CN1942543A - Aqueous coating substance compositions for decorative paint effects - Google Patents
Aqueous coating substance compositions for decorative paint effects Download PDFInfo
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- CN1942543A CN1942543A CNA2006800000043A CN200680000004A CN1942543A CN 1942543 A CN1942543 A CN 1942543A CN A2006800000043 A CNA2006800000043 A CN A2006800000043A CN 200680000004 A CN200680000004 A CN 200680000004A CN 1942543 A CN1942543 A CN 1942543A
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/54—Polycondensates of aldehydes
- C08G18/548—Polycondensates of aldehydes with ketones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8048—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/34
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/02—Condensation polymers of aldehydes or ketones only
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Manufacturing & Machinery (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to aqueous coating substance compositions for decorative paint effects, consisting of at least one binding agent, one modified ketone/aldehyde resin, one pigment creating an effect and, optionally, auxiliary agents and additional substances.
Description
Technical field
The present invention relates to by at least a base-material, a kind of modification ketone/urea formaldehyde, a kind of effect pigment and auxiliary agent and additive are formed when wishing, effect aqueous coating based coating composition.
This coating composition is used as effect varnish and effect coating, and for example metal, effect degree coated material that interfere or pearliness (pearly-lustre) are used to be coated with the article of making such as by metal and plastics, and this coating does not have formaldehyde to a great extent.This coating composition is applicable to all typical application processes that adopt in current metal coated and plastic-coated and the seal China ink industry, and spray application for example comprises that electrostatic spray uses and use various printing technology printing.This coating composition because of the extra high beginning do speed, also the optical property because of excellence merits attention.
Background technology
The article of being made by metal and plastics typically are equipped with an organic coating and (see R mppLexikon; Lacke und Druckfarben; Dr.Ulrich Zorll compiles; GeorgThieme Verlag; the Stuttgart; 1998), on the one hand-because of the use field different-be intended to protect this material (for example, protect that these article avoid wearing out, time effect, physical disturbance, make dirty etc.).On the other hand, this organic coating is being born the decoration function.For modern utility product and consuming product, increasing importance is being born in the decoration aspect.Therefore, in recent years, the painting effect coating for example number of the article of metal and/or pearliness effect coating constantly increases.Except that tradition is used (for example automobile), the also such coating of application progressively of the utility product of low value and consuming product relatively.Example is the shell of mobile telephone or notebook.In addition, aspect printing ink, effect pigment is used for for example advertisement brochure just progressively.
The coating that contains metal, interference and/or pearliness effect pigment, except that a lot of other used, be used for the automobile final lacquer and as the industrial coating of finish paint material, see R mpp Lexikon, Lacke und Druckfarben, Dr.Ulrich Zorll compiles, Georg ThiemeVerlag, the Stuttgart, 1998.They are processed into one and are coated with or two are coated with system, and consider the effect pigment that they are contained, so that more or less significantly metal effect or pearliness effect are characteristic.Isochromatic the reaching of best and/or desirable geometric condition it is essential the orientation of effect pigment on the light or tone for color.The fixed effect of this pigment during this is subjected to application technique (for example do/wet spray) and volatile component and evaporates and/or afterwards.
After coating is used, in order to ensure further processing rapidly and preventing that it is desirable beginning dried rapidly such as the pollutent defective that causes such as dust and dirt for example.Specifically, for effect coating, be necessary to prevent the mistake orientation of effect pigment during the volatile component evaporation.Therefore, for this purpose, often add the influential additive of rheology in hydrotropisms's coating.
The known hardness that can improve coating of hardened resin based on ketone and aldehyde.The reaction product that the water of ketone and aldehyde or derivatives thereof can disperse condensation product and may contain such product is described in EP 0,617 103 A1, EP 0838485, EP 0838486 (DE 19643704), DE 25 42090, DE-A 31 44 673 and DE-A 3406474 (EP 0154835).
DE-A 25 42 090 described have sulfonic and-depart from the inventive method-can be at the water-soluble cpds that from the associating condensation reaction of naphthenone, formaldehyde and basic metal hydrosulphite, obtains.
DE-A 31 44 673 has introduced equally by ketone, aldehyde and can import the water-soluble condensation product that the association response of the compound of acidic group obtains.The latter's example is sulphite and amide group sulfonate, Glycinates and phosphite.
DE-A 25 42 090 and DE-A 31 44 673 produce the product that contains ionogen (for example Na ion).Yet one of effect of such resin is the water tolerance of infringement vanish system.
EP 0 617 103 A1 have described and have not contained the group (for example carboxyl) that can change into ionic groups but contain for example reaction of ester group or polyisocyanates ether, molecular weight 500～5000 (a) and dihydroxy compound (b) of other functional group (seeing p.3 the 17th～21 row).The urethane that obtains so further with compound (c) reaction that except that the NCO reactive group, also contains the group that can change into ionic groups, and when wishing with the glycol that does not have further functional group, molecular weight 60～500 or many alcohol (d) reaction (seeing p.4 the 5th～15 row).This reaction product is subsequently with the reaction of a kind of condensation resins and transfer to aqueous phase.
