CN1942542A - Aqueous paint compositions for wood - Google Patents
Aqueous paint compositions for wood Download PDFInfo
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- CN1942542A CN1942542A CNA2006800000077A CN200680000007A CN1942542A CN 1942542 A CN1942542 A CN 1942542A CN A2006800000077 A CNA2006800000077 A CN A2006800000077A CN 200680000007 A CN200680000007 A CN 200680000007A CN 1942542 A CN1942542 A CN 1942542A
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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
- C08G18/08—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
- C08G18/70—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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Manufacturing & Machinery (AREA)
- Paints Or Removers (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
The invention relates to aqueous paint compositions for wood, consisting of at least one binding agent, one modified ketone/aldehyde resin and, optionally, auxiliary agents and additional substances.
Description
The present invention relates to be used for the water base paint compositions of timber, wherein comprise at least a tackiness agent, a kind of ketone/urea formaldehyde of modification and assistant agent and additive when needing.
This coating composition is used to the outer application and the interior application of timber-work, and it is substantially free of formaldehyde.All coating processes commonly used that this coating composition is fit to use in the present wood working.Be characterized in extra high initial rate of drying and extra high hardness, and good elasticity and cementing property.
Timber-work has organic coating (seeing " R mpp Lexikon; Lacke undDruckfarben; Dr.Ulrich Zorll compiles; Georg Thieme Verlag; Stuttgart; 1998 ") usually; so that (depending on Application Areas) protection timber (for example protecting these goods to exempt from aging, animal or plant insect, burn into weathering, physical disturbance, contamination etc.) on the one hand; on the other hand; this organic coating plays decoration functions, for example outstanding timber texture and texture, supply a gap, painted or cover effect.
No matter be aspect industrial wood working or family expenses self-control, wish that all coating is initial rapidly dry, cause defective by for example contamination of dust, foul, insect etc. so that guarantee further to process apace and prevent.
In order to guarantee the effect of sufficiently high anti-mechanism stress, wish that coating has high hardness.But for the coating of routine, the increase of hardness can be accompanied by flexibility decrease.Yet good elasticity also needs, because timber-work more or less is soft, therefore can be out of shape, and constantly change owing to volume takes place in for example humidity variation.For the substrate protection of being carried out, advantages of good caking property matter is absolutely necessary.
The known hardness that can increase coating of hardened resin based on ketone and aldehyde.
In EP 0 617 103 A1, EP 0838485, EP 0838486 (DE 19643704), DE 25 42 090, DE-A 31 44 673 and DE-A 3406474 (EP 0154835), describe the water-dispersible polycondensation product of ketone and aldehyde or derivatives thereof and/or can comprise the reaction product of this class product.
DE-A 25 42 090 has described the water-soluble cpds that has sulfonic acid group, and is different with method of the present invention, and it can be obtained by the associating polycondensation by naphthenone, formaldehyde and basic metal hydrosulphite.
DE-A 31 44 673 has showed equally the water-soluble polycondensation product that the association response of compound that can be by ketone, aldehyde and introducing acidic-group obtains.The latter's example is sulphite, sulfamate, Glycinates and phosphoric acid salt.
Obtained containing ionogen product (for example containing the Na ion) according to DE-A 25 42 090 and DE-A 31 44 673.But one of this resinoid effect is the water tolerance that weakens coating system.
EP 0 617 103 A1 have described polymeric polyisocyanate (a) and molecular weight is the reaction of the dihydroxy compound (b) of 500-5000, compound (b) does not contain the group that can change into ionic group (for example hydroxy-acid group), but contain other functional group, for example ester group or ether (seeing that page 3 17-21 is capable).The urethane that obtains so further with the compound (c) that also contains certain group that can change into ionic group except the NCO-active group, and glycol when needing or polyvalent alcohol (d) reaction, (d) molecular weight is 60-500, and does not contain other functional group (see page 4,5-15 is capable).This reaction product and a kind of condensation resin reaction subsequently, and be transferred to water.
DE 3406474 (EP 0154835) has described the ketone resin that uses organic protective colloid or the water dispersion of ketone/urea formaldehyde.In follow-up coating, leave protective colloid and this shortcoming of disadvantageous effect may be arranged water-fast and moisture resistance properties, hinder their application in the high grade paint composition.
EP 0838485 has described the ketonize product.Hydrolysis can take place in known ester group, therefore causes polymer fracture and package stability is had disadvantageous effect.In addition, can free approaching acidic-group can cause reaction or uncompatibility with pigment.
