WO1997013817A1 - Pates pigmentaires aqueuses et leur utilisation pour produire des peintures aqueuses - Google Patents
Pates pigmentaires aqueuses et leur utilisation pour produire des peintures aqueuses Download PDFInfo
- Publication number
- WO1997013817A1 WO1997013817A1 PCT/EP1996/004442 EP9604442W WO9713817A1 WO 1997013817 A1 WO1997013817 A1 WO 1997013817A1 EP 9604442 W EP9604442 W EP 9604442W WO 9713817 A1 WO9713817 A1 WO 9713817A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- water
- pigment
- dilutable
- iron oxide
- Prior art date
Links
Classifications
-
- 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
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
- C09D5/028—Pigments; Filters
-
- 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
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
- C09D17/007—Metal oxide
Definitions
- the invention relates to aqueous pigment pastes and their use for the production of aqueous lacquers.
- the pigmentation of aqueous paints takes place by adding aqueous pigment concentrates, so-called pigment pastes, to the other paint components.
- Pigment pastes consist of water, at least one pigment, at least one water-thinnable binder and, if applicable, organic solvents, wetting agents and other additives customary for pigment pastes (cf.Volker Radke in "Pigments for paints", Technical Academy Esslingen, Chapter 7, dispersion of pigments, Export Verlag, 1990).
- the pigment particles contained in the pigment paste are not smaller than the primary particles and not larger than 10 ⁇ m and that the pigment particles are wetted as completely as possible by the binder. Otherwise, the coloristic properties of the paints and the stability of the pigment pastes are unsatisfactory.
- the pigment in powder form is mixed with water, binder and, if appropriate, other additives, such as, for example, wetting agents. The mixture obtained in this way is then sheared in a dissolver and ground in a grinding unit (e.g.
- the object underlying the present invention was to provide pigment pastes containing water, at least one pigment, at least one water-dilutable binder and solvents, wetting agents and other additives customary for pigment pastes, which can be prepared without time-consuming and energy-consuming grinding processes.
- the pigment pastes preferably contain
- the pigment pastes according to the invention have a solids content of 20 to 70, preferably 35 to 50% by weight, a pH of 7 to 9, preferably 7.5 to 8.5 and a temperature of 23 ° C. and a shear rate of 50 sl Viscosity from 100 to 4000, preferably 600 to 1000 mPas and at a shear rate of 1000 sl a viscosity of 100 to 1000 mPas, preferably 200 to 400 mPas.
- iron oxide pigments suitable for aqueous lacquers can be used as component B.
- Iron oxide pigments that can be used are: iron oxide red (hematite, ⁇ -dieisen trioxide), iron oxide yellow (iron oxide hydroxide) and iron oxide brown (mixed pigment of iron oxide red, iron oxide yellow and iron oxide black).
- the water-dilutable polyurethane resins used as component (C) can by reacting
- a polyester and / or polyether polyol with a number average molecular weight of 400 to 5000 or a mixture of such polyester and / or polyether polyols (ii) a polyisocyanate or a mixture of polyisocyanates, optionally (iii) a hydroxyl and / or Organic compound containing amino groups with a molecular weight of 60 to 400 (number average) or a mixture of such compounds and optionally (iv) a compound which contains only one group which is reactive toward isocyanate groups in the molecule.
- the polyurethane resins used as component (C) usually have a number average molecular weight of at least 1000.
- the number average molecular weight of the polyurethane resins should preferably be at least 4000, particularly preferably between 5000 and 8000.
- the data on the number average molecular weights relate to gel permeation chromatography measurements which are carried out using a polystyrene standard.
- incorporation of (iii) components containing amino groups is preferably carried out in such a way that first a (N) group-containing prepolymer is prepared from (i), (ii) and optionally a hydroxyl group-containing component (iii), which is then in aqueous phase with an amino group-containing (iii) Component is further implemented (cf. EP-A-89 497).
