WO1999040123A2 - Verfahren zur herstellung farbstoffenthaltender, wässriger polymerisatdispersionen - Google Patents
Verfahren zur herstellung farbstoffenthaltender, wässriger polymerisatdispersionen Download PDFInfo
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- WO1999040123A2 WO1999040123A2 PCT/EP1999/000157 EP9900157W WO9940123A2 WO 1999040123 A2 WO1999040123 A2 WO 1999040123A2 EP 9900157 W EP9900157 W EP 9900157W WO 9940123 A2 WO9940123 A2 WO 9940123A2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/32—Polymerisation in water-in-oil emulsions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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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
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/101—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an anthracene dye
- C09B69/102—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing an anthracene dye containing a perylene dye
Definitions
- Dye-containing polymer dispersions based on polyurethanes are known from DE-A 195 21 500. These are also secondary dispersions with the disadvantages mentioned above.
- EP-A 566 448 describes dye-containing, aqueous polymer dispersions based on ethylenically unsaturated monomers, which are obtainable by preparing a first
- a radical, aqueous emulsion polymerization of ethylenically unsaturated monomers is carried out and the polymer dispersions thus obtained are impregnated with a solution of dyes in organic solvents.
- the polymer dispersions obtainable in this way also do not have satisfactory migration stability of the dyes.
- This document also points out that dyes that are sufficiently water-compatible can also be added during the polymerization.
- specific references to this embodiment cannot be found in the cited document. The disadvantage of this procedure is the use of larger amounts of organic solvents.
- No. 4,680,332 also recommends the impregnation of aqueous polymer dispersions with solutions of organic dyes in solvents such as toluene or chlorobenzene and the impregnation for the preparation of dye-containing polymer dispersions with oil-in-water emulsions of such dye solutions. This approach also does not lead to satisfactory products.
- DE-A 44 24 817 describes "fluorescent pigments" in which a fluorescent dye is present in solution in a polymer matrix based on crosslinked poly (meth) acrylates.
- Such polymers can be obtained by radical suspension polymerization of ethylenically unsaturated monomers which comprise at least one crosslinking monomer in the presence of the fluorescent dye.
- Such "fluorescent pigments” are characterized by a reduced tendency of the fluorescent dyes to migrate.
- sedimentation-stable polymer dispersion is not obtained in this way. Therefore, such "fluorescent pigments" are out of the question for a large number of applications, for example ink-jet processes.
- the object of the present invention is to provide a process for the preparation of dye-containing polymer dispersions, in which the polymer particles have at least one organic dye homogeneous, ie. H. contain molecularly dispersed, these polymer particles are characterized by a high migration stability of the dyes contained in them. Furthermore, this process is intended to provide access to finely divided, dye-containing, stable polymer dispersions.
- This object is achieved by a process for free-radical, aqueous emulsion polymerization, in which an oil-in-water emulsion of the monomers is used for the polymerization, the monomers having the dye in dissolved form, provided that the monomer droplets are essentially one Have a diameter ⁇ 500 nm.
- Conventional emulsion polymerization does not lead to success.
- the present invention thus relates to a process for the preparation of dye-containing aqueous polymer dispersions by free-radical, aqueous emulsion polymerization of ethylenically unsaturated monomers in the presence of initiators which form free radicals, at least some of the monomers being used in the form of an oil-in-water emulsion E1, whose disperse phase contains at least one oil-soluble dye, which is characterized in that the disperse phase of El essentially from dye-containing monomer droplets with a diameter ⁇ 500 nm is formed.
- the oil-soluble dyes also include organic optical brighteners, ie. H. organic molecules with an extensive, conjugated ⁇ -electron system which, in contrast to the ⁇ -electron system of conventional organic dyes, does not absorb radiation in the visible range but ultraviolet radiation and emits it again as bluish fluorescence (see Römpp Chemielexikon, 9th edition).
- organic optical brighteners ie. H. organic molecules with an extensive, conjugated ⁇ -electron system which, in contrast to the ⁇ -electron system of conventional organic dyes, does not absorb radiation in the visible range but ultraviolet radiation and emits it again as bluish fluorescence (see Römpp Chemielexikon, 9th edition).
- Optical brighteners for example, increase the whiteness of white substrates treated with them, such as paper or fabrics.
