CN105176369A - Water-based wood paint modified by vegetable oil and preparation method of water-based wood paint - Google Patents
Water-based wood paint modified by vegetable oil and preparation method of water-based wood paint Download PDFInfo
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- CN105176369A CN105176369A CN201510710395.9A CN201510710395A CN105176369A CN 105176369 A CN105176369 A CN 105176369A CN 201510710395 A CN201510710395 A CN 201510710395A CN 105176369 A CN105176369 A CN 105176369A
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Abstract
The invention discloses water-based wood paint modified by vegetable oil and a preparation method of the water-based wood paint. The water-based wood paint is prepared from, by weight, 60-85 parts of aliphatic series modified polyurethane dispersoid, 1-3 parts of hardness-enhancing resin, 7-12 parts of water, 1-3 parts of wax emulsion, 2-5 parts of coalescing agents, 0.2-0.7 part of wetting dispersant, 0.1-0.5 part of flatting agents, 0.2-0.7 part of deforming agents, 1-2 parts of antifreezing agents and 0.3-0.7 part of thickening agents. According to the water-based wood paint modified by the vegetable oil and the preparation method of the water-based wood paint, formula adjustment is utilized, the environment-friendly type water-based hardness-enhancing resin is matched, and the hardness-enhancing resin comprises solvent-free water-based modified aldehyde ketone resin dispersoid. The water-based wood paint can reach or exceeds oil-based wood paint in physical and chemical technical index, and all comprehensive properties are excellent.
Description
Technical field
The present invention relates to aqueous woodware paint technical field, disclose a kind of plant oil modified aqueous woodware paint and preparation method thereof especially.
Background technology
Polyurethane coating has various excellent performance, is widely used in coating and paint.Solvent type polyurethane paint is due to the volatility of solvent and toxicity, and inadequate environmental protection, is replaced by aqueous polyurethane paint gradually.
Polyurethane aqueous paint also can be used in woodwork coating, adopt aminosilane coupling agent modifying aqueous emulsion of polyurethane can improve the sticking power of corresponding coating, water tolerance and mechanical property (" development of aminosilane coupling agent modifying waterborne polyurethane wood coatings ", Hou Menghua etc., decorating and renovating material).But the performances such as the hardness of such polyurethane carpentry paint film, erosion resistance, solvent resistance, glossiness, scuff resistance and resistance to blocking are excellent not, and the time of drying of film is also long.
Patent CN104099000A discloses a kind of without benzene clean taste type scratch-resistant polyurethane matte varnish, its first component resin paint and second curing components agent composition, first component resin enamel-cover is containing Synolac, aldehyde ketone resin, flatting silica, dispersion agent, modification flow agent, defoamer, anti-settling agent and solvent; Second component comprises solidifying agent and solvent.Although the scratch resistance capability of this varnish is comparatively strong, it is not water-borne coatings, inadequate environmental protection, and more complicated when dual-component coating uses, and other performances of this varnish are also excellent not.
Patent CN104342013A discloses a kind of marine antifouling corrosion resistant coating, and its raw material comprises: castor oil modified aqueous polyurethane, aldehyde ketone resin, voltalef, hydrogenated nitrile-butadiene rubber, kaolin, hollow glass micropearl, calcium sulfate, mica powder, zinc oxide, silane coupling A-172, solidifying agent, biocides, pigment.Although this coating is corrosion-resistant, be single-component and water-based emulsion, it is not wood lacquer yet, and its over-all properties is also still excellent not.
But the major member that woodenware is decorated as interior decoration, its aesthetic appearance and over-all properties require all higher, must be also very high to the requirement of the wood lacquer that its surface uses.Therefore, be badly in need of a kind of environmental protection, higher, the strong adhesion of hardness of film, corrosion-resistant, solvent resistant, water-fast, can quick-drying glossiness good, the wood lacquer that various over-all properties is all more excellent.
Summary of the invention
The object of the present invention is to provide a kind of plant oil modified aqueous woodware paint, it adopts special Hardening resin to carry out modification to aliphatic modified polyurethane dispersions.This modified polyurethane wood lacquer not only environmental protection, and various over-all properties is all excellent, and it can surmount oiliness wood lacquer in physics and chemistry technical indicator.