DE 3406474 (EP 0154835) has described and has used aqueous liquid dispersion organic protective colloid, ketone resin or ketone/urea formaldehyde.Protective colloid is stayed in the coating subsequently and may be influenced some performances nocuously and for example the shortcoming of the tolerance of water and moisture hindered their purposes in the high value coating composition.
EP 0838485 has described esterification products.Thereby hydrolysis can take place known ester group causes polymer degradation, and influences package stability nocuously.And then, the acidic group that can freely touch also may induce reaction and/or with the non-compatibility of pigment.
EP 0838486 has described the aqueous resin dispersion that can obtain by the reaction or the partial reaction of following ingredients:
I. contain hydroxyl ketone resin, ketone/urea formaldehyde, urea/urea formaldehyde or its hydroderivating thing and
II. at least a have at least one free NCO group, can be by making the reaction of at least a isocyanic ester and/or polyisocyanates and some compounds the hydrophilic modifying isocyanic ester and/or the polyisocyanates that obtain, described compound except that containing hydrophilic radical or potential hydrophilic radical, also have at least one can be with the functional group of isocyanic ester radical reaction, have when testing active hydrogen and have at least one hydrophilic radical and/or a potential hydrophilic radical with Zerewitinoff
With in this and the combination subsequently of resin and water.
Summary of the invention
An object of the present invention is to find the water-based paint compositions of effect coating and effect printing ink, being intended that this coating should not have formaldehyde on very big degree.This coating composition should have dried speed of high beginning, and should positive especially influence be arranged to representing of this effect.
The purpose of institute of the present invention foundation is to reach by the following use of special coating composition in greater detail surprisingly.
The invention provides the water-based paint compositions of article effect coating, comprise in fact
A) at least a water-based base-material of 20wt%～94.5wt% and
B) 5wt%～79.5wt% hydrophilization ketone/urea formaldehyde and/or a kind of hydrophilization hydrogenation ketone/urea formaldehyde and
C) at least a effect pigment of 0.5wt%～25wt% and
D) at least a additive of 0wt%～74.5wt%,
Composition A)～D) weight amount sum is 100wt%.
Have been found that the following stated and by composition A)～combination of the coating composition that D) constitutes meets whole needed benchmark.
Embodiment
Composition A)
The water-based base material A at center of the present invention) be to use with the quantity of 20wt%～94.5wt%, better 30wt%～79.5wt%.
Give preferential one group the water-based base-material that is selected from following composition that is to use: urethane, polyacrylic ester, polyethers, polyester, Synolac, ether of cellulose, derivatived cellulose, polyvinyl alcohol and derivative, rubber, maleic acid ester resinoid, phenol/urea-formaldehyde resin, aminoresin (for example melamine resin, benzo guanamine resin), epoxy acrylate, Resins, epoxy, silicon ester and alkalimetal silicate (for example water glass) and/or silicone resin.This water-based base-material can be external crosslinking and/or self-crosslinking, air-dry (physical dryness) and/or oxidative cure.
Composition B)
The composition B at center of the present invention) be to use with the quantity of 5wt%～79.5wt%, better 10wt%～60wt%.
As composition B) suitability had by the aqueous resin dispersion that can obtain by the reaction or the partial reaction of following ingredients:
I. contain the ketone/urea formaldehyde of hydroxyl or its hydroderivating thing and
II. at least a have at least one free NCO group, can be by making the reaction of at least a isocyanic ester and/or polyisocyanates and some compounds the hydrophilic modifying isocyanic ester and/or the polyisocyanates that obtain, described compound except that containing hydrophilic radical or potential hydrophilic radical, also have at least one can with the functional group of isocyanic ester radical reaction
After the reaction with resin-neutralize when needing-make up with water.
The ketone that is applicable to preparation ketone/urea formaldehyde (composition I) comprises all ketone, especially acetone, phenyl methyl ketone, methylethylketone, heptan-2-ketone, penta-3-ketone, methyl iso-butyl ketone (MIBK), cyclopentanone, cyclododecanone, 2,2,4-and 2,4,4-trimethylammonium cyclopentanone, suberone and cyclooctanone, pimelinketone and one or more mixtures that the alkyl substituted cyclohexanone is arranged that contain the alkyl that adds up to 1～8 carbon atom are all arranged are separately or form of mixtures.There is the possible example of alkyl substituted cyclohexanone to comprise 4-tert-pentyl pimelinketone, 2-sec.-butylcyclohexanone, 2-tertiary butyl pimelinketone, 4-tertiary butyl pimelinketone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone.
