this type of coating.
Above-mentioned purpose is achieved through the following technical solutions: this polyvinylidene fluoride type fluorocarbon resin super weather-resistant coating is formed by following raw materials according and weight part proportioning thereof: 20-25 part polyvinylidene fluoride resin is the PVDF resin, 8-11 part thermoplastic methacrylic resin, 12-16 part is as the R-902 golden red type titanium dioxide or the aluminium paste of pigment, 35-40 part mixed solvent, 0.2-0.4 divide the BYK-306 flow agent, 0.1-0.3 part BYK-141 defoamer, 0.3-0.5 part BYK-P104S dispersion agent, 0.4-0.6 portion 3390 anti-settling agents, 15-20 part is as the dimethyl formamide or the N,N-DIMETHYLACETAMIDE of solvent.
Said mixed solvent is by commercially pure methylethylketone, isophorone and the valerone weight ratio blended mixed solvent by 1: 2: 1.
The production method of this polyvinylidene fluoride type fluorocarbon resin super weather-resistant coating is characterized in that through following steps:
(1) get the raw materials ready by following weight part: 20-25 part PVDFT-1 resin is buied by fluorine chemical Science and Technology Ltd. to east, Shanghai, buy 8-11 part B-44 thermoplastic methacrylic resin to U.S. Rhom and Hass, buy 12-16 part R-902 golden red type titanium dioxide or buy 12-16 part aluminium paste to Japanese E.I.Du Pont Company to emerging Industrial Co., Ltd. of Shenzhen family, buy BYK-306 flow agent 0.2-0.4 part and BYK-141 defoamer 0.1-0.3 part and BYK-P104S dispersion agent 0.3-0.5 part to German Bi Ke chemical company, 3390 anti-settling agent 0.4-0.6 parts are buied by company to the public Longhua in Taiwan, buy commercially pure methylethylketone to the industrial and commercial shop of domestication, your ketone and valerone of different fluorine, the three is 1: 2: 1 proportioning amount that can be made into 35-40 part by weight, buy commercially pure dimethyl formamide or N,N-DIMETHYLACETAMIDE 15-20 part again;
(2) preparation of PVDF resin dispersion liquid: 8-11 part methacrylic resin and the 15-20 part dimethyl formamide of making solvent or N,N-DIMETHYLACETAMIDE are mixed, after stirring and dissolving, add sand milling 4h in the sand mill with 20-25 part PVDF resin, controlled temperature 25-30 ℃, detecting fineness＜30 μ m, being coated with 4 glasss of viscosity is 50-70s, has promptly made the PVDF resin dispersion liquid;
(3) preparation of PVDF type fluorine carbon super weather-resistant coating: the PVDF resin dispersion liquid that step (2) is made mixes with 50-60 part mixed solvent; stir at a slow speed by (300-400) r/min; add the liquid aluminium paste of 12-16 part again or grind through shredder; the R-902 golden red type titanium dioxide of granularity＜30 μ m; keeping adding 0.2-0.4 part flow agent again in the stirring at a slow speed; 0.1-0.3 part defoamer; 0.3-0.5 part dispersion agent; 0.4-0.6 part four kinds of auxiliary agents of anti-settling agent; powdery auxiliary agent wherein adds after all need grinding to form granularity＜30 μ m in advance; whole process stirs at a slow speed by (300-400) r/min earlier; stir 10-15min by (600-800) r/min middling speed again; detect fineness＜30 μ m; shut down blowing when being coated with 4 glasss of viscosity 20-30s; barreled.
The invention has the beneficial effects as follows that the coating that makes with present method has superpower weathering resistance, life-time service need not maintain out of doors, the high shock strength of filming and guarantor's colour properties can be applied in metallic surface, building wall and end face application, and color and luster for years is as newly.