Another object of the present invention is to provide a kind of method preparing plant oil modified aqueous woodware paint.This preparation method is simple to operate, can industrialization produce.
The invention provides a kind of plant oil modified aqueous woodware paint, it comprises the component of following weight part: aliphatic modified polyurethane dispersions 60-85 part, Hardening resin 1-3 part, water 7-12 part, wax emulsion 1-3 part, film coalescence aid 2-5 part, wetting dispersing agent 0.2-0.7 part, flow agent 0.1-0.5 part, defoamer 0.2-0.7 part, frostproofer 1-2 part and thickening material 0.3-0.7 part, wherein, Hardening resin is solvent-free watersoluble modified aldehyde ketone resin dispersion.
Wherein, preferably, aliphatic modified polyurethane dispersions adopts vegetables oil, isophorone diisocyanate, polyether Glycols and aminopropyl triethoxysilane to be raw material, and being synthesized by prepolymer blend method, is a kind of Novel aliphatic aqueous polyurethane gloss oil.The preferred Viscotrol C of described vegetables oil (CO).Preferred further, the synthesis material weight proportion of above-mentioned aliphatic modified polyurethane dispersions is as follows: Viscotrol C (CO) 95-96.4 part, isophorone diisocyanate 0.5-0.8 part, polyether Glycols 1-1.2 part, aminopropyl triethoxysilane 0.2-0.5 part.
Owing to containing aminopropyl triethoxysilane in raw material, therefore above-mentioned aliphatic modified urethane be with polysiloxane be soft section synthesis synthesis of polysiloxane-polyurethane block copolymer, with the excellent properties of polysiloxane and urethane, show good low-temperature flexibility, dielectricity, surface enrichment and excellent biocompatibility etc., the shortcoming of polysiloxane bad mechanical property can be overcome, also can make up the deficiency of urethane weathering resistance difference.In addition, the Viscotrol C in raw material belongs to vegetables oil, is a kind of renewable resources, wide material sources, cheap, is easy to obtain and buy, and it can significantly improve again the glossiness of material.
Aforementioned prepolymer blend method is actually performed polymer-from aggressiveness hybrid system.This technique is the prepolymer first prepared band hydrophilic radical and contain-NCO end group, in water at low temperature after dispersion, utilizes diamine or dibasic alcohol chain extension, when prepolymer viscosity is higher, can suitably add a small amount of solvent, make prepolymer be easy to dispersed with stirring at about 40 DEG C.Advantage is that technique is simple, can obtain containing the macromolecular emulsion of emulsification.Such as: by N methyldiethanol amine and dimethylol propionic acid (DMPA) synthesis of polyurethane dispersion, carboxylic acid on DMPA is because steric hindrance is with isocyanate groups sluggish, with amine by hydroxy-acid group and after, dilute with water obtains water dispersion, then chain extension, but strictly must control viscosity when rear chain extension, otherwise difficulties in dispersion, even can not disperseing, in order to improve performance further, adding as linking agents such as melamine resins.
Aliphatic modified polyurethane dispersions take water as the binary colloid system of medium, its particle diameter is less than 0.1nm, there is good dispersion stabilization, not only remain the premium properties that traditional solvent borne polyurethane rate of drying is fast, but also it is low, free from environmental pollution, easy to operate to have production cost, transparency is good, has the good feature of environmental protection simultaneously.The advantages such as the hardness of water-based aliphatic modified polyurethane dispersions film is high, strong adhesion, corrosion-resistant, solvent resistant is good, meet " three prerequisites " (resource of development coating, the energy, pollution-free) and the requirements of the times of " four E principles " (economic ECONOMY, efficiency EFFICIENCY, ecological ECOLOGY, energy ENERGY).
Preferably, described solvent-free watersoluble modified aldehyde ketone resin dispersion is with aldehyde ketone resin, hydrophilic monomer dimethylolpropionic acid and dihydroxyl Soxylat A 25-7, polyneopentyl glycol adipate, isophorone diisocyanate for main raw material, adopts the modification aldehyde ketone resin dispersion of prepolymer method synthesis.
