CN1942544A - Aqueous coating substance compositions having an improved resistance to stoning - Google Patents
Aqueous coating substance compositions having an improved resistance to stoning Download PDFInfo
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- CN1942544A CN1942544A CNA2006800000081A CN200680000008A CN1942544A CN 1942544 A CN1942544 A CN 1942544A CN A2006800000081 A CNA2006800000081 A CN A2006800000081A CN 200680000008 A CN200680000008 A CN 200680000008A CN 1942544 A CN1942544 A CN 1942544A
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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
-
- 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
-
- 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
- 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
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/02—Condensation polymers of aldehydes or ketones only
Abstract
The invention relates to aqueous substance coating compositions having an improved resistance to stoning, made of at least one binding agent, one modified ketone/aldehyde resin and, optionally, auxiliary agents and additional substances for coating metals and plastics.
Description
Technical field
The present invention relates to by at least a base-material, a kind of modification ketone resin and auxiliary agent and additive are formed when wishing be used for coating metal and plastics, have a water-based paint compositions that improves anti-rubble damage effect.
This coating composition is used in particular for improving the anti-rubble damage effect on plastics and metal, and this coating does not have formaldehyde to a great extent.This coating composition is applicable to employed usual method of application in all modern metal coated and the plastic-coated, and for example spraying is as helpless spraying and electrostatic spraying.
This coating composition was done speed and extra high hardness and extraordinary elasticity and tackiness and is merited attention because of the extra high beginning.Being worth ben is, for by strong short and small object collision, for example particularly collides the physical abuse that may cause by rubble and has excellent protection effect.
Background technology
The article of being made by metal or plastics that high value uses that are intended to all are equipped with an organic coating (seeing " R mpp Lexikon; Lacke und Druckfarben; Dr.Ulrich Zorll volume; Georg Thieme Verlag; Stuttgart; 1998 ") now, 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, burn into timeization effect, physical disturbance, make dirty etc.).On the other hand, this organic coating is being born the decoration function.
For example, the printing of paper and film is information (brochure, wrapping material) service on the one hand; On the other hand, by means of topological design, make this information change into can be noticeable form.Except that performances such as dried speed of maximum beginning, such as not only excellent bonds and elastic performance but also excellent abrasive resistance also are important.
In order to ensure further processing rapidly and prevent such as the pollutent defective that causes such as dust and dirt for example, to do be desirable to coating economically the beginning rapidly.
To the sufficiently high protection of mechanical stress, require coating to have high hardness in order to ensure for example.Yet, with regard to conventional coatings, improve hardness and will follow elasticity to reduce.And the good elasticity performance equally also needs.
Extraordinary adhesive performance is very important for the lasting protection of base material.For metal base, especially need extraordinary adhesive power, so that obtain high corrosion control effect.For for the application in the multiple tracks layer of lacquer system, excellent adhering between coatings power is very important.In addition, therefore the mechanical stress that many commodity all will stand to continue, is all having strict requirement for coating aspect wear resistance and the anti-external action.
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 (DE19643704), DE 25 42 090, DE-A 31 44 673 and DE-A 3406474 (EP0154835).
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.
Obtain containing the product of ionogen (for example Na ion) according to DE-A 25 42 090 and DE-A 31 44 673.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 ketone resin, ketone/urea formaldehyde and/or the urea/urea formaldehyde of hydroxyl or its hydrogenation modification product 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 seek a kind of water-based paint compositions that can form coating with good adhesion and the damage of anti-crushing stone.This coating should not have formaldehyde on very big degree.In addition, this coating composition also should have dried speed of high beginning.
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 the anti-crushing stone damage performance that especially is intended to strengthen various base materials, comprise in fact
A) at least a water-based base-material of 20wt%～98wt% and
B) 2wt%～80wt% hydrophilization ketone/urea formaldehyde and/or a kind of hydrophilization hydrogenation ketone/urea formaldehyde and
C) at least a additive of 0wt%～75wt%,
Composition A)～C) weight amount sum is 100wt%.