EP 0838486 has described the resin water dispersion that can obtain by the reaction or the partial reaction of following material:
The ketone of hydroxyl, ketone/aldehyde and/or urea/urea formaldehyde or its hydrogenated products and
2. the isocyanic ester that at least one free NCO group is arranged and/or the polymeric polyisocyanate of at least a hydrophilic modifying, it can obtain by at least a isocyanic ester and/or polymeric polyisocyanate and compound reaction, this compound also has at least one and to contain the functional group who is active hydrogen in the Zerewitinoff test with the isocyanic ester radical reaction except that hydrophilic or potential hydrophilic group, and also have at least one hydrophilic radical and/or potential hydrophilic group
Resin that will neutralize and water combination subsequently.
An object of the present invention is to find to be used for the outer application of timber-work and the water base paint compositions of interior application, wherein this coating should be substantially free of formaldehyde.This coating should have high initial rate of drying, and has good elasticity and close-burning while at the film of doing, and high hardness is arranged.
This target as basis of the present invention is accomplished by using special coating composition described in detail below astoundingly.
The invention provides and be used for timber-work, wood based material is medium-density fiberboard (MDF) or high density fiberboard (HDF) for example, or class woodwork for example lumber layer stampings or the outer application of tarsia-work and the water base paint compositions of interior application, mainly contains
A) at least a aqueous-based adhesive of 20-95% weight and
B) the hydrogenation ketone/urea formaldehyde of the ketone/urea formaldehyde of the hydrophilization of 5-80% weight and/or hydrophilization and
C) at least a additive of 0-75% weight,
Component A) to C) the weight sum constitute 100% weight.
Have been found that the following component A that contains) to C) coating composition meet desired whole standard.
Component A)
Aqueous-based adhesive A) be basal component of the present invention, its consumption is a 20-95% weight, preferred 30-80% weight.
Aqueous-based adhesive below preferred use the: urethane, polyacrylic ester, polyethers, polyester, Synolac, ether of cellulose, derivatived cellulose, polyvinyl alcohol and derivative, rubber, maleic acid resin, phenolic aldehyde/urea-formaldehyde resin, aminoresin (for example melamine resin and benzoguanamine resin), epoxy acrylate, ring ammonia resin, silicon ester and alkalimetal silicate (for example water glass) and/or silicone resin.This aqueous-based adhesive can be external crosslinking and/or self-crosslinking, dry air (physical dryness) and/or oxidative cure.
B component)
B component) be basal component of the present invention, its consumption is a 5-80% weight, preferred 10-60% weight.
Suitable B component) comprise the resin water dispersion that can obtain by following substance reaction or partial reaction:
I. ketone/the urea formaldehyde of hydroxyl or its hydrogenated products and
II. the isocyanic ester that at least one free NCO group is arranged and/or the polymeric polyisocyanate of at least a hydrophilic modifying, it can obtain by at least a isocyanic ester and/or polymeric polyisocyanate and compound reaction, this compound except that hydrophilic or potential hydrophilic radical, also have at least one can with the functional group of isocyanic ester radical reaction
Subsequently resin (neutralizing when needing) and water are made up,
The ketone that is fit to preparation ketone/urea formaldehyde (component I) comprises all ketone, especially acetone, methyl phenyl 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, suberone and cyclooctanone, the pimelinketone that pimelinketone and all alkyl that have total to contain one or more alkyl groups of 1-8 carbon atom replace, and their mixture.The possible example of the pimelinketone that alkyl replaces comprises 4-tertiary butyl pimelinketone, 2-sec.-butylcyclohexanone, 2-tertiary butyl pimelinketone, 4-tertiary butyl pimelinketone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone.Although not too desirable, also can use in principle also to contain other functional group, for example the ketone of amino and/or acidic-group.
But, also can use in the document as being fit to synthetic described all the various ketone of ketone resin and ketone/urea formaldehyde; In general, the acid ketone of all C-H-.Methyl phenyl ketone, pimelinketone, the 4-tertiary butyl pimelinketone, 3,3 of preferably independent or mixed form, 5-trimethylcyclohexanone and heptanone.
As the aldehyde component (component I) of ketone/urea formaldehyde, the aldehyde of straight chain or straight chain in principle, for example formaldehyde, acetaldehyde, butyraldehyde-n and/or isobutyric aldehyde, valeral and lauric aldehyde are suitable.Usually can use in the document as being fit to the synthetic all aldehyde mentioned of ketone/urea formaldehyde.But preferably use formaldehyde or its mixture.
Required formaldehyde is that the water of about 20-40% weight or the form of alcohol (for example methyl alcohol or ethanol) solution are used usually with concentration.Also can use other type of service of formaldehyde, comprise and for example use paraformaldehyde or three alkane.
The particularly preferred initial compounds that is used for the ketone/urea formaldehyde of component I is independent or the methyl phenyl ketone of form of mixtures, pimelinketone, 4-tertiary butyl pimelinketone, 3,3,5-trimethylcyclohexanone and heptanone, and formaldehyde.