Better, each raw material weight proportioning is as follows: aldehyde ketone resin 96-98 part, hydrophilic monomer dimethylolpropionic acid 0.5-1 part and dihydroxyl Soxylat A 25-7 0.5-1 part, polyneopentyl glycol adipate 0.2-0.7 part, isophorone diisocyanate 1-1.5 part.
Water-based aldehyde ketone resin, through modified, have better glossiness, high rigidity, resistance to blocking, drying property, the transparency, chemical resistant properties, stain resistance and water-soluble, separately has fabulous stability, wettability and color developing.Because it has good polishing performance, so Hardening resin also can be used to improve pigmenting power, even if thus also can obtain high gloss when coloured wood lacquer pigment concentration is high.
Research shows, the zeta-potential of polyurethane dispersions PUD is all greater than-30mV, has good stability of emulsion, and the moon/non-ionic type PUD has lower surface tension and better Calcium ion stability.The increase of hydrophilic radical content (HGC), the minimizing of the moon/nonionic mol ratio, aldehyde ketone resin consumption, NCO/OH mol ratio makes micelle median size reduce, and emulsion viscosity increases.Aldehyde ketone resin modification PUD particle diameter presents bimodal distribution, transmission electron microscope display dispersion micelle structure spherical in shape.After aldehyde ketone resin modification PUD, the pencil hardness of corresponding film improves, and film has more excellent sticking power, snappiness and water tolerance.
Preferably, the water in raw material is deionized water, and tap water is owing to the addition of chlorinated lime etc., more containing impurity, and the stability in storage of aqueous woodware paint product may be caused not good.
Preferably, the wax emulsion in raw material is the water-borne wax auxiliary agent of German import, and preferred German Keim-Attitec company produces
d-816 water-borne wax auxiliary agent, it can strengthen the performance such as smooth feeling, agglomeration resistance, rub resistance, water tolerance, anti scuffing of product.
Various auxiliary components in aqueous woodware paint can adopt conventional known kind.But by selecting specific various auxiliary agent, the various performances of film can be improved further.
Preferably, the environment-friendly type film coalescence aid ester alcohol 12 that provides for Yi Shiman Teanol of film coalescence aid.This auxiliary agent is a kind of coalescing aid excellent especially, is the film coalescence aid of emulsion, is also the good solvent of polymerized emulsion simultaneously, effectively can reduces the minimum film-forming temperature of polymerized emulsion.This auxiliary agent has certain volatility, is trapped in film and plays filming function, all volatilize after film forming in film process, does not remain in dry film, therefore also can not affect film performance.The solvability of itself and water is low, adds the stability not affecting polymerized emulsion after using, but can significantly improve the film forming properties of film, improve the weathering resistance of film, wear resistance, stain resistance and chemical resistant properties, can improve coating color developing simultaneously.
The BYK-192 that the preferred BYK company of wetting dispersing agent produces, this wetting dispersing agent is exclusively used in water-miscible paint, plays reduction surface tension soak ground, colored paint played to the effect of dispersion water-miscible paint.
The BYK-375 of the preferred Bi Ke chemistry of flow agent, it is specially adapted to, in the water-based system of low solubility promoter content, to have good consistency with these systems.It is reacted by its primary hydroxyl and base-material, and be thus applicable to very much cross-linking type system, this flow agent can promote slipping, and solvent resistant is weather-proof, few laying dust.Compared with the non-reactive organic silicone of standard, this auxiliary agent is cross-linked due to its active group and paint film, and above-mentioned performance can be more lasting in coating system, obvious reduction surface tension, promote ground to soak, they promote again flowing and levelling, and prevent the formation of Bei Nade whirlpool simultaneously.
The preferred propylene glycol of frostproofer, its environmental protection and cost performance is high.The 2020NPR non-ionic polyurethane association type that the preferred Rhom and Hass of thickening material produces, plays efficient middle shear thickening, promotes flow levelling, provide good paint film fullness ratio.