- the process according to the invention essentially differs from conventional emulsion polymerizations by the droplet size of the monomer emulsion to be polymerized.
- the monomer droplets in the polymerization vessel generally have diameters above 1000 nm.
- the failure of the conventional emulsion polymerization in the preparation of dye-containing polymers can presumably be attributed to the fact that in conventional emulsion polymerization the monomer droplets only serve as a reservoir for the monomers to be polymerized, while the actual polymerization reaction takes place in the aqueous dispersion medium or on the polymer particles formed in the course of the polymerization .
- the monomers which generally have a certain water solubility, diffuse from the monomer droplets to the polymerization centers (a detailed discussion of the mechanism of free-radical, aqueous emulsion polymerization can be found, for example, in A. Echte, Handbuch der Technische Polymerchemie, p. 322 to p. 345).
- the dye on the other hand, which generally does not have sufficient water solubility, remains in the monomer droplets; homogeneous incorporation of the dyes into the polymer particles is therefore not guaranteed.
- the polymerization in the monomer droplets presumably takes place in deviation from the course of polymerization outlined above. This results in a homogeneous incorporation of the dyes into the polymer matrix.
- Suitable ethylenically unsaturated monomers in the process according to the invention are in principle all monomers which can usually be used in the context of free-radical, aqueous macroemulsion polymerization.
- the majority of the monomers to be polymerized are preferably formed from monoethylenically unsaturated monomers A with a water solubility> 0.01 g / l.
- the monomers A furthermore also comprise those monomers A 'whose homopolymers have an increased solubility in water (ie> 60 g / 1 at 25 ° C.).
- Such monomers A ' serve as modifying monomers and are generally used in amounts of ⁇ 20% by weight, based on the total amount of the monomers to be polymerized, preferably ⁇ 10% by weight, for example in amounts of 0.1 to 20% by weight. -%, based on the monomers to be polymerized.
- the amount of monomers A ' based on the total amount of monomers, can be up to
- monoethylenically unsaturated anionic monomers A 'are 3 to 6 carbon atoms, monoethylenically unsaturated mono- and dicarboxylic acids e.g. As acrylic acid, methacrylic acid, maleic acid, itaconic acid, acrylamidoglycolic acid, methacrylamidoglycolic acid, acryloyloxyglycolic acid, methacryloyloxyg
- vinyl sulfonic acid allylsulfonic acid, methallylsulfonic acid, styrene sulfonic acid, vinylnaphthalenesulfonic acid and (meth) acrylamido-2-methylpropanesulfonic acid, further vinylphosphonic acid, allylphosphonic acid, methallylphosphonic acid, styrenephosphonic acid, and (meth) acrylamido-2-methylpropanephosphonic acid, and their water-soluble salts, e.g. B. their alkali metal salts or their ammonium salts, especially their sodium salts.
- the quaternization products of 1-vinylimidazoles are also referred to below as vinylimidazolium salts, the quaternization products of aminoalkyl acrylates or methacrylates as (meth) acrylic loyloxyalkyl ammonium salts.
- the monomers to be polymerized also comprise those monomers B which have a water solubility ⁇ 0 , 01 g / 1 (at 25 ° C and 1 atm).
- the ethylenically unsaturated monomers to be polymerized preferably comprise at least 50 to 99.5% by weight, based on the total amount of monomers A and B, in particular 80 to 99% by weight and very particularly preferably 90 to 98% by weight of a monomer A and 0.5 to 50% by weight, in particular 1 to 20% by weight and very particularly preferably 2 to 10% by weight, of at least one monomer B.
- Examples of monomers B which have a low water solubility as required above are 2- and 4-n-butylstyrene, p-tert-butylstyrene, esters of 3 to 6 carbon atoms containing ⁇ , ⁇ -monoethylenically unsaturated carboxylic acids and ⁇ 12 C atoms (usually up to 30 C atoms) containing alkanols such as B. lauryl acrylate and stearyl acrylate. But also esters from vinyl alcohol or allyl alcohol and ⁇ 9 carbon atoms (usually up to 30 carbon atoms) containing alkane carboxylic acids, such as. B.
- VEOVA® 9-11 VEOVA X is a trade name of Shell and stands for vinyl esters of carboxylic acids, which are also referred to as Versatic® X acids), are such monomers B.