Also can under the pressure of the highest 300 crust, use hydrogen hydrogenation in the presence of the appropriate catalyst by the resin that ketone and aldehyde form.In hydrogenation process, some carbonyls of ketone/urea formaldehyde change into secondary hydroxyl.In the situation that forms resin by aldehyde that also contains hydrogenatable functional group (for example aromatic structure) except carbonyl and ketone, these other structure also can transform by suitable hydrogenation.For example, the situation at aromatic structure obtains alicyclic structure.
The hydrophilic modifying that may need reacts with component I I by for example resin 1 to be finished, contain at least a isocyanic ester and/or the polymeric polyisocyanate that contains the hydrophilic modifying of at least one free NCO group among the component I I, it can obtain by at least a isocyanic ester and/or polymeric polyisocyanate and compound reaction, this compound remove hydrophilic or potential hydrophilic (promptly, just after neutralization, just become hydrophilic) group outside, also contain at least one can with the functional group of isocyanic ester radical reaction, for example hydroxyl or amino.
The examples for compounds that this class is used for the hydrophilic modifying of (gathering) isocyanic ester is amino acid, hydroxyl sulfoacid, thionamic acid and hydroxycarboxylic acid.Preferred neopentanoic acid and the derivative thereof of using.Hydrophilic modifying also can carry out with non-ionic group (for example using polyethers) or with the compound that has been neutralized.
Preferred especially hydroxycarboxylic acid, dimethylol propionic acid especially for example, because of its in volatile alkali (for example amine) and the time demonstrate the intensive hydrophilic interaction, after volatile alkali evaporates, then sharply go down.Therefore, coating can be because of contacting with moisture and losing defencive function, because initial swelling does not take place.
Dimethylol propionic acid is also desirable especially because it can carry out (potential) hydrophilic modifying of two hydrophobic polymeric polyisocyanates by its two hydroxyls.
The polymeric polyisocyanate of suitable preparation II is two to four functional polymeric polyisocyanates preferably.The example is a cyclohexyl diisocyanate, methylcyclohexane diisocyanate, the ethylcyclohexane vulcabond, the propyl cyclohexane vulcabond, methyl diethyl cyclohexane vulcabond, phenylene vulcabond, inferior cresyl vulcabond, two (isocyano-phenyl) methane, the propane vulcabond, the butane vulcabond, the pentane vulcabond, hexane diisocyanate (hexamethylene diisocyanate (HDI) or 1 for example, 5-two isocyano-s-2-methylpentane (MPDI)), the heptane vulcabond, octane vulcabond, nonane vulcabond (for example 1,6-two isocyanatos-2,4,4-trimethyl cyclohexane or 1,6-two isocyanatos-2,2,4-trimethyl cyclohexane (TMDI)), nonane triisocyanate (for example 4-isocyanato methyloctane 1,8-vulcabond (TIN)), decane vulcabond and triisocyanate, undecane vulcabond and triisocyanate, dodecane vulcabond and triisocyanate, isophorone diisocyanate (IPDI), dicyclohexyl methyl hydride 4,4 '-vulcabond (H
12MDI), isocyano-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 (isocyano-methyl) hexanaphthene (1,4-H
6-XDI), use separately or the mixing use.
Another kind of preferred polymeric polyisocyanate is the compound that the isocyanate groups more than 2 is arranged in each molecule, they are by making simple vulcabond by two polymerizations or trimerization, allophanic acid esterification, biuretized and/or urethane, the example is these simple vulcabond, for example IPDI, HDI and/or H
12MDI, with the reaction product of polyvalent alcohol (for example glycerol, TriMethylolPropane(TMP), tetramethylolmethane) and/or polyfunctional polyamines, or can be by simple vulcabond for example IPDI, HDI and H
12The triisocyanate that MDI obtains by trimerization reaction.
Particularly preferably be by dimethylol propionic acid or derivatives thereof and IPDI and/or TMDI and/or H
12MDI and/or HDI are by the polymeric polyisocyanate (II) of the hydrophilic modifying of 1: 2 mol ratio formation.
B component) in melt or in the solution of suitable solvent, prepares, can after preparation, isolate this solvent when needing with distillation method.
If react in solution, preferred solids content is a 30-95% weight, more preferably 60-80% weight.
The suitable secondary solvent that uses is lower boiling inert solvent, it does not form miscible gap with water at least in very wide scope, boiling point under the normal atmosphere is lower than 100 ℃, therefore separate with distillation method easily, residual quantity is low to moderate is less than 2% of final dispersion or aqueous solution weight, particularly be less than 0.5%, and can reuse.The example of this suitable kind solvent comprises acetone, methylethylketone and tetrahydrofuran (THF).High boiling solvent such as normal-butyl ethylene glycol, di-n-butyl ethylene glycol and N-Methyl pyrrolidone also are suitable in principle, and they then are retained in the dispersion.
Yet, B component) an advantage particularly in, can accomplish not contain organic solvent in the final resin water dispersion fully, but still obtain the solid dispersion of stable height.