Embodiment
The present invention is described in further detail below in conjunction with embodiment: each raw material and weight part thereof is as follows by eight embodiment tabulations (table 1):
Table 1
Material name is sometimes with being called for short in last table and the literary composition, and the actual raw material that adopts (1) corresponding material name (comprising model) of buying in getting the raw materials ready set by step is as the criterion.
Embodiment 1 (embodiment 1 corresponding raw material and weight part proportioning value in showing in the contrast): 8 parts of acrylic resins and 15 parts of dimethyl formamides are mixed, after stirring and dissolving, added in the sand mill sand milling 4 hours with 20 parts of PVDF resins, controlled temperature 25-30 ℃, detect fineness＜30 μ m, be coated with 4 glasss of viscosity 50-70 seconds, promptly make the PVEF resin dispersion liquid; The whole dispersion liquids that to make again mix with 50 parts of mixed solvents; stir at a slow speed by (300-400) r/min; add 12 parts of titanium dioxides that grind to form granularity＜30 μ m through shredder again; keeping adding 0.2 part of flow agent again in the stirring at a slow speed; 0.1 part defoamer; 0.3 part dispersion agent and 0.4 portion of anti-settling agent; all genus powder-materials all grind to form granularity＜30 μ m in advance after add; add the back and disperse roughly to transfer to again behind the mixing earlier (900-1100) r/min middling speed dispersion 10-15min at a slow speed, detect fineness＜30 μ m; shut down when being coated with 4 glasss of viscosity for 20-30s; blowing; barreled.
Mixing solutions wherein mixes with methylethylketone, isophorone and the valerone weight part by 1: 2: 1.
The raw material of corresponding embodiment and weight part ratio and embodiment 1 same procedure are made in the equal synopsis of all the other embodiment 2-8.
PVDF (polyvinylidene difluoride (PVDF)) resin is meant the multipolymer of vinylidene fluoride homopolymer or vinylidene and other a small amount of fluorine-containing vinyl monomers, the PVDF resin has the characteristic of fluoro-resin and paint field resins for universal use concurrently, except that having good chemical resistance, high thermal resistance, scale resistance, weathering resistance, anti-x radiation x performance, also have properties such as piezoelectricity, dielectricity, pyroelectricity.
The PVDF resin is one of main raw material in the fluorocarbon coating, because of the PVDF resin has superpower weathering resistance, and life-time service out of doors, service free.
PVDF coating is with its excellent weathering resistance, chemical-resistant, stain resistance, ease for maintenance etc., out of doors have a wide range of applications market and prospect of building field.
The development of domestic PVDF fluorine carbon technique falls behind relatively and is slow, in recent years, fluorocarbon coating has been obtained very big progress at home, and become a big focus of coating industry Recent study and exploitation, promote the progress of production of resins, coating manufacturing and construction application aspect, guided and promoted the development in market.
Confirm through the contrast experiment, PVDF resin and acrylic resin weight ratio are about 7: 3 in this coating, keep the color and luster effect especially remarkable, substantially need not select solvent truly when producing this coating for use, only need be dispersed in the dispersion liquid that acrylic resin and mixed solvent form and get final product, reach the requirement fineness by high speed dispersion or grinding, promptly can be made into the PVDF dispersion liquid.
With this coating several main structure, performance characteristics and the physical and chemical effect that is risen, make brief of the introduction below:
The a.PVDF resin
The electronegativity energy of fluorine atom maximum makes that the fluorine carbon bond that forms is very firm, adds the unique symmetrical structure of its molecule, makes PVDF have extraordinary stability, ultraviolet light photodissociation performance and excellent insulating property and mechanical property.
The PVDF resin has following characteristics: have very high tensile strength and impact strength, have good wear resistance, rigidity and snappiness.Good thermostability, fabulous UV resistant and nuclear radiation, well electrical property and flame retardant properties, well chemical resistance, splendid, high purity, the fungus resistance energy of osmotic-pressure-tolerant are arranged.
B. acrylic resin
Usually select the thermoplastic acrylic resin of methacrylic for use.Main effect is:
Increase pigment-dispersing, increase the dispersion stabilization that paint film coheres sticking power, improves the coating each component.