The BYK-022 of the preferred Bi Ke chemistry of defoamer, this defoamer is water-borne coatings silicone antifoam agent, on color acceptance and gloss without impact.Adding fashionable, needing enough high shear forces to avoid shrinkage cavity.This defoamer has excellent long-term stability and to microvesicle pole effective force, not containing VOC, has the very high feature of environmental protection.
In addition, according to the actual needs of wood lacquer product pH value, pH adjusting agent can be added again, when the pH value of the finished product is not between 8-9, then add appropriate pH adjusting agent.The AMP-96 that the preferred the Dow Chemical Company of pH adjusting agent produces, can improve the performance of thickening material in water-miscible paint, instead of traditional ammoniacal liquor, decrease the ammonia taste of coating.
In addition, according to plant oil modified aqueous woodware paint product needs of different nature, other materials can also be added.Such as in order to obtain the product of different colours, different pigment can be added again, such as Organic Black mill base, titanium dioxide (titanium dioxide), organic middle Huang slurry etc.Wherein Organic Black mill base is preferably ColanylBlackN.The R-996 of titanium dioxide preferred Sichuan Long Mangtai industry company limited, its surface, through silicon, aluminium, zirconium coating and organic process, has without physiological-toxicity, stable chemical performance, pigment performance brilliance, whiteness, brightness, good luster, opacifying power, reducing power and mobility strong.The organic middle Huang slurry ColanylYellow2GXD of the preferred Clariant of organic middle Huang slurry.Organic Black mill base and organic middle Huang are starched containing harmful heavy metal has environmental protection, color developing is good, strong covering power, the performance of high gloss.
Such as, then add organic black slurry ColanylBlackN5-7 weight part; Deionized water 2.5-5 weight part can form plant oil modified aqueous black lacquer as woodenware finish.
, then add titanium dioxide (titanium dioxide) R-99620-25 weight part for another example; Deionized water 2.5-5 weight part can form plant oil modified aqueous white lacquer as woodenware finish.
And for example, then add organic middle Huang slurry ColanylYellow2GXD12-20 weight part; Deionized water 2.5-7 weight part can form the yellow lacquer as woodenware finish of plant sterilization function for expelling pests type water-based.
In addition, also according to the needs of plant oil modified aqueous woodware paint transparency and glossiness, can select whether add flatting silica again.Do not add flatting silica when usually doing high-gloss paint, when adding flatting silica, the glossiness of product reduces, and can make dumb light, middle smooth product.The OK-520 nano level flatting silica of the preferred Degussa of flatting silica.
Add nanometer flatting silica OK-5200-12 weight part again; Deionized water 2.5-7 weight part can form the aqueous woodware paint of bright seven light splitting entirely, five light splitting, three light splitting, the modification of dumb light transparent vegetable oil.
According to the length of aqueous woodware paint product duration of service, can select whether to add sanitas, as fruit product was directly finished using in one week, can not adding preservative agent.When using the long period, more preferably sanitas is added, the high-performance fungicidal preservative KathonLxe that its preferred ROHM AND HAAS is produced, its the growing of anti-bacteria and fungi in production inventory process, there is higher field of activity, can effectively anti-bacteria (comprising Gram-positive, Gram-negative) mould, yeast, not release formaldehyde, hypotoxicity.
The present invention also provides a kind of method preparing above-mentioned plant oil modified aqueous woodware paint, this preparation method comprises the following steps: water, wetting dispersing agent, defoamer are put in container and carry out high-speed stirring, add aliphatic modified polyurethane dispersions, Hardening resin afterwards, frostproofer, wax emulsion is added after abundant stirring, regulate pH after abundant stirring, and add thickening material.This preparation technology is simple to operate, can industrialization produce.
Preferably, high-speed stirring speed is 1200-1600 rpm, and the time is 20-30 minute; Stirring velocity when adding aliphatic modified polyurethane dispersions is that 800-1100 turns, and churning time is 5-15 minute; After adding Water Soluble Compound nanometer anion powder, churning time is 2-10 minute; Final ph is 8-9.
Same with aforementioned, the needs different according to the finished product, can add pigment, flatting silica etc. again.According to the needs of product final viscosity, according to customer requirement, thickening material adjustment can be added again.