The reaction of I and II can preferably proceed to such degree, makes remaining NCO content (measuring according to DIN 53185) be lower than 1%NCO, and especially preferably proceeding to NCO content remaining in the product that is formed by I and II is 0.1-0.5%.According to existing technology, keeping unreacted NCO functional group can be used for by adding the transfer reaction that polyamines or water take place in the reaction of I and II, is that the compound (for example monohydroxy-alcohol, monoamine) of simple function brings out chain termination reaction by adding with respect to the NCO group when needed perhaps.
In the situation of potential hydrophilic radical, can in product of the present invention, add neutralizing agent, thereby obtain water-dilutable, water is dispersible or water-soluble products.
Potential hydrophilic radical according to the resin of the present invention preparation can neutralize with organic and/or mineral alkali, for example organic amine or ammonia.Preferred primary amine, secondary amine and/or tertiary amine, for example ethamine, propylamine, dimethylamine, dibutylamine, hexahydroaniline, benzylamine, morpholine, piperidines and the trolamine of using.In the situation of the potential group of anionic, preferred especially volatile tertiary amine, especially dimethylethanolamine, diethylethanolamine, 2-dimethylamino-2-methyl isophthalic acid-propyl alcohol, triethylamine, tripropyl amine and Tributylamine.Cationic potential ionic group can be with organic and/or mineral acid, for example neutralizations such as acetate, formic acid, phosphoric acid, hydrochloric acid.
Degree of neutralization is preferably in the stoichiometry and the 50-130% of required dosis neutralisata.
The hydrophilic resin or the resin solution that neutralized are added in the entry, or in resin, add water, preferably under agitation carry out.Before adding water, if desired, can be with the reaction product of I and II and other resin without hydrophilic modifying, or other component is mixed together, and then each component disperseed together.Because this measure might obtain having the dispersion of the solid content of industrial superiority above 45% weight.Solids content is generally 20-70% weight, is preferably 25-60% weight.
After disperseing, can remove organic assistant agent, preferably under reduced pressure remove, and can handle again when needing.
Component C)
Component C) consumption is a 0-75% weight, is preferably 5-60% weight.
Suitable component C) is assistant agent and additive, for example co-inhibitor, organic solvent, surfactant, oxygen scavenqer and/or free-radical scavengers, catalyzer, photostabilizer, colored brightening agent, photosensitizer and light trigger, influence the additive (for example thixotropic agent and/or thickening material) of rheological property, flow control agent, anti, softening agent, defoamer, static inhibitor, lubricant, wetting agent, dispersion agent, sanitas (comprising mycocide and/or biocides), thermoplastic additive, dyestuff, pigment, matting agent, fire retardant, in execute releasing agent, filler, isocyanate curing agent and/or pore forming material.
By component A to C) the preparation coating composition:
By each component thorough mixing under 20-80 ℃ temperature being prepared coating composition (" Lehrbuch der Lacktechnologie ", Th.Brock, M.Groteklaes, P.MIschke, V.Zorll writes, Vincentz Verlag, Hannover, 1998,229 pages and after).If desired, elder generation forms solution with the component of on-liquid form in suitable solvent or water before mixing, under agitation adds all the other components then.In the situation of for example pigment and/or filler, disperse.
The formaldehyde content of this coating composition is lower than 100ppm, preferably is lower than 50ppm, more preferably less than 10ppm.
Described this water base paint compositions is fit to the outer application and the interior application of woodwork, deutero-forest product or class woodwork.They have high initial rate of drying, therefore also have very high resistance to blocking.
Drying, curing and/or crosslinked film have high-caliber hardness and good elasticity and cementing property, and this is shown as good indentation cohesiveness or pendulum hardness and/or Buckholts hardness value and erichsen test value to fine grade.Penetrating power on various timber and wood based material and substrate wettability and wear resisting property are fine.In addition, the solvent resistance of these films is very high.
Described this water base paint compositions flows on the wood substrate of using perfectly, and does not have surface imperfection, for example pit and wetting defective.
The solids content of this water base paint compositions is 15-18%, preferred 20-60%.
Coating composition of the present invention can be used as filler, sealing clay (putters), and impreg, wood coating, for example staining agent, undercoat, primer coating, whole coating materials, wash primer and end face coating are used for the substrate of timber and/or class wood.
The following examples are to be used for further specifying the present invention rather than to limit its range of application:
Embodiment
B component) preparation
1. the preparation of affixture
The mixture that with 134g dihydroxypropionic acid, 380g acetone and 6g concentration is the dibutyl tin dilaurate acetone soln of 10% weight under agitation mixes with the 444g isophorone diisocyanate, and mixing velocity should make this thermopositive reaction keep control easily.With this mixture heating up to 60 ℃ and keep this temperature, be 9.2% until the NCO number.