- the polyurethane resins used as component (C) must contain hydrophilic groups which ensure the water-thinnability of the polyurethane resins. These hydrophilic groups can be nonionic or ionic, and the polyurethane resins can also contain both ionic and nonionic hydrophilic groups. Particularly suitable nonionic hydrophilic groups are poly (oxyalkylene) groups. These poly (oxyalkylene) groups can be introduced into the polyurethane resin molecules both via component (i) and via poly (oxyalkylene) group-containing (iii) components. Polyrethane resins containing anionic groups are preferably used.
- the groups capable of forming anions which are preferably carboxyl groups, can be introduced into the polyurethane resin molecules via component (i) (in particular as polyester polyols containing carboxyl groups, as described in DE-A-39 03 804) and / or via component (iii) . It is preferred to use (iii) components containing carboxyl groups.
- the polyurethane resins used as component (C) preferably have an acid number of 7 to 50, particularly preferably 15 to 35.
- the water-dilutable polyurethane resins used according to the invention are preferably produced by using components (i), (ii) and optionally (iii) an isocyanate group-containing prepolymer is prepared, which is then reacted with an (iii) component having at least three hydroxyl groups.
- the carboxyl groups are then neutralized with the aid of preferably tertiary amines and the polyurethane resin is dispersed in water.
- the reaction with (iii) components containing amino groups is less preferred (cf. DE-A-- 35 45 618).
- polyester and polyether polyols which can be used as component (i), which are preferably polyester and polyether diols, are described in EP-A-89497, DE-A-35 45 618, EP-A-355 433, US-A-4,719,132 and DE-A-39 03 804 described in detail.
- Polyester diols are preferably used as component (i).
- Component (i) is preferably used in an amount such that it makes up 50 to 80, particularly preferably 60 to 70% by weight of the polyurethane resin.
- polyisocyanates which can be used are tetramethylxylylene diisocyanate (TMXDI), phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate,
- Propylene diisocyanate, ethyl ethylene diisocyanate and trimethylhexane diisocyanate called.
- polyisocyanates with functionalities over two can also be used. If necessary, the average functionality can be reduced by using monoisocyanates.
- polyols with up to 44 carbon atoms per molecule such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,2-butylene glycol, 1,6- Hexanediol, trimethylolpropane, castor oil or hydrogenated castor oil, ditrimethylolpropane ether, pentaerythritol, 1,2-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, bisphenol F, neopentylglycol, hydroxypivalic acid neopentylglycol esters, hydroxyethylated or hydroxypropylated bisphenol are used.
- Groups (iii) capable of forming anions can also be introduced into the polyurethane resin molecules via component (iii).
- Carboxyl groups are preferably introduced into the polyurethane resin molecules via component (iii). This can be done, for example, with the aid of dihydroxypropionic acid, dihydroxysuccinic acid and dihydroxybenzoic acid.
- Carboxyl groups in the polyurethane resin molecules are 2,2-dimethylolalkanoic acids such as 2,2-dimethylolacetic acid, 2,2-
- Carboxyl groups can also be via amino group-containing (iii) components such as e.g. ⁇ , ⁇ -diaminovaleric acid and 3,4-diaminobenzoic acid are introduced.
- (iii) components containing amino groups is less preferred.
- Compounds (molecular weight) of 60 to 400 (number average) which contain either a hydroxyl or a primary amino or a secondary amino group can be used in particular as component (iv).
- component (iv) are preferably aliphatic alcohols having 1 to 6 carbon atoms such as. B. methanol, ethanol, propanol, butanol, pentanol or hexanol.
- Both organic and inorganic bases can be used to neutralize the groups capable of forming anions.
- Primary, secondary and tertiary amines such as ethylamine, propylamine, dimethylamine, dibutylamine, cyclohexylamine, benzylamine, morpholine, piperidine and triethanolamine are preferably used.