C. pigment
PVDF is a kind of ultraviolet perviousness resin, therefore to pigment and supporting require high.Pigment is must be high weather-proof and can intercept the destruction of ultraviolet ray to priming paint.Usually can select high weather-proof Rutile type Titanium Dioxide or the high weatherable Lacquer finish varnish aluminium paste that adds for use.
D. solvent
At room temperature, the PVDF resin can be dissolved in the minority polar solvent, in dimethyl formamide and N,N-DIMETHYLACETAMIDE.But the viscosity height of solution paint, solid content is low, be unfavorable for construction, and above-mentioned solvent price is higher, and human body is had certain murder by poisoning.Therefore, the PVDF resin should not be mixed with solution paint, and makes organosol.So-called organosol is the dispersion liquid of PVDF subparticle in organic solvent, at high temperature can sinter into and film.The PVDF organosol can adopt mixed solvent system single or mixing latent solvent or latent solvent and thinner.So-called latent solvent refers to does not at room temperature have solvency action, but solvent that at high temperature can dissolve polymer.The latent solvent of PVDF is a lot, and gylcol ether, ester class and ketone etc. are arranged, and thinner has aromatic hydrocarbon and ketone etc., and thinner can be used for regulating the solid content and the viscosity of dispersion liquid.
Through test relatively, select the solvent system of methylethylketone/isophorone/valerone ternary mixed solvent as the PVDF organosol paint for use, can obtain that viscosity is lower, levelling property coating preferably, coatingsurface is smooth, and compactness is good.This solvent system convenient sources, price is lower.Because the boiling point of each solvent height is different in the mixed solvent, so coating is difficult for bubbling during baking.The effect of mixed solvent be fixedly composition carrier, regulate paint viscosity dissolving PVDF resin when reaching construction requirement and baking film forming, be beneficial to the acrylic resin baking and form good polymer fusion crystal.
E. auxiliary agent
Auxiliary agent includes flow agent, dispersion agent, defoamer, anti-settling agent etc.Trace adds with the correlated performance after adjustment production, storage, construction, the film forming.
The correlated performance parameter of filming with this coating of standard testing of reference below with the tabular form introduction:
Two are coated with a baking film performance parameter
Table 2
| Sticking power | ??100/100 | ??лS?K5400?8.5.2(1mm) |
| Impact | Qualified | л SK5400 8.3.2 (Du Pont) 1/2 ￠ * 1000g*50cm |
| Salt spray resistance | 1.5mm in | л SK5400 9.1 (4000 hours) |
| Wet fastness | No abnormal | 50 ℃ of л SK5400 9.2.2 (4000 hours) * 98%RH*4000 hour |
| Acid resistance | No abnormal | л S K5100 8.22 5%H2SO4.20 ℃ * 1 month |
| Alkali resistance | No abnormal | л S K5400 8.21 5%NaOH.20 ℃ * 1 month |
| Promote weathering resistance | The above aberration of efflorescence ASTM8 is (white efflorescence 6) below 5 | Spend, be exposed to the sun 10 years in continent, Florida in the south 45 |
Three are coated with a baking film performance parameter
Table 3
| Test subject | Performance | Test method-condition |
| Gloss (60 °) | ??30-40 | ??лS?K5400?7.6 |
| Pencil hardness | ??2H | ??лS?K5400?8.4.2(b) |
| Sticking power | ??100/100 | ??лS?K5400?8.5.2(1mm) |
| Impact | Qualified | л S K5400 8.3.2 (Du Pont) 1/2 ￠ * 1000g*50cm |
| Salt spray resistance | 1.5mm in | л S K5400 9.1 (4000 hours) |
| Wet fastness | No abnormal | 50 ℃ of л S K5400 9.2.2 (4000 hours) * 98%RH*4000 hour |
| Acid resistance | No abnormal | л S K5400 8.22 5%H2SO4.20 ℃ * 1 month |
| Alkali resistance | No abnormal | л S K5400 8.21 5% NaOH.20 ℃ * 1 month |
| Promote weathering resistance | The above aberration of efflorescence ASTM8 is below 5 | Spend, be exposed to the sun 10 years in continent, Florida in the south 45 |
Claims (3)
1. polyvinylidene fluoride type fluorocarbon resin super weather-resistant coating is characterized in that being formed by following raw materials according and weight part proportioning thereof: to be PVDF resin, 8-11 part thermoplastic methacrylic resin, 12-16 part divide BYK-306 flow agent, 0.1-0.3 part BYK-141 defoamer, 0.3-0.5 part BYK-P104S dispersion agent, 0.4-0.6 part 3390 anti-settling agents, 15-20 part dimethyl formamide or N,N-DIMETHYLACETAMIDE as solvent as the R-902 golden red type titanium dioxide of pigment or aluminium paste, 35-40 part mixed solvent, 0.2-0.4 to 20-25 part polyvinylidene fluoride resin.