After being cooled to room temperature, with this solution under agitation with hydrogenated acetophenone/formaldehyde resin (Kunstharz SK of 2300g concentration 55% weight, Degussa AG) the DBTL acetone soln of acetone soln and 12g concentration 10% weight mixes, with this mixture heating up to about 60 ℃ reflux temperature.Under this temperature, continue to stir, reduce to below the 0.1%NCO until the NCO of this solution number.
2. be transferred to water
Alternatives A:
With 1) in the solution of resin of hydrophilic modifying of preparation add the neutralization of 89g dimethylaminoethanol in room temperature with under stirring, under agitation add the complete deionized water of 4200g then solution disperseed.Secondary solvent acetone and a part of water are removed in decompression, obtain shelf-stable, tiny, slightly opalescent resin dispersion, and its solids content is about 33% weight.
Alternatives B:
With 1) in preparation solution under agitation with hydrogenated acetophenone/formaldehyde resin (Kunstharz SK of 3300g concentration 55% weight, Degussa AG) acetone soln mixes, this product, adds the complete deionized water of 4400g solution stirring is disperseed with the neutralization of 89g dimethylaminoethanol in room temperature with under stirring.Secondary solvent acetone and a part of water are removed in decompression, obtain the micro white dispersion of shelf-stable, and its solids content is about 50% weight.
The character of dispersion
Package stability
To deriving from 2) dispersion A and B, study its package stability with regard to its pH, viscosity and appearance change.
| Character | A | B |
| pH | ||
| Initially | 8.9 | 8.8 |
| After 6 months | 8.9 | 8.8 |
| 23 ℃ viscosity * | ||
| Initially | 375-714mPa·s | 69-138mPa·s |
| After 6 months | 335-563mPa·s | 67-135mPa·s |
| Outer existing | ||
| After the preparation | Opalescence slightly | White |
| After 6 months | Opalescence slightly | White |
*Rotational viscosimeter; D:100 to 900s
-1
The embodiment of coating composition:
| Mixture 1 | Quality/g |
| Aquacat(Münzing) | 0.50 |
| Zircat(Münzing) | 0.50 |
| DI-H 2O | 1.00 |
| Base-material | Quality/g |
| Halwedrol OX TN 7735/40W(Hüttenes Albertus) | 27.00 |
| Byk 024(Byk) | 0.80 |
| Byk 346(Byk) | 0.35 |
| Syloid ED 50(Grace) | 2.00 |
| Lanco Wax PP 1362(Lubrizol) | 0.50 |
| Mixture 1 | 2.00 |
Each component mixed under high degree of agitation in high speed dispersor and homogenizing 10 minutes.
| Contrast | Varnish I | Varnish II | Varnish III | |
| 0 | 10 | 20% B component | 30% B component | |
| Base-material | 32.65 | 32.65 | 32.65 | 32.65 |
| Halwedrol OX TN 7735/40W | 27.50 | 22.05 | 16.60 | 11.14 |
| Dowanol DPnB (Dow) | 1.00 | 1.00 | 1.00 | 1.00 |
| DI-H 2O | 19.70 | 19.70 | 19.70 | 19.70 |
| Collacral PU 75 is (with DI-H 2O 1∶1) (BASF AG) | 1.40 | 1.40 | 1.40 | 1.40 |
| Rheolate 350 (Elementis) | 1.25 | 1.25 | 1.25 | 1.25 |
| B component | - | 6.60 | 13.20 | 19.80 |
| Formaldehyde content | ＜1ppm | ＜1ppm | ＜1ppm | ＜1ppm |
DI-H
2O=removes mineral substance (deionization) water fully
All quantity are g/g
This varnish is coated on deal board and the sheet glass with scraper, coat-thickness 200 μ m are at room temperature dry.
All films all demonstrate flowing of no blemishes, and free of surface defects.
Scraper indentation cohesiveness on the deal board
| To in the same old way | Varnish I | Varnish II | Varnish III | |
| Estimate | 3 | 2 | 0 | 0 |
The 0=bonding is fine; 10=is non-caked
Description of drawings
Fig. 1 shows the difference when coating becomes dust-dry.Obviously, along with the increase of B component content, rate of drying significantly improves.
Fig. 2 shows the development of surface hardness (Konig pendulum hardness).Obviously, along with B component content increases, pendulum hardness significantly improves.
Claims (33)
1. water base paint compositions that is used for woodwork, mainly contain:
A) at least a aqueous-based adhesive of 20-95% weight,
B) the hydrogenation ketone/urea formaldehyde of the ketone/urea formaldehyde of a kind of hydrophilization of 5-80% weight and/or a kind of hydrophilization and
C) at least a additive of 0-75% amount amount,
Component A) to C) the quantity sum constitute 100% weight.