Have been found that the following stated and comprise composition A)～combination of C) coating composition meets whole needed benchmark.
Embodiment
Composition A)
The substantial water-based base material A of the present invention) be to use with the quantity of 20wt%～98wt%, better 30wt%～80wt%.
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 substantial composition B of the present invention) be to use with the quantity of 2wt%～80wt%, better 4wt%～60wt%.
The composition B that is suitable for) comprise 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 hydrogenation modification product 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 the boiling point that is lower than 100 ℃ thereby can easily separate with distillation method is arranged with water in broad range at least, be reduced to the final dispersion liquid or the aqueous solution be benchmark be lower than 2wt%, especially be lower than 0.5wt% residual level, and utilize once more.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 DIN 53185) 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-4-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 C)
Composition C) be to use with the quantity of 0～75wt%, better 5～60wt%.
The composition C 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, antistatic agent, softening agent, lubricant, wetting agent, dispersion agent, sanitas comprises mycocide and/or biocide etc., thermoplastic additive, dyestuff, pigment, matting agent, fire retardant, in release agent, filler, isocyanate curing agent and/or whipping agent.
From composition A)～C) preparation coating composition
This coating composition is by making (" Lehrbuch der Lacktechnologie ", Th.Brock, the M.Groteklaes of each composition 20～80 ℃ temperature intense mixing preparation, P.Mischke, V.Zorll compiles, Vincentz Verlag, Hannover, 1998, the 229 ff 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.
The formaldehyde content of this coating composition be lower than 100ppm, better be lower than 50ppm, better be lower than 10ppm.Water-based paint compositions required for protection has 15%～80%, better 20%～60% solids content.
Water-based paint compositions required for protection is particularly suitable for being coated with the article of being made by metal and plastics.This coating composition has dried speed of high beginning, therefore also has very good non-stick property.
Drying, curing and/or crosslinked film have good adhesion property; 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.
Coating composition of the present invention is as for example single coating finishing paint such as finish paint and transparent coating material, dipping systems, and the undercoat material of painted, surperficial, priming paint and multiple tracks layer of lacquer system, and also be used as printing-ink and adhesives system.
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 (priming paint):
| Composition | Relatively | Embodiment | |
| Part 1 | Dynapol EP HW 112-56 (Degussa AG) | 47.8g | 47.8g |
| Maprenal MF 900 (Vianova Resins GmbH) | 4.2g | 4.2g | |
| DMEA/DI water=1/1 | 0.6g | 0.6g | |
| Dispersion/replacement scheme A of embodiment) | 0g | 5.1g | |
| DI (deionization) water | 2.3g | 2.3g | |
| Byketol WS (Byk-Chemie) | 1.4g | 1.4g | |
| Add up to | 56.3g | 61.4g | |
| Under 1000rpm, add each composition of part 1 with high speed dispersor, disperseed then 10 minutes by described order. | |||
| Part 2 | Part 1 | 61.4g |
| Butyldiglycol | 2.3g | |
| Kronos 2059(Kronos Titan) | 21.0g | |
| Blanc fixe micro (Sachtleben Chemie) | 4.9g | |
| Aerosil(Degussa AG) | 0.7g | |
| Byk 348(Byk-Chemie) | 0.2g | |
| DI (deionization) water | 9.5g | |
| Add up to | 100.0g | |
| Under 1000rpm, add each composition of part 2 with high speed dispersor, in ball mill, under 1200rpm, disperseed 20 minutes then by described order | ||
DI-H
2Softening entirely (deionization) water of O=
With DMEA/DI water with pH regulator to about 8.2～8.8, use DI water (No. 4 Ford cup, 23 ℃) with viscosity adjustment to 40～45 second again.
The formaldehyde content of two kinds of coating all is lower than 1ppm.
Test board: the lacquer system (spraying) on the phosphatizing steel plate: cathode electrodip painting, according to the priming paint of embodiment, the metal bottom coating.