- Tertiary amines are particularly preferably used as neutralizing agents, in particular dimethylethanolamine, triethylamine, tripropylamine and tributylamine.
- the molecular weight can be influenced, for example, by the ratio between the equivalents of NCO groups used and the equivalents used of groups reactive toward NCO groups in components (i), (iii) and (iv).
- the molecular weight can also be controlled by the reaction of an NCO group-containing prepolymer prepared from (i), (ii) and optionally (iii) with component (iii) by the amount of component (iii) used.
- (iii) acts as an end group former or chain extender.
- the molecular weight can also be controlled by stopping the reaction at the point in time when the desired molecular weight has been reached.
- the reaction can e.g. B. can be terminated by rapidly lowering the reaction temperature and / or adding a reactant which reacts with the isocyanate groups still present without chain extension occurring (for example water, component (iv) or component (iii) in high excess ).
- the pigment pastes according to the invention can contain, as component (D), any water-dilutable polyester resin suitable for pigment pastes or a mixture of such polyester resins.
- Water-dilutable polyester resins are known and commercially available in a large selection. They can be prepared by reacting polyols with polycarboxylic acids or their anhydrides and generally contain carboxylate groups which ensure that the polyester resins can be diluted with water.
- Water-dilutable polyesters are those with free carboxyl groups, i.e. High acid number polyester.
- the second possibility is the formation of partial esters of di- or polycarboxylic acids with hydroxyl-rich polyesters with a low acid number. Anhydrides of dicarboxylic acids are usually used for this reaction, which are reacted with the hydroxyl component under mild conditions to form a free carboxyl group.
- the amines which can be used as component D can include primary, secondary or tertiary amines. Examples are dimethylethanolamine, aminomethylpropanol, NH3, triethylamine, tripropylamine, tributylamine, ethylamine, propylamine, dimethylamine, dibutylamine, cyclohexylamine, morpholine, piperidine and triethanolamine.
- the coating compositions according to the invention can also contain other customary additives, such as solvents, fillers, plasticizers, stabilizers, wetting agents, dispersing aids, leveling agents, defoamers and catalysts, individually or in a mixture in the customary amounts. These substances can be added to the individual components and / or the overall mixture.
- Dispersing aids (component G) which can be used are, for example, polyalkylene oxides, in particular poloxyethylene.
- Suitable fillers are e.g. Talc, mica, kaolin, chalk, quartz flour, asbestos flour, slate flour, barium sulfate, various silicas, silicates, glass fibers, organic fibers or the like.
- ethylene glycol dimethyl ether Contain ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, cyclohexanone, methyl ethyl ketone, acetone, isophorone or mixtures thereof.
- the pigment pastes according to the invention are distinguished in that they can be produced in the desired quality without grinding. This means that the iron oxide pigment particles contained in the pigment pastes according to the invention achieve the required particle size even without grinding. It is sufficient if the pigment pastes according to the invention are mixed well in a dissolver and, if appropriate, in an inline mixer and then, if appropriate, filtered. Dissolver times of 10 to 60, preferably 15 to 30 minutes at shear rates of 10 to 30, preferably 15 to 25 m / s are sufficient.
- the present invention accordingly also relates to a method for producing a pigment paste containing water, at least one pigment, at least one water-dilutable binder and solvents, wetting agents and other additives customary for pigment pastes.
- This is characterized in that (A) 25 to 80% by weight of deionized water (B) 10 to 65% by weight of at least one iron oxide pigment
- (G) 0 to 2% by weight of at least one dispersing agent are mixed in a dissolver and, if appropriate, in an inline mixer and then, if appropriate, filtered.