2. the water base paint compositions of claim 1, wherein the solids content of coating composition is a 15-80% weight; The formaldehyde content of coating composition is lower than 100ppm, preferably is lower than 50ppm, more preferably less than 10ppm; The content of organic solvent is lower than 20% weight, preferably is lower than 10% weight, more preferably less than 2% weight.
3. claim 1 or a kind of water base paint compositions of 2, wherein use following aqueous-based adhesive independent or form of mixtures as component A): urethane, polyacrylic ester, polyethers, polyester, Synolac, ether of cellulose, derivatived cellulose, polyvinyl alcohol and derivative, rubber, maleic acid resin, phenolic aldehyde/urea-formaldehyde resin, aminoresin (for example melamine resin and benzoguanamine resin), Resins, epoxy, silicon ester and alkalimetal silicate (for example water glass), silicone resin, and fluoropolymer.
4. a kind of water base paint compositions of claim 3 is wherein preferably as component A) aqueous-based adhesive be external crosslinking and/or self-crosslinking, dry air (physical dryness) and/or oxidative cure.
5. the water base paint compositions of aforementioned each claim wherein uses resin water dispersion as B component), they can obtain by the reaction or the partial reaction of following material:
I. ketone/the urea formaldehyde of hydroxyl or its hydrogenated products and
II. the isocyanic ester that at least one free NCO group is arranged and/or the polymeric polyisocyanate of at least a hydrophilic modifying, it can obtain by at least a isocyanic ester and/or polymeric polyisocyanate and compound reaction, this compound except that hydrophilic or potential hydrophilic radical, also have at least one can with the functional group of isocyanate groups reaction, subsequently with this resin (neutralizing when needing) and water combination.
6. the water base paint compositions of claim 5 wherein uses the resin that contains the acid ketone of C-H-as being used to prepare B component) component I.
7. the water base paint compositions of claim 6 wherein uses the acid ketone of C-H-, and it is selected from following compound independent or form of mixtures: acetone, methyl phenyl ketone, methylethylketone, heptan-2-ketone, penta-3-ketone, methyl butyl ketone, cyclopentanone, cyclododecanone, 2,2,4-and 2,4, the mixture of 4-trimethylammonium cyclopentanone, suberone and cyclooctanone, pimelinketone, and to contain one or more the total number of carbon atoms be the pimelinketone that all alkyl of the alkyl of 1-8 replace.
8. the water base paint compositions of claim 7, wherein use 4-tert-pentyl pimelinketone independent or form of mixtures, 2-sec.-butylcyclohexanone, 2-tertiary butyl pimelinketone, 4-tertiary butyl pimelinketone, 2-methylcyclohexanone and 3,3, the pimelinketone that the 5-trimethylcyclohexanone replaces as alkyl.
9. a kind of water base paint compositions of claim 5 wherein uses to contain urea formaldehyde as being used to prepare B component) component I.
10. the water base paint compositions of aforementioned each claim wherein uses formaldehyde, acetaldehyde, butyraldehyde-n and/or isobutyric aldehyde, valeral and dodecanal independent or mixing and form to be used for preparing B as the aldehyde component) component I.
11. the water base paint compositions of aforementioned each claim, wherein use by methyl phenyl ketone independent or form of mixtures, pimelinketone, 4-tertiary butyl pimelinketone, 3,3, the hydrogenated products of the resin that 5-trimethylcyclohexanone and heptanone and formaldehyde form is as component I.
12. the water base paint compositions of aforementioned each claim wherein uses uncle's amino alcohol, aminocarboxylic acid, carboxyl sulfonic acid, thionamic acid and/or hydroxycarboxylic acid to prepare B component) component I I.
13. the water base paint compositions of aforementioned each claim, wherein B component) component I I prepare with dimethylol propionic acid.
14. the water base paint compositions of aforementioned each claim, wherein B component) component I I with component I reaction before be neutralized.
15. the water base paint compositions of aforementioned each claim wherein uses the functional polymeric polyisocyanate of difunctionality to four to prepare B component) component I I.
16. the water base paint compositions of aforementioned each claim wherein uses the polymeric polyisocyanate have with the isocyanate groups of aromatics, aliphatic series and/or the connection of alicyclic form to prepare B component) component I I.
17. the water base paint compositions of aforementioned each claim wherein uses 1-isocyanato-3,3 independent or form of mixtures, 5-trimethylammonium-5-isocyanato methylcyclohexane (isophorone diisocyanate; IPDI), trimethyl hexamethylene diisocyanate (TMDI), 1,6-two isocyanato hexanes (HDI) and two (4-isocyanato hexyl) methane (H
12MDI).
18. the water base paint compositions of aforementioned each claim wherein uses the polymeric polyisocyanate with biuret, uretdione or isocyanurate structure to prepare B component) II.
19. the water base paint compositions of aforementioned each claim wherein uses the polymeric polyisocyanate that is obtained by polyvalent alcohol and/or amine and monomeric diisocyanate reaction to prepare B component) II.