Drying conditions: about 10 minutes of flash-off time, then 160 ℃ of dryings 20 minutes.
| Properties： | Relatively | Embodiment |
| K nig pendulum hardness | 135-143 | 152-159 |
| Mark signature tack to base material | 2 | 0 |
| The mark signature tack of undercoat (interlayer tack) | 2 | 0 |
| 20 °/60 ° of gloss | 85/87 | 92/98 |
| Mist degree | 47-53 | 49-55 |
| Anti-rubble damage (VW specification 2 * 500g/2bar) | 4 | 2 |
Add substantive composition B of the present invention) improved hardness, ply adhesion, gloss and the damage effect of anti-rubble of coating.
Claims (34)
1. one kind has the water-based paint compositions that improves anti-rubble damage effect, comprises in fact
A) at least a water-based base-material of 20wt%～95wt% and
B) 5wt%～80wt% hydrophilization ketone/urea formaldehyde and/or a kind of hydrophilization hydrogenation ketone/urea formaldehyde and
C) at least a additive of 0wt%～75wt%,
Composition A)～C) weight amount sum is 100wt%.
2. claim 1 water-based paint compositions required for protection; wherein; the solids content of this coating composition is 15wt%～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 or 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), Resins, epoxy, silicon ester and alkalimetal silicate (for example water glass), silicone resin and fluoropolymer, 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 hydrogenation modification product 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 isocyanate groups 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 mixture, suberone and the cyclooctanone of 4-trimethylammonium cyclopentanone, 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 and 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 and 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 groups 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) and two (4-isocyanato-hexyl) methane (H12MDI), separately 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, makes used additives and additive as composition C).
29. 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 composition C): 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; dyestuff; pigment; matting agent; fire retardant; in release agent; filler; isocyanate curing agent and/or whipping agent.
30. the preparation method of a water-based paint compositions, said composition comprises in fact
A) at least a water-based base-material of 23wt%～95wt% and
B) the hydrogenation ketone/urea formaldehyde of the ketone/urea formaldehyde of 2wt%～80wt% hydrophilization and/or a kind of hydrophilization and
C) at least a additive of 0～75wt%,
Composition A)～C) 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.
31. at least one item water-based paint compositions required for protection is used for the purposes of coated article in the above claim.
32. at least one water-based paint compositions required for protection is used for the purposes of the article that coating metal and/or plastics make in the above claim.
33. at least one item water-based paint compositions required for protection is as the purposes of the priming paint of automobile finish in the above claim.
34. a coated article of being made by metal or plastics, it is with at least one coating composition production required for protection and/or covering with paint in the above claim.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE200510010947 DE102005010947A1 (en) | 2005-03-10 | 2005-03-10 | Aqueous coating compositions with improved stone chip protection |
| DE102005010947.0 | 2005-03-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1942544A true CN1942544A (en) | 2007-04-04 |
Family
ID=36577458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800000081A Pending CN1942544A (en) | 2005-03-10 | 2006-01-16 | Aqueous coating substance compositions having an improved resistance to stoning |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1942544A (en) |
| DE (1) | DE102005010947A1 (en) |