Beneficial effect of the present invention has:
1, contain castor oil modified polyurethane dispersions and the solvent-free watersoluble modified aldehyde ketone resin dispersion of Hardening resin in raw material, make aqueous woodware paint can surmount oiliness wood lacquer in physics and chemistry technical indicator.Paint product has that dried coating film is fast, hardness is high, fullness ratio is good, glossiness is good, resistance to blocking, corrosion-resistant, water tolerance, solvent resistance etc.In addition, castor-oil plants oil is renewable, wide material sources, cheap, makes wood lacquer product cost low.
2, by adding different auxiliary agents, the wood lacquer product of different performance can be obtained.And the selection of different auxiliary agent more can improve the various performances of film further.Product category of the present invention is enriched, and is widely used, and the preparation method of wood lacquer is also simple, with low cost, can industrialization produce.
3, do not add the solubility promoter containing volatile organic compounds in formula for a product design, not containing harmful heavy metal, product can reach zero VOC, has the good feature of environmental protection.
Embodiment
Can be well understood to the present invention further by specific embodiments of the invention given below, but they not limitation of the invention.The part do not described in detail in specific embodiment adopts prior art, known technology means and industry standard to obtain.
Except as otherwise noted, the number adopted in the present invention is weight part.
The raw material of aliphatic modified polyurethane dispersions weight part is as shown in Table 1 prepared by prepolymer blend method.
The raw material of Hardening resin modified aldehyde ketone resin weight part is as shown in Table 2 prepared by pre-polymerization method.
The formula of the aliphatic modified polyurethane dispersions of table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Viscotrol C | 95 | 96.4 | 96 | 95 |
| Isophorone diisocyanate | 0.6 | 0.5 | 0.7 | 0.8 |
| Polyether Glycols | 1.1 | 1.0 | 1.2 | 1.2 |
| Aminopropyl triethoxysilane | 0.3 | 0.2 | 0.5 | 0.4 |
The formula of table 2 Hardening resin
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Aldehyde ketone resin | 97 | 96 | 98 | 97 |
| Hydrophilic monomer dimethylolpropionic acid | 0.8 | 1.0 | 0.5 | 0.6 |
| Hydrophilic monomer dihydroxyl Soxylat A 25-7 | 0.5 | 0.6 | 0.8 | 1.0 |
| Polyneopentyl glycol adipate | 0.5 | 0.2 | 0.6 | 0.7 |
| Isophorone diisocyanate | 1.2 | 1.5 | 1.0 | 1.3 |
Embodiment 1
Prepare plant oil modified aqueous black lacquer as woodenware finish by formulation weight part of table 3, comprise the following steps:
A) raw material is equipped with according to the weight part of formula setting, water, wetting dispersing agent, black slurry ColanylBlackN, defoamer are dropped into container high speed and stir 1200 ~ 1400 rpms, stir 15 minutes, rotating speed drops to 1000 rpms, add aliphatic modified polyurethane dispersions, Hardening resin while stirring, stir to add frostproofer after 10 minutes successively, wax emulsion, vegetalitas composite Nano sterilization powder stir 5 minutes, rotating speed drops to 600 rpms, add pH adjusting agent and pH value is adjusted to 8, add thickening material and adjust to viscosity required for client.
B) detect-filter-pack-keep sample.
Embodiment 2
The adjustment of this Example formulations ratio refers to table 3, and wherein pigment adopts titanium dioxide, is specially R-996; Specific implementation process is substantially the same manner as Example 1, and difference is only that high-speed stirring speed is 1400-1600 rpm, and churning time is 30 minutes.
Embodiment 3
The adjustment of this Example formulations ratio refers to table 3, and wherein pigment is yellow in adopting starches, and is specially ColanylYellow2GXD; Specific implementation process is substantially the same manner as Example 1, and difference is only that high-speed stirring speed is 1200-1400 rpm, and churning time is 15 minutes.
Embodiment 4
The adjustment of this Example formulations ratio refers to table 3, and specific implementation process is substantially the same manner as Example 1, and difference is only that high-speed stirring speed is 1200-1400 rpm, and churning time is 20 minutes.