20. the water base paint compositions in aforementioned at least one the claim, wherein using mol ratio is 1: 2 dimethylol propionic acid and isophorone diisocyanate, trimethyl hexamethylene diisocyanate, 1, and 6-two isocyanato hexanes and/or two (4-isocyanato) methane prepare B component) II.
21. the water base paint compositions in aforementioned at least one the claim, wherein B component) I and the reaction of II and dispersion subsequently to become block mode (solvent-free) or in the presence of solvent, to carry out.
22. the water base paint compositions of aforementioned at least one claim, the boiling point of use therein secondary solvent under 1013hPa is lower than 100 ℃.
23. the water base paint compositions of aforementioned each claim, use therein secondary solvent are acetone and/or methylethylketone and/or tetrahydrofuran (THF).
24. the water base paint compositions of aforementioned each claim, wherein B component) neutralization carry out with organic or inorganic alkali.
25. the water base paint compositions of aforementioned each claim wherein uses dimethylethanolamine and/or diethylethanolamine and/or 2-dimethylamino-2-methyl isophthalic acid-propyl alcohol to neutralize.
26. the water base paint compositions of aforementioned each claim wherein uses in the stoichiometry and the 50-130% of aequum neutralizes.
27. the water base paint compositions of aforementioned each claim wherein before adding water, is added in one or more components of not dissolving in the water or can not dilute with water earlier.
28. the water base paint compositions of aforementioned each claim wherein uses assistant agent and additive as component C).
29. the water base paint compositions of aforementioned each claim wherein uses assistant agent independent or form of mixtures and additive as component C), they are selected from: co-inhibitor, organic solvent, surfactant, oxygen scavenqer and/or free-radical scavengers, catalyzer, photostabilizer, colored brightening agent, photosensitizer and light trigger, influence the additive (for example thixotropic agent and/or thickening material) of rheological property, flow control agent, anti, defoamer, softening agent, antistatic agent, lubricant, wetting agent, dispersion agent, sanitas (comprising mycocide and/or biocides), thermoplastic additive, dyestuff, pigment, matting agent, fire retardant, in execute releasing agent, filler, isocyanate curing agent and/or pore forming material.
30. a method for preparing water base paint compositions, said composition mainly contains
A) at least a aqueous-based adhesive of 20-95% weight and
B) the hydrogenation ketone/urea formaldehyde of the ketone/urea formaldehyde of the hydrophilization of 5-80% weight and/or hydrophilization and
C) at least a additive of 0-75% weight,
Component A) to C) the quantity sum constitute 100% weight, described method is utilize to stir under+20 to+80 ℃ temperature and/or disperse each component thorough mixing.
31. the water base paint compositions in aforementioned at least one the claim is used for the purposes of coated articles.
32. the water base paint compositions in aforementioned at least one the claim is used to apply the purposes of woodwork, wood based material (for example medium density fibre board (MDF) (MDF) or high density fiberboard (HDF)) goods or class woodwork (for example lumber layer stampings or tarsia-work).
33. with the water base paint compositions manufacturing and/or the cated woodwork of enhanced of aforementioned at least one claim, wood based material (as medium density fibre board (MDF) (MDF)) or high density fiberboard (HDF) goods or class woodwork (for example lumber layer stampings or tarsia-work).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE200510010967 DE102005010967A1 (en) | 2005-03-10 | 2005-03-10 | Aqueous paint compositions for wood |
| DE102005010967.5 | 2005-03-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1942542A true CN1942542A (en) | 2007-04-04 |
Family
ID=36087853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800000077A Pending CN1942542A (en) | 2005-03-10 | 2006-01-16 | Aqueous paint compositions for wood |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1942542A (en) |
| DE (1) | DE102005010967A1 (en) |
| WO (1) | WO2006094848A2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965032A (en) * | 2012-12-05 | 2013-03-13 | 中南林业科技大学 | Silicon-based wood adhesive with interpenetrating polymer network structure and preparation method thereof |