- macromonomers such as oligopropene acrylate are also such monomers B (very generally, macromonomers are polymeric or oligomeric compounds which have at least one, mostly terminal, ethylenically unsaturated double bond; their relative number-average molecular weight should preferably not be more than 100,000 for use as the least water-soluble monomer B; this will generally be relative number average molecular weights are 1,000 to 50,000 or 2,000 to 50,000; macromonomers are known to the person skilled in the art; their preparation is described, for example, in Makromol. Chem. 223 (1994) pp. 29 to 46).
- the least water-soluble monomers B are all those whose molar solubility at 25 ° C.
- Such monomers B are e.g. B. also the methacryloyl polybutyl acrylate AB-6 and the methacryloyl polystyrene A5-6 from Toa Gosei Kagaku KK (JP), both of which have a number average relative molecular weight of 6000.
- Polyol 130 and Polyol 110 from Hüls AG (stereospecific, low-viscosity polybutadiene (75% 1,4-cis, 24% 1,4-trans, 1% vinyl), whose dynamic viscosity at 20 ° C is 3000 mPa-s) form compounds B which can be used as macromonomers with low water solubility
- the stability of the emulsion E1 can also be improved by using non-copolymerizable compounds B 'with a water solubility ⁇ 0.01 g / 1.
- Such compounds B ' can be used together with the monomers B or instead of the monomers B.
- Compounds B ' are preferably used in amounts less than 10% by weight, based on the total amount of monomers A and B.
- Acronal® A 150 F a poly-n-butyl acrylate from BASF AG, whose 50% strength by weight solution in ethyl acetate at 23 ° C. and 1 atm has a viscosity (determined according to ISO 3219, DIN 53019, at 250 S " 1 ) of 33 mPa-s.
- PnBa a high-temperature solution polymer of n-butyl acrylate (120 ° C. in isopropanol) with a K value of 24 at 25 ° C. in isopropanol
- the K value is a relative viscosity number that is determined in analogy to DIN 53726. It contains the flow rate of the pure solvent relative to the flow rate of the 0.1% by weight solution of the polymer in the same solvent (see also Cellulose Chemistry, Vol. 13 (1932), Pp. 58-64, and Kirk-Othmer Encyclopedia of Chemical Technology, vol. 23, pp. 967-968).
- the K value is a measure of the average molecular weight of a polymer. A high K value corresponds to a high average molecular weight.
- the monomers to be polymerized also comprise crosslinking monomers C.
- These are in particular monomers C which have at least 2 non-conjugated double bonds. If desired, such monomers C are present in an amount of 0.1 to 30% by weight, based on the total amount of the monomers to be polymerized, in particular 0.5 to 20% by weight and very particularly preferably 1 to 10% by weight. -%, used.
- Suitable monomers C include e.g. B. the vinyl, allyl and methyl allyl esters of the above-mentioned ethylenically unsaturated carboxylic acids as well as the esters of these acids with tricyclodecenyl alcohol, in particular the esters of methacrylic acid and acrylic acid, the esters of the above-mentioned ethylenically unsaturated
- Carboxylic acids with polyhydric alcohols such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, triethylene glycol diacrylate, trieethylene glycol trimethacrylate, triethylene glycol and triethyl acrylate, triethyl acrylate, triethyl acrylate, triethyl acrylate, triethyl acrylate, triethyl acrylate, triethyl acrylate, triethyl acrylate, triethyl acrylate, and and methallyl esters of polyfunctional carboxylic acids, such as diallyl maleate, diallyl fumarate, diallyl phthalate.
- polyhydric alcohols such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, but
- Typical monomers C are also compounds such as divinylbenzene, divinylurea, diallylurea, triallylcyanurate, N, N'-divinyl and N, N'-diallylimidazolidine-2-one, and also methylenebisacrylamide and methylenebismethacryla- id.
- the anhydrides monomers C can also be mono- ethylenically unsaturated carboxylic acids, such as methacrylic acid anhydride, are used.
- monoethylenically unsaturated monomers D which, instead of the at least one further ethylenically unsaturated bond, have a functional group which is used for the subsequent crosslinking of the polymer or for a reaction with a functional group of the dye does not belong to the chro ophor of the dye.