Also can use for example ketone of amino and/or acidic group of further functional group in principle, although not so good.
Yet, in general, can use report on the document, be applicable to ketone resin and ketone/all ketone of urea formaldehyde synthetic; In general, the acid ketone of all C-H-.Give preferential phenyl methyl ketone, pimelinketone, the 4-tertiary butyl pimelinketone, 3,3 of being based on, 5-trimethylcyclohexanone and heptanone are separately or form of mixtures.
As the aldehyde composition of ketone/urea formaldehyde (composition I), what have suitability in principle is the aldehyde of no branching or branching, for example formaldehyde, acetaldehyde, butyraldehyde-n and/or isobutyric aldehyde, valeral and 12 (alkane) aldehyde.In general, can use bibliographical information to be applicable to ketone/all aldehyde of urea formaldehyde synthetic.Yet, give preferentially to be individually or to mix ground and use formaldehyde.
Needed formaldehyde normally as concentration for the aqueous solution of about 20wt%～40wt% or the use of alcohol (for example methyl alcohol or butanols) solution.Other type of service of formaldehyde comprises such as the use of paraformaldehyde or three alkane, is fine equally.Aromatic aldehyde for example phenyl aldehyde may reside among the mixture with formaldehyde equally.
The good especially initial compounds that is used for ketone/urea formaldehyde of composition I is phenyl methyl ketone, pimelinketone, 4-tertiary butyl pimelinketone, 3,3, and 5-trimethylcyclohexanone and heptanone are separately or form of mixtures, and formaldehyde.
The resin that generates from ketone and aldehyde also can be in the presence of suitable catalyzer, can be up to the pressure of 300bar hydrogen hydrogenation.In the process of this hydrogenation, some carbonyls of ketone/urea formaldehyde change into secondary hydroxyl.But from aldehyde and ketogenetic, except that the carbonyl segment, also have further hydrogenation official for example under the situation of the resin of aromatic structure, these further structures also can transform by suitable hydrogenation.Under situation, obtained cyclo-aliphatic structure such as aromatic structure.
Hydrophilic modifying that may be necessary is such as realizing by resin I and composition II are reacted, the latter is made up of at least a hydrophilic modifying isocyanic ester and/or polyisocyanates by at least one free NCO group, can obtain by making the reaction of at least a isocyanic ester and/or polyisocyanates and some compounds, this compound removes hydrophilic radical or potential hydrophilic radical-the hydrophilic group that promptly just becomes after neutralization-in addition at least one to the group of responding property of isocyanate group for example hydroxyl or amino etc.This being used for, the examples for compounds of (many) isocyanic ester hydrophilic modifying was amino acid, hydroxyl sulfoacid, thionamic acid and hydroxycarboxylic acid.Give preferential two (methylol) propionic acid or derivatives thereof that is to use.This hydrophilic modifying also can carry out with non-ionic type group (for example using polyethers) or with neutral compound.
Hydroxycarboxylic acid, especially for example two (methylol) propionic acid is good especially, this is due to the following facts: when with volatile alkali for example in the amine etc. and the time, they demonstrate strong hydrophilic effects, but, this effect rapidly disappears after this volatile alkali evaporation.Therefore, coating can be owing to not losing its defencive function, because any initial stage swelling does not take place such as humidity exposure.
Because it carries out the ability of (potential) hydrophilic modifying of two hydrophobic polyisocyanates by two hydroxyl, two (methylol) propionic acid also is good especially.
The polyisocyanates that is applicable to prepared composition II better is the functional polyisocyanates of two senses to four.The example is a cyclohexyl diisocyanate, methylcyclohexane diisocyanate, the ethylcyclohexane vulcabond, the propyl cyclohexane vulcabond, methyl diethyl cyclohexane vulcabond, phenylene diisocyanate, tolylene diisocyanate, two (isocyanato-phenyl) methane, the propane vulcabond, the butane vulcabond, the pentane vulcabond, hexane diisocyanate is hexamethylene diisocyanate (HDI) or 1 for example, 5-two isocyanato-s-2-methylpentane (MPDI), the heptane vulcabond, the octane vulcabond, nonane vulcabond for example 1,6-two isocyanato-s-2,4,4-trimethyl cyclohexane or 1,6-two isocyanato-s-2,2,4-trimethyl cyclohexane (TMDI), nonane triisocyanate is 4-isocyanato-methyloctane-1 for example, 8-vulcabond (TIN), decane vulcabond and triisocyanate, undecane vulcabond and triisocyanate, dodecane two isocyanide ester and triisocyanates, isophorone diisocyanate (IPDI), dicyclohexyl methyl hydride-4,4 '-vulcabond (H
12MDI), isocyanato-methyl cyclohexyl isocyanate, 2,5 (2,6)-two (isocyanato-methyl) dicyclos [2.2.1] heptane (NBDI), 1,3-two (isocyanato-methyl) hexanaphthene (1,3-H
6-XDI) or 1, and 4-two (isocyanato-methyl) hexanaphthene (1,4-H
6-XDI), independent or its mixture.