2. polyvinylidene fluoride type fluorocarbon resin super weather-resistant coating as claimed in claim 1 is characterized in that said mixed solvent is by commercially pure methylethylketone, isophorone and the valerone weight ratio blended mixed solvent by 1: 2: 1.
3. the production method of polyvinylidene fluoride type fluorocarbon resin super weather-resistant coating as claimed in claim 1 is characterized in that through following steps:
(1) get the raw materials ready by following weight part: 20-25 part PVDFT-1 resin is buied by fluorine chemical Science and Technology Ltd. to east, Shanghai, buy 8-11 part B-44 thermoplastic methacrylic resin to U.S. Rhom and Hass, buy 12-16 part R-902 golden red type titanium dioxide or buy 12-16 part aluminium paste to Japanese E.I.Du Pont Company to emerging Industrial Co., Ltd. of Shenzhen family, buy BYK-306 flow agent 0.2-0.4 part and BYK-141 defoamer 0.1-0.3 part and BYK-P104S dispersion agent 0.3-0.5 part to German Bi Ke chemical company, 3390 anti-settling agent 0.4-0.6 parts are buied by company to the public Longhua in Taiwan, buy commercially pure methylethylketone to the industrial and commercial shop of domestication, your ketone and valerone of different fluorine, the three is 1: 2: 1 proportioning amount that can be made into 35-40 part by weight, buy commercially pure dimethyl formamide or N,N-DIMETHYLACETAMIDE 15-20 part again;
(2) preparation of PVDF resin dispersion liquid: 8-11 part methacrylic resin and the 15-20 part dimethyl formamide of making solvent or N,N-DIMETHYLACETAMIDE are mixed, after stirring and dissolving, add sand milling 4h in the sand mill with 20-25 part PVDF resin, controlled temperature 25-30 ℃, detecting fineness＜30 μ m, being coated with 4 glasss of viscosity is 50-70s, has promptly made the PVDF resin dispersion liquid;
(3) preparation of PVDF type fluorine carbon super weather-resistant coating: the PVDF resin dispersion liquid that step (2) is made mixes with 50-60 part mixed solvent; stir at a slow speed by (300-400) r/min; add the liquid aluminium paste of 12-16 part again or grind through shredder; the R-902 golden red type titanium dioxide of granularity＜30 μ m; keeping adding 0.2-0.4 part flow agent again in the stirring at a slow speed; 0.1-0.3 part defoamer; 0.3-0.5 part dispersion agent; 0.4-0.6 part four kinds of auxiliary agents of anti-settling agent; powdery auxiliary agent wherein adds after all need grinding to form granularity＜30 μ m in advance; whole process stirs at a slow speed by (300-400) r/min earlier; stir 10-15min by (600-800) r/min middling speed again; detect fineness＜30 μ m; shut down blowing when being coated with 4 glasss of viscosity 20-30s; barreled.
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