- Phthalic anhydride 12.5 g 1,6-hexanediol, 65 g O 97/13817 PC17EP96704442
- IPDI isophorone diisocyanate
- the reaction mixture is followed by adding 10 ml of N-methylpyrrolidone to each 10 ml of the reaction mixture and measuring the viscosity of this sample solution at 23 ° C. using a plate-cone viscometer. As soon as the sample solutions obtained according to this procedure have a viscosity of 5 dPas (after about 5 hours), the reaction is stopped by adding 54 g of butanol. Then 38 g of dimethylethanolamine and 3254 g of deionized water are added to the reaction product obtained within 2 hours with vigorous stirring. Finally it will be performed.
- the resulting aqueous polyurethane resin dispersion has a solids content of 27% by weight.
- trimellitic anhydride After cooling to 180 ° C., 768 parts by weight of trimellitic anhydride are added and further esterification is carried out until an acid number of 30 is reached. It is then cooled to 120 ° C. and dissolved in 1410 parts by weight of butanol. After cooling to 90 ° C., 16.2 parts by weight of dimethylethanolamine and then 1248 parts by weight of deionized water are slowly stirred in. A finely divided dispersion with a pH of 7.8, a non-volatile content of 60% by weight and an acid number of 30 mg KOH / g is obtained.
- component C 450 g of component C were placed together with 30 g of component F and 100 g of deionized water. Then 300 g of the iron oxide pigment (component B) were incorporated with stirring (1000 rpm). The batch was then dissolvered for 20 minutes using a laboratory dissolver (disk diameter 60 mm, number of revolutions 6000 rpm, shear rate 20 m / s). The temperature remains below 40 0C. The achieved fineness of the pigment paste was less than 10 ⁇ m. 30 g of component E were then added to adjust the pH. The properties of the paste produced in this way, as well as its varnishing, already met the requirements for automotive serial painting. However, the level of gloss of the formulation should also be increased. For this purpose, the paste prepared as described above was sheared again with an inline mixer for 60 seconds.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
Abstract
L'invention concerne une pâte pigmentaire contenant de l'eau, au moins un pigment, au moins un liant diluable dans l'eau, ainsi qu'un solvant, des agents mouillants et d'autres additifs habituels pour pâtes pigmentaires. Cette pâte pigmentaire contient (A) entre 25 et 80 % en poids d'eau désionisée, (B) entre 10 et 65 % en poids d'au moins un pigment d'oxyde de fer, (C) entre 5 et 30 % en poids d'au moins une résine polyuréthane diluable dans l'eau, (D) entre 5 et 30 % en poids d'au moins une résine polyester diluable dans l'eau, (E) entre 0,2 et 10 % en poids d'ammoniaque et/ou d'au moins une amine, (F) entre 0 et 25 % en poids d'au moins un solvant organique au moins partiellement miscible dans l'eau et (G) entre 0 et 5 % en poids d'au moins un auxiliaire de dispersion.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE1995138148 DE19538148C1 (de) | 1995-10-13 | 1995-10-13 | Wäßrige Pigmentpasten und deren Verwendung zur Herstellung von wäßrigen Lacken |
DE19538148.3 | 1995-10-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997013817A1 true WO1997013817A1 (fr) | 1997-04-17 |
Family
ID=7774767
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1996/004442 WO1997013817A1 (fr) | 1995-10-13 | 1996-10-11 | Pates pigmentaires aqueuses et leur utilisation pour produire des peintures aqueuses |
Country Status (2)
Country | Link |
---|---|
DE (1) | DE19538148C1 (fr) |