Another kind of polyisocyanates preferably has the compound of more than 2 isocyanate group by making simple vulcabond dimerization or trimerization, allophanic acid esterification, biuretized and/or polyurethane-reinforcement preparation, per molecule, and example is for example IPDI, HDI and/or H of these simple vulcabond
12The reaction product of MDI etc. and polyvalent alcohol (for example glycerine, TriMethylolPropane(TMP), tetramethylolmethane) and/or multifunctional polyamines maybe can be by making simple vulcabond for example IPDI, HDI and H
12The triisocyanate that trimerizations such as MDI obtain.
Giving preferential especially is from two (methylol) propionic acid or derivatives thereof and IPDI and/or TMDI and/or H
12MDI and/or HDI are with the hydrophilically modified polyisocyanates (II) of 1: 2 mol ratio generation.
Composition B) be that this solvent can be separated with distillation method after preparation when wishing with melt or the formulations prepared from solutions in being suitable for organic solvent.
Under the situation with solution reaction, solids content is 30wt%～95wt%, better 60wt%～80wt% preferably.
Employed suitable secondary solvent is an inert, this solvent does not form the compatibility gap, under atmospheric pressure has and be lower than 100 ℃ boiling point thereby can easily separate with distillation method when wish with water in broad range at least, and being reduced to the final dispersion liquid or the aqueous solution is that benchmark is lower than 2wt%, especially is lower than residual level, and the utilization once more of 0.5wt%.The example of this kind solvent that is suitable for comprises acetone, methylethylketone and tetrahydrofuran (THF).What also be suitable in principle is the more for example positive butyleneglycol of high boiling solvent, two positive butyleneglycols and N-Methyl pyrrolidone etc., and they are stayed in the dispersion liquid subsequently.
Yet, specifically, composition B) advantage be the following fact: in final aqueous resin dispersion, can not have organic solvent fully, and can also obtain stable high solid and disperse liquid.
On the reaction of I and II better can proceed to so a bit: residual NCO content (measuring according to DIN53185) was lower than 1%NCO; Preferential especially is on reaching so a bit: the residual NCO content of the product that generates from I and II is in 0.1%～0.5%NCO scope.According to current state of the art, still the NCO function of unreacted can be used to increase chain reaction by adding polyamines or water etc. in the reaction of I and II, otherwise, when wishing, can cause chain termination by the compound (for example monohydroxy-alcohol, monoamine) that adds NCO group simple function.
Under the situation of potential hydrophilic radical, the neutralizing agent that is suitable for can be added in the product of the present invention, thereby provide water-dilutable, water can disperse or the product of water dissolvable.
Potential hydrophilic radical according to the resin of the present invention preparation can use organic bases and/or mineral alkali for example organic amine or ammonia neutralization.Give preferential primary amine, secondary amine and/or the tertiary amine of being to use, for example ethamine, propylamine, dimethylamine, dibutylamine, hexahydroaniline, benzylamine, morpholine, piperidines and trolamine.Under the situation of the potential group of anionic, giving preferential especially is volatility tertiary amine, especially dimethylethanolamine, diethylethanolamine, 2-dimethylin-2-methyl-2-propyl alcohol, triethylamine, tripropyl amine and Tributylamine.Cationic potential ionic groups can use for example neutralizations such as acetate, formic acid, phosphoric acid, hydrochloric acid of organic acid and/or mineral acid.
The neutral degree better be in the stoichiometric quantity and required dosis neutralisata 50%～130%.
Neutral hydrophilic resin or resin solution are imported in the water, otherwise water is added to wherein, stirring is better arranged.Before adding water, the reaction product of I and II can be merged with the further resin that does not carry out hydrophilic modifying as yet or with other composition when wishing, these compositions are disperseed together.As the result of this measure, can obtain in this dispersion liquid more than the 45wt%, technical favourable highly filled.This solid fraction is positioned at 20wt%～70wt%, better 25wt%～60wt% scope in principle.
After the dispersion, this organic secondary solvent can remove, better under reduced pressure remove, and can reprocess when wishing.
Composition B) can be used as the base-material composition, and composition C) dispersion resin.
Composition C)
The composition C at center of the present invention) be to use with the quantity of 0.5wt%～25wt%, better 2wt%～20wt%.Have as composition C) suitability be, for example, metal effect pigments is aluminium, copper, copper/zinc and zinc pigment for example, the bronze of oxidation, ferric oxide-alumina pigment, coated interference pigment and pearliness effect pigment be metal oxide-pigments, mica, Bismuth Oxychloride, white lead carbonate, pearlescence or micronized titanium dioxide, foliated lamellar graphite, foliated lamellar ferric oxide, the multi-layer effect pigment and liquid crystal (polymkeric substance) pigment that comprise the PVD film or produce with CVD (chemical vapour deposition) method for example.