The aqueous wooden ware paint formula that table 3 is plant oil modified
The plant oil modified aqueous woodware paint of above-mentioned preparation, according to standard GB/T/T23999-2009 " indoor decorating use woodwork coating ", it is carried out to the detection of technical feature, detected result is in table 4.
The technical feature detected result of the aqueous woodware paint that table 4 is plant oil modified
Above disclosedly be only the preferred embodiments of the present invention, certainly can not limit the interest field of the present invention with this, therefore according to the equivalent variations that the present patent application the scope of the claims is done, still belong to the scope that the present invention is contained.
Claims (10)
1. a plant oil modified aqueous woodware paint, it is characterized in that: the component comprising following weight part: aliphatic modified polyurethane dispersions 60-85 part, Hardening resin 1-3 part, water 7-12 part, wax emulsion 1-3 part, film coalescence aid 2-5 part, wetting dispersing agent 0.2-0.7 part, flow agent 0.1-0.5 part, defoamer 0.2-0.7 part, frostproofer 1-2 part and thickening material 0.3-0.7 part, wherein, described Hardening resin is solvent-free watersoluble modified aldehyde ketone resin dispersion.
2. plant oil modified aqueous woodware paint according to claim 1, is characterized in that: the synthesis material of described aliphatic modified polyurethane dispersions comprises vegetables oil, isophorone diisocyanate, polyether Glycols and aminopropyl triethoxysilane.
3. plant oil modified aqueous woodware paint according to claim 2, is characterized in that: described vegetables oil is Viscotrol C.
4. plant oil modified aqueous woodware paint according to claim 3, it is characterized in that: described aliphatic modified polyurethane dispersions is synthesized by prepolymer blend method, comprise each raw material of following weight part: Viscotrol C 95-96.4 part, isophorone diisocyanate 0.5-0.8 part, polyether Glycols 1-1.2 part and aminopropyl triethoxysilane 0.2-0.5 part.
5. plant oil modified aqueous woodware paint according to claim 1, is characterized in that: the synthesis material of described solvent-free watersoluble modified aldehyde ketone resin dispersion comprises: aldehyde ketone resin, hydrophilic monomer dimethylolpropionic acid and dihydroxyl Soxylat A 25-7, polyneopentyl glycol adipate and isophorone diisocyanate.
6. plant oil modified aqueous woodware paint according to claim 5, is characterized in that: described solvent-free watersoluble modified aldehyde ketone resin dispersion is synthesized by prepolymer method; Comprise each raw material of following weight part: aldehyde ketone resin 96-98 part, hydrophilic monomer dimethylolpropionic acid 0.5-1 part and dihydroxyl Soxylat A 25-7 0.5-1 part, polyneopentyl glycol adipate 0.2-0.7 part and isophorone diisocyanate 1-1.5 part.
7. plant oil modified aqueous woodware paint according to claim 1, is characterized in that: described aqueous woodware paint also comprises sanitas 0.1-0.2 weight part and/or pH adjusting agent 0.1-0.2 weight part.
8. the plant oil modified aqueous woodware paint according to any one of claim 1 to 6, is characterized in that: also comprise in pigment, flatting silica one or more; Described pigment is Organic Black mill base, titanium dioxide or organic middle Huang slurry.
9. the preparation method of the plant oil modified aqueous woodware paint according to any one of claim 1 to 8, it is characterized in that: comprise the following steps: water, wetting dispersing agent and defoamer are put in container and carries out high-speed stirring, add aliphatic modified polyurethane dispersions, Hardening resin afterwards, add film coalescence aid, frostproofer, wax emulsion, flow agent after abundant stirring and after fully stirring, add pH adjusting agent adjustment pH, finally add thickening material.
10. according to the preparation method described in claim 9, it is characterized in that: high-speed stirring speed is 1200-1600 rpm, the time is 15-30 minute; Stirring velocity when adding aliphatic modified polyurethane dispersions is 800-1100 rpm, and churning time is 5-15 minute; Final ph is 8-9.
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