| WO (1) | WO2006094850A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073975A (en) * | 2012-10-15 | 2013-05-01 | 怀远县巨龙机械制造有限公司 | Alkyd resin vehicle primer and preparation method thereof |
| CN103333594A (en) * | 2013-05-30 | 2013-10-02 | 蚌埠市时代电子有限公司 | Self-cleaning heat-dissipation coating and preparation method thereof |
| CN103333540A (en) * | 2013-05-30 | 2013-10-02 | 蚌埠市时代电子有限公司 | Aging resistance thermal dissipation coating and preparation method thereof |
| CN103351773A (en) * | 2013-05-30 | 2013-10-16 | 蚌埠市时代电子有限公司 | Ultraviolet resistant heat dissipation coating and preparation method thereof |
| CN103351772A (en) * | 2013-05-30 | 2013-10-16 | 蚌埠市时代电子有限公司 | Acid and alkali resistant heat dissipating coating and preparation method thereof |
| CN103468113A (en) * | 2013-08-16 | 2013-12-25 | 安徽快来防水防腐有限公司 | Weather-resistant polyurethane waterproof coating |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8946351B2 (en) | 2012-11-19 | 2015-02-03 | King Saud University | Environmental friendly poly(ether-fattyamide) resin composition |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3075935A (en) * | 1959-12-17 | 1963-01-29 | Shawinigan Resins Corp | Coating compositions of aqueous vinyl acetate polymer emulsions modified with ketone-aldehyde resins |
| IT1087205B (en) * | 1977-10-24 | 1985-06-04 | Moplefan Spa | POLYALEFINECHE FILMS COATED WITH A HEAT-SEALING LACQUER BASED ON A KETONIC RESIN |
| DE4309079A1 (en) * | 1993-03-20 | 1994-09-22 | Basf Ag | Aqueous dispersion of a polyurethane and a condensation resin |
| DE19643704A1 (en) * | 1996-10-23 | 1998-04-30 | Huels Chemische Werke Ag | Aqueous resin dispersions |
| US5977227A (en) * | 1997-09-30 | 1999-11-02 | Ncr Corporation | Method for forming aqueous dispersions of ketone resins |
| AT407253B (en) * | 1997-10-06 | 2001-02-26 | Vianova Kunstharz Ag | WATER-THINNABLE RESINS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| ES2216764T3 (en) * | 1999-06-21 | 2004-11-01 | Surface Specialties Austria Gmbh | DILUABLE RESINS WITH WATER, PROCEDURE FOR ITS PREPARATION AND ITS USE. |
| DE102004034303A1 (en) * | 2004-07-15 | 2006-02-09 | Degussa Ag | Functionalized, aqueous resins |
-
2005
- 2005-03-10 DE DE200510010947 patent/DE102005010947A1/en not_active Withdrawn
-
2006
- 2006-01-16 WO PCT/EP2006/050231 patent/WO2006094850A1/en not_active Application Discontinuation
- 2006-01-16 CN CNA2006800000081A patent/CN1942544A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073975A (en) * | 2012-10-15 | 2013-05-01 | 怀远县巨龙机械制造有限公司 | Alkyd resin vehicle primer and preparation method thereof |
| CN103073975B (en) * | 2012-10-15 | 2016-03-02 | 怀远县巨龙机械制造有限公司 | A kind of Alkyd resin vehicle primer and preparation method thereof |
| CN103333594A (en) * | 2013-05-30 | 2013-10-02 | 蚌埠市时代电子有限公司 | Self-cleaning heat-dissipation coating and preparation method thereof |
| CN103333540A (en) * | 2013-05-30 | 2013-10-02 | 蚌埠市时代电子有限公司 | Aging resistance thermal dissipation coating and preparation method thereof |
| CN103351773A (en) * | 2013-05-30 | 2013-10-16 | 蚌埠市时代电子有限公司 | Ultraviolet resistant heat dissipation coating and preparation method thereof |
| CN103351772A (en) * | 2013-05-30 | 2013-10-16 | 蚌埠市时代电子有限公司 | Acid and alkali resistant heat dissipating coating and preparation method thereof |
| CN103351772B (en) * | 2013-05-30 | 2016-06-15 | 蚌埠市时代电子有限公司 | A kind of acid and alkali-resistance heat radiation coating and its preparation method |
| CN103351773B (en) * | 2013-05-30 | 2016-06-29 | 蚌埠市时代电子有限公司 | A kind of anti-ultraviolet heat radiation coating and preparation method thereof |
| CN103468113A (en) * | 2013-08-16 | 2013-12-25 | 安徽快来防水防腐有限公司 | Weather-resistant polyurethane waterproof coating |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2006094850A8 (en) | 2006-11-09 |
| DE102005010947A1 (en) | 2006-09-14 |
| WO2006094850A1 (en) | 2006-09-14 |
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Open date: 20070404 |