One piece of summary sees R mpp Lexikon for details, Lacke und Druckfarben, Dr.Ulrich Zorll compiles, Georg Thieme Verlag, the Stuttgart, 1998, also see BASF-Handbuch Lackiertechnik, ArturGoldschmidt, Hans-JoachimStreitberger, Vincentz-Verlag, Hanover, 2002.
Components D)
Components D) be to use with the quantity of 0～74.5wt%, better 5wt%～60wt%.
The components D that is suitable for) be auxiliary agent and additive, for example, inhibitor, organic solvent, surfactant, oxygen scavenqer and/or free-radical scavengers, catalyzer, photostabilizer, the color brightener, photosensitizer and light trigger, the additive that influences rheologic behavio(u)r is thixotropic agent and/or thickening material for example, flow control agent, anti, defoamer, softening agent, antistatic agent, lubricant, wetting agent, dispersion agent, sanitas comprises mycocide and/or biocide etc., thermoplastic additive, tinting material is dyestuff and pigment for example, matting agent, fire retardant, in release agent, filler, isocyanate curing agent and/or whipping agent.
From composition A)～D) preparation coating composition
This coating composition is by making (Lehrbuch der Lack-technologie, Th.Brock, the M.Groteklaes of each composition 20～80 ℃ temperature intense mixing preparation, P.Mischke, V.Zorll compiles, Vincentz Verlag, Hanover, 1998, the 229ff pages or leaves).The composition that is not liquid form is made into the solution in the appropriate solvent or in the water earlier before mixing when wishing, under agitation add remaining component then.Under the situation of pigment and/or filler etc., disperse.However, effect pigment is not a dispersive, and just under agitation import.
The formaldehyde content of this coating composition be lower than 100ppm, better be lower than 50ppm, better be lower than 10ppm.
The water-based paint compositions of being advocated is suitable for being coated with and/or prints by wide variety of materials metal, plastics, timber, paper, inorganic substance any article of making in concrete, stone material or the pottery etc. for example for example.They have, and the high beginning is done speed and excellent effect represents.
Drying, curing and/or crosslinked film have good adhesion property to undercoat; In addition, contraposition coating thereon is coated with that interlayer is bonding to be subjected to favourable influence.
Water-based paint compositions required for protection is zero defect ground levelling on employed base material, and does not have surface imperfection for example paint face and wetting defective etc.
Water-based paint compositions required for protection has 10%～80%, better 20%～60% solids content.
Coating composition of the present invention is used as one coating or as the undercoat material of multiple tracks lacquer system, and is used as printing ink.
Embodiment subsequently is intended to further specify the present invention but does not limit its range of application.
Embodiment
Composition B) preparation
1. the preparation of adducts
The mixture of 134g two (methylol) propionic acid, 380g acetone and 6g 10wt% concentration dibutyl tin laurate acetone soln under agitation with the 444g isophorone diisocyanate with the blending of speed so so that this thermopositive reaction still can be managed at leisure.With this mixture heating up to 60 ℃ and to keep this temperature be 9.2% until nco value.
After cool to room temperature, this solution under agitation with 2300g 55wt% concentration hydrogenation phenyl methyl ketone/formaldehyde resin (Kunstharz SK, available from Degussa AG) acetone soln and the blending of 12g10wt% concentration DBTL acetone soln, this mixture heating up is arrived about 60 ℃ reflux temperature., be reduced to below the 0.1%NCO its further stirring in this temperature until the nco value of this solution.
2. shift to aqueous phase
Replacement scheme A:
1) solution of the hydrophilic modifying resin of preparation neutralizes by add the 89g dimethylamino-ethanol under stirring at room in, and this solution is by adding the full softening water dispersed with stirring of 4200g then.Secondary solvent, acetone, under reduced pressure remove, provide solids content and be resin dispersion liquid about 33wt%, shelf-stable, fine, shallow lacteous together with the water of a certain ratio.
Replacement scheme B:
1) in the preparation solution under agitation with 3300g 55wt% concentration hydrogenation phenyl methyl ketone/formaldehyde resin (Kunstharz SK, available from Degussa AG) the acetone soln blending, with the neutralization of 89g dimethylamino-ethanol, this solution under agitation disperses by importing the full softening water of 4400g product under stirring at room.Secondary solvent, acetone, under reduced pressure remove together with the water of a certain ratio, provide solids content and be about 50wt%, shelf-stable, albescent dispersion liquid.