| CN103013319A (en) * | 2013-01-09 | 2013-04-03 | 江苏科泰绝热新材料有限公司 | Moisture-proof coating for polyurethane rigid foam and preparation method of moisture-proof coating |
| CN103087625A (en) * | 2013-01-31 | 2013-05-08 | 安徽蓝柯复合材料有限公司 | High-adhesion silver paint |
| CN103525238A (en) * | 2013-10-21 | 2014-01-22 | 陆君军 | Aqueous phenolic resin environment-friendly paint |
| CN103525237A (en) * | 2013-10-21 | 2014-01-22 | 陆君军 | Preparation process of aqueous phenolic resin environment-friendly paint |
| CN104774583A (en) * | 2015-04-30 | 2015-07-15 | 黄琳 | Anti-static adhesive |
| TWI596171B (en) * | 2015-10-28 | 2017-08-21 | Plant antiseptic deworm-functional water-based wood paint and its preparation method | |
| CN107793881A (en) * | 2017-10-30 | 2018-03-13 | 郭艳玲 | A kind of coating protection materials and preparation method thereof |
| CN111699051A (en) * | 2018-01-23 | 2020-09-22 | 芬兰国家技术研究中心股份公司 | Coated wood veneer and method for treating a wood veneer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9232670B2 (en) | 2010-02-02 | 2016-01-05 | Apple Inc. | Protection and assembly of outer glass surfaces of an electronic device housing |
| CN103599879B (en) * | 2013-11-11 | 2016-05-18 | 惠州市长润发涂料有限公司 | A kind of coating process of musical instrument surface coating |
| EP3115389B1 (en) * | 2015-07-07 | 2020-04-01 | Evonik Operations GmbH | Preparation of polyurethane foam |
| CN105587101B (en) * | 2015-12-31 | 2017-11-24 | 福州皇家地坪有限公司 | Non-solvent epoxy antistatic floor |
| EP3275952B1 (en) * | 2016-07-25 | 2019-01-30 | Daw Se | Aqueous coating material |
| EP3830158A4 (en) * | 2018-08-02 | 2022-03-23 | Dow Global Technologies LLC | Methods for reducing aldehyde emissions in polyurethane foams |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2249100B1 (en) * | 1973-10-24 | 1979-02-02 | Goldschmidt Ag Th | |
| IT1160123B (en) * | 1983-05-03 | 1987-03-04 | Vibac Spa | PRESSURE-SENSITIVE SELF-ADHESIVE TAPE PROVIDED WITH A PRINTABLE NON-STICKER LACQUER AND LACQUER COMPOSITION FOR THE DEPOSITION OF SUCH LAYER |
| DE3406474A1 (en) * | 1984-02-23 | 1985-08-29 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING AQUEOUS KETONE RESIN OR KETONE / ALDEHYDE RESIN DISPERSIONS AND USE THEREOF |
| US5627261A (en) * | 1994-03-15 | 1997-05-06 | National Starch And Chemical Investment Holding Corporation | Aldehyde resins with reduced and stabilized free-formaldehyde content |
| DE19643704A1 (en) * | 1996-10-23 | 1998-04-30 | Huels Chemische Werke Ag | Aqueous resin dispersions |
| ATE260310T1 (en) * | 1999-06-21 | 2004-03-15 | Surface Specialties Austria | WATER-DILUTIBLE RESINS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
-
2005
- 2005-03-10 DE DE200510010967 patent/DE102005010967A1/en not_active Withdrawn
-
2006
- 2006-01-16 CN CNA2006800000077A patent/CN1942542A/en active Pending
- 2006-01-16 WO PCT/EP2006/050229 patent/WO2006094848A2/en not_active Application Discontinuation
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965032A (en) * | 2012-12-05 | 2013-03-13 | 中南林业科技大学 | Silicon-based wood adhesive with interpenetrating polymer network structure and preparation method thereof |
| CN103013319A (en) * | 2013-01-09 | 2013-04-03 | 江苏科泰绝热新材料有限公司 | Moisture-proof coating for polyurethane rigid foam and preparation method of moisture-proof coating |
| CN103013319B (en) * | 2013-01-09 | 2015-05-13 | 江苏科泰绝热新材料有限公司 | Moisture-proof coating for polyurethane rigid foam and preparation method of moisture-proof coating |
| CN103087625A (en) * | 2013-01-31 | 2013-05-08 | 安徽蓝柯复合材料有限公司 | High-adhesion silver paint |
| CN103525238A (en) * | 2013-10-21 | 2014-01-22 | 陆君军 | Aqueous phenolic resin environment-friendly paint |
| CN103525237A (en) * | 2013-10-21 | 2014-01-22 | 陆君军 | Preparation process of aqueous phenolic resin environment-friendly paint |
| CN104774583A (en) * | 2015-04-30 | 2015-07-15 | 黄琳 | Anti-static adhesive |
| TWI596171B (en) * | 2015-10-28 | 2017-08-21 | Plant antiseptic deworm-functional water-based wood paint and its preparation method | |
| CN107793881A (en) * | 2017-10-30 | 2018-03-13 | 郭艳玲 | A kind of coating protection materials and preparation method thereof |
| CN111699051A (en) * | 2018-01-23 | 2020-09-22 | 芬兰国家技术研究中心股份公司 | Coated wood veneer and method for treating a wood veneer |
| CN111699051B (en) * | 2018-01-23 | 2024-02-13 | 芬兰国家技术研究中心股份公司 | Coated wood veneer and method for treating a wood veneer |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2006094848A2 (en) | 2006-09-14 |
| WO2006094848A3 (en) | 2006-12-21 |
| DE102005010967A1 (en) | 2006-09-14 |
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