- Such functional groups are usually selected from epoxy, hydroxy, N-methylol or carbonyl groups.
- monomers D are N-alkylolamides of the above-mentioned ethylenically unsaturated carboxylic acids, e.g. B.
- vinyl, allyl and methallyl trimethoxysilane further acrylic, oxyalkyl and methacryloxyalkyltrialkoxysilanes such as methacryloxypropyltrimethoxysilane and methacryloxypropyltriethoxysilane, and also ⁇ -mercaptoalkyltrialkoxysilanes, such as 3-mercaptopropyltrimethoxysilane.
- Such compounds also belong to the crosslinking monomers D and can be polymerized in amounts of up to 20% by weight, in particular up to 10% by weight, based on the total amount of the monomers to be polymerized.
- alkyl is to be understood to mean both linear or branched alkyl which, if indicated, can be interrupted by one or more non-adjacent oxygen atoms, sulfur atoms, imino groups or alkylimino groups and / or can be substituted one or more times by halogen or hydroxyl.
- unsubstituted alkyl groups include methyl, ethyl, n-propyl, i-propyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert.
- -Pentyl hexyl, 2-methylpentyl, heptyl, 1-ethylpentyl, n-octyl, 2-ethylhexyl, isooc- tyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl , Hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl.
- alkyl groups interrupted by oxygen include 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-isopropoxypropyl, 2- or 3-isopropoxypropyl, 2- or 3-butoxypropyl, 2- or 3- (2-ethylhexyloxypropyl) etc.
- Halogen-substituted alkyl groups include in particular perfluoroalkyl groups with 1 to 4 carbon atoms, such as trifluoromethyl.
- hydroxy-substituted alkyl groups are hydroxymethyl, 1- or 2-hydroxyethyl, 1-, 2- or 3-hydroxypropyl, 1,2-bishydroxyethyl.
- Aryl is understood to mean, in particular, phenyl or naphthyl, which is optionally substituted by 1, 2 or 3 substituents, selected from C 1 -C 4 -alkyl, C 1 -C 4 alkyloxy, halogen, hydroxy, which may optionally also be ethoxylated.
- Arylalkyl stands for aryl which is bonded by an alkylene group which preferably has 1 to 6 and in particular 1 to 4 carbon atoms. Examples of -CC 4 alkylene include methylene, 1,1-ethylene, 1,2-ethylene, 1,1-propylene, 1,2-propylene, 2,2-propylene, 1,3-propylene and 1,4-butylene. Examples of arylalkyl include in particular benzyl and 2-phenylethyl, which are optionally also substituted.
- cycloalkyl examples include aliphatic monocycles such as cyclopentyl, cyclohexyl and cycloheptyl and aliphatic polycycles such as norbornyl, adamantyl or decahydronaphthyl, which can be substituted like aryl.
- Heterocycloalkyl means aliphatic mono- and polycyclic radicals which have at least one heteroatom, e.g. S, 0 and / or N, in the ring. Examples include pyrrolidinyl, furanyl, piperidinyl, oxazolidinyl, morpholinyl and tetrahydropyranyl.
- Heteroaryl is understood to be residues which are derived from optionally substituted or benzannelated heteroaromatics such as thiophene, pyrrole, pyrazole, imidazole, oxazole, thiazole, pyridine, pyrimidine, pyridazine, triazine, quinoline, quinazoline and the like. derive.
- the organic, oil-soluble dyes are selected, for example, from oil-soluble derivatives of naphthalene, perylene, terrylene, quarterrylene, diketopyrrolopyrrole, perinone dyes, coumarin dyes, oxazine dyes, anthracene dyes, naphthacen dyes, methine dye, anthrachine dyes, anthrachine dyes Azamethine dyes, isoindoline and isoindolinone dyes, porphyrins, phthalocyanines and naphthalocyanines, as well as the metal complexes of the last three classes of dyes.
- the oil-solubility of the dye means that the dye is at least partially soluble in the monomers to be polymerized, so that it is dissolved in the monomers under polymerization conditions or, if appropriate, molecularly dispersed (ie homogeneously in the form of bi- or higher-molecular aggregates) distributed in the monomer phase) is present.
- Suitable oil-soluble copper aryne dyes are described, for example, in US Pat. No. 3,880,869 and DE-A 44 24 817, to which reference is hereby made in full.