The dispersion liquid performance
Package stability
To saving 2) dispersion liquid A and B carry out shelf-stable sex investigation about the change of pH, viscosity and visual appearance.
| Performance | A | B |
| pH | ||
| Initially | 8.9 | 8.8 |
| After 6 months | 8.9 | 8.8 |
| 23 ℃ of viscosity * | ||
| Initially | 375-714mPa·s | 69-138mPa·s |
| After 6 months | 335-563mPa·s | 67-135mPa·s |
| Outward appearance | ||
| Post precipitation | Shallow lacteous | White |
| After 6 months | Shallow lacteous | White |
*Rotational viscosimeter; D:100 to 900s
-1
Coating composition embodiment:
| The base-material composition | Quality/g | |
| Item 1 | Dynapol HW 112-56(Degussa) | 257.0 |
| Cymel 327(Cytech) | 11.0 | |
| Each composition under agitation merges (600rpm) by described order | ||
| Relatively | CM I | ||
| Metal pasty state composition | Quality/g | Quality/g | |
| Item 2 | Composition B from embodiment | - | 132.0 |
| Base-material from item 1 | 93 | - | |
| DI water | 23.0 | - | |
| Hydroxal 8154(Eckhart-Werke) | 50.0 | 50.0 | |
| Each composition under agitation merges by described order, material restir 24 hours | |||
| Relatively | CM I | ||
| Transfer rare composition | Quality/g | Quality/g | |
| Item 3 | Base-material from item 1 | 80.0 | 80.0 |
| DI water | 11.2 | 16.0 | |
| Butyleneglycol | 2.0 | 2.0 | |
| N-Methyl pyrrolidone | 2.0 | 2.0 | |
| Tego 7447,10% aqueous solution (Tego) | 3.0 | 3.0 | |
| Metal mashed prod from item 2 | 30.0 | 36.4 | |
| Each composition under agitation merges by described order | |||
DI water=full deionization (softening) water
CM=coating
Item 2 slowly adds, and continuously stirring is to item 3.Viscosity has slight rising.After the merging, material restir 15 minutes.Viscosity is transferred to 30～40s (4,23 ℃ of Ford Cup) with DI water.
The formaldehyde content of coating is lower than 1ppm.
Paint spay-coating is to aluminium Bonder plate, and about 14～17 μ m of build were room temperature flash evaporation 8 minutes.Use standard commercial single component PU varnish colour then, solidified 25 minutes at 140 ℃ subsequently.
The coating of embodiment is better than comparative example coating, and the effect pigment orientation and the remarkable chromatic effects such as geometric condition of remarkable excellence arranged.
Claims (36)
1. the water-based paint compositions of article effect coating comprises in fact
A) at least a water-based base-material of 20wt%～94.5wt% and
B) 5wt%～79.5wt% hydrophilization ketone/urea formaldehyde and/or a kind of hydrophilization hydrogenation ketone/urea formaldehyde and
C) at least a effect pigment of 0.5wt%～25wt% and
D) at least a additive of 0wt%～74.5wt%,
Composition A)～D) weight amount sum is 100wt%.
2. claim 1 water-based paint compositions required for protection; wherein; the solids content of this coating composition is 10wt%～80wt%, better 20wt%～60wt%; the formaldehyde content of this coating composition be lower than 100ppm, better be lower than 50ppm, better be lower than 10ppm, and organic solvent content be lower than 20wt%, better be lower than 10wt%, better be lower than 2wt%.
3. claim 1 and 2 water-based paint compositions required for protection; wherein; use is selected from following one group water-based base-material as composition A): urethane, polyacrylic ester, polyethers, polyester, Synolac, ether of cellulose, derivatived cellulose, polyvinyl alcohol and derivative, rubber, maleic acid ester resinoid, phenol/urea-formaldehyde resin, aminoresin (for example melamine resin, benzo guanamine resin), epoxy acrylate, Resins, epoxy, silicon ester and alkalimetal silicate (for example water glass) and/or silicone resin, independent or its mixture.
4. claim 3 water-based paint compositions required for protection is wherein, as composition A) preferably the water-based base-material be external crosslinking and/or self-crosslinking, air-dry (physical dryness) and/or oxidative cure.
5. any one water-based paint compositions required for protection in the above claim, wherein, the aqueous resin dispersion that use can obtain by the reaction or the partial reaction of following ingredients is as composition B):
I. contain the ketone/urea formaldehyde of hydroxyl or its hydroderivating thing and
II. at least a have at least one free NCO group, can be by making the reaction of at least a isocyanic ester and/or polyisocyanates and some compounds the hydrophilic modifying isocyanic ester and/or the polyisocyanates that obtain, described compound except that containing hydrophilic radical or potential hydrophilic radical, also have at least one can with the functional group of isocyanic ester radical reaction
After the reaction with resin-neutralize when needing-make up with water.