WO (1) | WO1997013817A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103937331A (zh) * | 2014-03-25 | 2014-07-23 | 浙江纳美材料科技有限公司 | 一种高保湿无voc氧化铁色浆及其制备方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2901774A1 (de) * | 1979-01-18 | 1980-07-24 | Elastogran Gmbh | Rieselfaehiges, mikrobenbestaendiges farbstoff- und/oder hilfsmittelkonzentrat auf basis eines polyurethan-elastomeren und verfahren zu seiner herstellung |
EP0184714A2 (fr) * | 1984-12-08 | 1986-06-18 | Bayer Ag | Agent de contraste magnétique coloré, son procédé de fabrication et son application |
EP0430290A2 (fr) * | 1989-12-01 | 1991-06-05 | BASF Corporation | Procédé de préparation de pâtes pigmentaires aqueuses et pâtes pigmentaires ainsi préparées |
EP0438090A1 (fr) * | 1990-01-13 | 1991-07-24 | Herberts Gesellschaft mit beschränkter Haftung | Composition liant pour la préparation de pâtes pigmentaires et compositions de revêtement aqueuses contenant ces pâtes pigmentaires |
EP0459634A2 (fr) * | 1990-05-01 | 1991-12-04 | Nippon Paint Co., Ltd. | Pâte aqueuse de pigment dispersé, procédé pour sa production et composition de peinture dérivant de celle-ci |
JPH0526794A (ja) * | 1991-07-22 | 1993-02-02 | Nippon Oil & Fats Co Ltd | 包埋用樹脂組成物 |
WO1993007191A1 (fr) * | 1991-10-10 | 1993-04-15 | Glasurit Do Brasil Ltda. | Polymerisats en emulsion diluables a l'eau, leur procede de fabrication, compositions aqueuses de revetement a base de polymerisats en emulsion, et leur utilisation comme resines a broyer et de dispersion et comme liants pour vernis a sechage physique |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4332015A1 (de) * | 1993-09-21 | 1995-03-23 | Basf Lacke & Farben | Verfahren zur Herstellung von Decklackschichten |
-
1995
- 1995-10-13 DE DE1995138148 patent/DE19538148C1/de not_active Expired - Fee Related
-
1996
- 1996-10-11 WO PCT/EP1996/004442 patent/WO1997013817A1/fr active Application Filing
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2901774A1 (de) * | 1979-01-18 | 1980-07-24 | Elastogran Gmbh | Rieselfaehiges, mikrobenbestaendiges farbstoff- und/oder hilfsmittelkonzentrat auf basis eines polyurethan-elastomeren und verfahren zu seiner herstellung |
EP0184714A2 (fr) * | 1984-12-08 | 1986-06-18 | Bayer Ag | Agent de contraste magnétique coloré, son procédé de fabrication et son application |
EP0430290A2 (fr) * | 1989-12-01 | 1991-06-05 | BASF Corporation | Procédé de préparation de pâtes pigmentaires aqueuses et pâtes pigmentaires ainsi préparées |
EP0438090A1 (fr) * | 1990-01-13 | 1991-07-24 | Herberts Gesellschaft mit beschränkter Haftung | Composition liant pour la préparation de pâtes pigmentaires et compositions de revêtement aqueuses contenant ces pâtes pigmentaires |
EP0459634A2 (fr) * | 1990-05-01 | 1991-12-04 | Nippon Paint Co., Ltd. | Pâte aqueuse de pigment dispersé, procédé pour sa production et composition de peinture dérivant de celle-ci |
JPH0526794A (ja) * | 1991-07-22 | 1993-02-02 | Nippon Oil & Fats Co Ltd | 包埋用樹脂組成物 |
WO1993007191A1 (fr) * | 1991-10-10 | 1993-04-15 | Glasurit Do Brasil Ltda. | Polymerisats en emulsion diluables a l'eau, leur procede de fabrication, compositions aqueuses de revetement a base de polymerisats en emulsion, et leur utilisation comme resines a broyer et de dispersion et comme liants pour vernis a sechage physique |
Non-Patent Citations (2)
Title |
---|
DATABASE WPI Week 7709, Derwent World Patents Index; AN 15448Y * |
PATENT ABSTRACTS OF JAPAN vol. 1, no. 48 (C - )<012> 11 May 1977 (1977-05-11) * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103937331A (zh) * | 2014-03-25 | 2014-07-23 | 浙江纳美材料科技有限公司 | 一种高保湿无voc氧化铁色浆及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
DE19538148C1 (de) | 1997-05-28 |
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