6. claim 5 water-based paint compositions required for protection wherein, uses the resin that comprises the acid ketone of C-H as prepared composition B) composition I.
7. claim 6 water-based paint compositions required for protection; wherein; use is selected from the acid ketone of following C-H: acetone, phenyl methyl ketone, methylethylketone, heptan-2-ketone, penta-3-ketone, methyl iso-butyl ketone (MIBK), cyclopentanone, cyclododecanone, 2; 2; 4-and 2,4, the mixture of 4-trimethylammonium cyclopentanone; the mixture of suberone and cyclooctanone, pimelinketone and one or more mixtures that the alkyl substituted cyclohexanone is arranged that contain the alkyl that adds up to 1～8 carbon atom are all arranged are separately or form of mixtures.
8. claim 7 water-based paint compositions required for protection; wherein; the pimelinketone that uses following conduct to have alkyl to replace: 4-tert-pentyl pimelinketone, 2-sec.-butylcyclohexanone, 2-tertiary butyl pimelinketone, 4-tertiary butyl pimelinketone, 2-methylcyclohexanone and 3; 3; the 5-trimethylcyclohexanone, independent or its mixture.
9. claim 5 water-based paint compositions required for protection wherein, uses to comprise the resin of aldehyde as prepared composition B) composition I.
10. any one water-based paint compositions required for protection in the above claim; wherein; use following as prepared composition B) the aldehyde composition of composition I: formaldehyde, acetaldehyde, butyraldehyde-n and/or isobutyric aldehyde, valeral or 12 (alkane) aldehyde, separately or its mixture.
11. any one water-based paint compositions required for protection in the above claim; wherein; use is from phenyl methyl ketone, pimelinketone, 4-tertiary butyl pimelinketone, 3,3,5-trimethylcyclohexanone, heptanone, separately or the hydrogenation products of the resin made of its mixture and formaldehyde as composition I.
12. any one water-based paint compositions required for protection in the above claim, wherein, composition B) composition II is to use tertiary amine groups alcohol, aminocarboxylic acid, hydroxyl sulfoacid, thionamic acid and/or hydroxycarboxylic acid preparation.
13. any one water-based paint compositions required for protection in the above claim, wherein, composition B) composition II is to use the preparation of two (methylol) propionic acid.
14. any one water-based paint compositions required for protection in the above claim, wherein, composition B) composition II with composition I reaction before neutralize.
15. any one water-based paint compositions required for protection in the above claim wherein, uses the functional polyisocyanates prepared composition of two senses to four B) II.
16. any one water-based paint compositions required for protection in the above claim, wherein, use aromatic series is arranged, the polyisocyanates of isocyanate group that aliphatics and/or cyclic aliphatic connect or these mixture prepared composition B) II.
17. any one water-based paint compositions required for protection in the above claim wherein, uses 1-isocyanato--3,3,5-trimethylammonium-5-isocyanato-methylcyclohexane (isophorone diisocyanate; IPDI), trimethyl hexamethylene diisocyanate (TMDI), 1,6-two isocyanato-hexanes (HDI), two (4-isocyanato-hexyl) methane (H
12MDI), independent or its mixture.
18. any one water-based paint compositions required for protection in the above claim wherein, uses the polyisocyanates prepared composition B that biuret, uretdione (uretdione) or isocyanurate structure are arranged) II.
19. any one water-based paint compositions required for protection in the above claim wherein, uses from polyvalent alcohol and/or amine and reacts the polyisocyanates prepared composition B that obtains with monomeric diisocyanate) II.
20. any one water-based paint compositions required for protection in the above claim; wherein; use two (methylol) propionic acid and isophorone diisocyanate, trimethyl hexamethylene diisocyanate, 1,6-two isocyanato-hexanes and/or two (4-isocyanato-hexyl) methane was with 1: 2 mol ratio prepared composition B) II.
21. any one water-based paint compositions required for protection in the above claim, wherein, composition B) I and the reaction of II and being dispersed in the body (solvent-free) or in the presence of secondary solvent are subsequently carried out.
22. water-based paint compositions required for protection in the above claim, wherein, employed secondary solvent has at 1013hPa and is lower than 100 ℃ boiling point.
23. water-based paint compositions required for protection in the above claim, wherein, employed secondary solvent is acetone and/or methylethylketone and/or tetrahydrofuran (THF).
24. any one water-based paint compositions required for protection in the above claim, wherein, composition B) be with organic bases or mineral alkali neutral.
25. water-based paint compositions required for protection in the above claim, wherein, neutralization is to use dimethylethanolamine and/or diethylethanolamine and/or 2-dimethylin-2-methyl isophthalic acid-propyl alcohol to carry out.
26. any one water-based paint compositions required for protection in the above claim, wherein, neutralization is to use in the stoichiometric quantity and 50%～130% the carrying out of needed dosis neutralisata.
27. any one water-based paint compositions required for protection in the above claim wherein, before adding water, adds one or more compositions water-insoluble or water-dilutable.
28. any one water-based paint compositions required for protection in the above claim, wherein, result of use pigment is as composition C).
29. any one water-based paint compositions required for protection in the above claim, wherein, the effect pigment that uses this group of pigment that is selected from metal, pearliness and/or interference effect is as composition C).
30. any one water-based paint compositions required for protection in the above claim; wherein; use aluminium; copper; copper/zinc; pigment with zinc; the bronze of oxidation; ferric oxide-alumina pigment; metal oxide-pigments, mica; metal oxide-aluminum oxide pigment; metal oxide-silicon oxide pigment; metal oxide-iron oxide pigment; Bismuth Oxychloride, white lead carbonate; pearlescence or micronized titanium dioxide; foliated lamellar graphite; the foliated lamellar ferric oxide; the multi-layer effect pigment that comprises the PVD film or produce with CVD (chemical vapour deposition) method; and liquid crystal (polymkeric substance) pigment is as composition C).
31. any one water-based paint compositions required for protection in the above claim wherein, makes used additives and additive as components D).
32. any one water-based paint compositions required for protection in the above claim; wherein, use be selected from following one group; separately or the auxiliary agent of mixture and additive as components D): inhibitor; organic solvent; surfactant; oxygen scavenqer and/or free-radical scavengers; catalyzer; photostabilizer; the color brightener; photosensitizer and light trigger; the additive that influences rheologic behavio(u)r is thixotropic agent and/or thickening material for example; flow control agent; anti; defoamer; antistatic agent; softening agent; lubricant; wetting agent; dispersion agent; sanitas comprises mycocide and/or biocide etc.; thermoplastic additive; tinting material is dyestuff and pigment for example; matting agent; fire retardant; in release agent; filler; isocyanate curing agent and/or whipping agent.
33. the preparation method of a water-based paint compositions, said composition comprises in fact
A) at least a water-based base-material of 20wt%～94.5wt% and
B) the hydrogenation ketone/urea formaldehyde of the ketone/urea formaldehyde of 5wt%～79.5wt% hydrophilization and/or a kind of hydrophilization and
C) at least a effect pigment of 0.5wt%～25wt% and
D) at least a additive of 0wt%～74.5wt%,
Composition A)～D) weight amount sum is 100wt%,
This method is included in+and 20～+ 80 ℃ temperature stirs and/or disperses each thorough mixing that becomes to assign to.
34. the purposes of at least one water-based paint compositions required for protection in the above claim is used for coating or printing item.
35. the purposes of at least one water-based paint compositions required for protection in the above claim, as one coating or as the base paint of multiple tracks vanish system, or as printing-ink.
36. the purposes of at least one water-based paint compositions required for protection is used to be coated with or print the article of being made by metal, plastics, timber, paper, glass and/or inorganic substrate in the above claim.
37. a coated article of being made by metal, plastics, timber, paper, glass and/or inorganic substrate, it is with at least one coating composition production required for protection and/or reinforcement in the above claim.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102005010964.0 | 2005-03-10 | ||
| DE200510010964 DE102005010964A1 (en) | 2005-03-10 | 2005-03-10 | Aqueous coating compositions for effect coatings |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1942543A true CN1942543A (en) | 2007-04-04 |
Family
ID=36113797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800000043A Pending CN1942543A (en) | 2005-03-10 | 2006-01-16 | Aqueous coating substance compositions for decorative paint effects |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1942543A (en) |
| DE (1) | DE102005010964A1 (en) |
| WO (1) | WO2006094849A1 (en) |
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| CN101679803A (en) * | 2007-05-18 | 2010-03-24 | 巴斯福涂料股份公司 | Aqueous, pigmented coating agent, method for the production thereof, and the use thereof for the production of multilayer coats of paint |
| CN103525281A (en) * | 2013-09-13 | 2014-01-22 | 任振州 | Waterborne ultrafast-drying and high-adhesion protective coating |
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| DE4309079A1 (en) * | 1993-03-20 | 1994-09-22 | Basf Ag | Aqueous dispersion of a polyurethane and a condensation resin |
| US5977227A (en) * | 1997-09-30 | 1999-11-02 | Ncr Corporation | Method for forming aqueous dispersions of ketone resins |
-
2005
- 2005-03-10 DE DE200510010964 patent/DE102005010964A1/en not_active Withdrawn
-
2006
- 2006-01-16 WO PCT/EP2006/050230 patent/WO2006094849A1/en not_active Application Discontinuation
- 2006-01-16 CN CNA2006800000043A patent/CN1942543A/en active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| DE102005010964A1 (en) | 2006-09-14 |
| WO2006094849A1 (en) | 2006-09-14 |
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