- Suitable non-polar perylene dyes are, for example, those as described in US Pat. No. 4,618,694, DE-A 24 51 782, US-A 379 934, US-A 4 446 324, EP-A 277 980, EP -A 657 436 or WO 96/22332. Further suitable non-polar perylene dyes can be found, for example, in EP-A 73 007. Reference is hereby made in full to the publications mentioned.
- Suitable naphthalene dyes include naphthalene-1,8-dicarboximides which are substituted on the imide nitrogen with unsubstituted, linear or branched C 1 -C 20 -alkyl or aryl, and which are in the 4- and / or the 5-position of the naphthalene ring can have -C 6 alkoxy substituents.
- Suitable anthracene dyes include 9,10-diphenylanthracene, 9, 10-bisphenylethynylanthracene, 1, 8-dichloro-9, 10-bisphenylethynylanthracene.
- suitable anthracene dyes can be found, for example, in Ullmann's Ecyclopedia of Industrial Chemistry, 5th Edition, Vol. A2, p. 402 f. remove.
- Suitable porphyrin dyes include, for example, tetraphenylporphyrin and octaethylporphyrin and their zinc or nickel complexes.
- R 1 represents an alkyl radical, in particular a C 1 -C 13 alkyl radical
- R 2 represents a hydrogen atom or a cyano group and R 3 represents a Ci-Cu alkyl group;
- R 4 is Cs-C 2 o-alkyl, which is optionally interrupted by one or more non-adjacent oxygen atoms, or phenyl which is optionally substituted by C ⁇ -Ci 3 -alkyl or C 1 -C 13 -alkoxy. or multiply substituted, and R 5 and R 6 are independently hydrogen, chlorine, bromine, phenoxy or by halogen, cyano, C 4 alkyl or C 1 -C 4 -alkoxy-substituted phenoxy;
- Suitable optical brighteners from the class of coumarins obey e.g. B. the formula
- a 6 is phenyl or 3-halopyrazol-l-yl, in particular 3-chloropyrazol-l-yl.
- dyes which have at least one copolymerizable, ethylenically unsaturated double bond which does not belong to the chromophore of the dye.
- these are dyes which are represented by the general formula I
- X ' is selected from -0-; -NO)-; -S-; -O-C (O) -?
- R stands for Hydrogen, linear or branched C ⁇ -C 6 -alkyl, aryl, aryl-C ⁇ -C 6 -alkyl, Ci-C ⁇ -alkylcarbonyl, arylcarbonyl or formyl and R ', R''independently of one another for hydrogen, linear or branched
- a and B independently of one another represent hydrogen, C ⁇ -C 6 -alkyl, phenyl or A and B together with the double bond to which they are attached form a cyclopentene or cyclohexene ring,
- Q stands for the chromophore of an organic dye.
- S is preferably selected from a single bond, C ⁇ -C ⁇ 2 alkylene, especially C ⁇ -C 6 alkylene, 1,2-, 1,3- or 1,4-phenylene.
- Q is preferably derived from one of the dyes mentioned above, in particular from perylene dyes.
- P stands for vinyl, allyl, methallyl, acrylamido, methacrylamido, acryloxy, methacryloxy, 3-vinylureido, 3-allylureido, 3-methallylureido, N-vinylaminocarbonyloxy, N-allylaminocarbonyloxy or N-methallylcarbonyloxy.
- Copolymerizable dyes of the general formula I are known in principle.
- EP-A-090 282 and EP-A-260 687 describe copolymerizable anthraquinone dyes of the general formula I.
- EP-A-090 282 also discloses copolymerizable azo dyes.
- copolymerizable perylene dyes of the general formula III are particularly preferred embodiments of the present invention.
- Dyes of the general formula III in which X 1 together with X 4 for a group of the general formula V as defined above and X 2 together with X 3 for a group of the general formula -C (0) -N (R "' ) -C (0) - are known from US-A-4, 667,036 and EP-A-422 535. These dyes are suitable for the process according to the invention, but their accessibility is due to the asymmetrical substitution pattern and the resultant result limited manufacturing.
- Dyes of the general formula III with the exception of those dyes in which X 1 together with X 4 for a group of the general formula V and X 2 together with X 3 for a group of the general formula -C (0) -N (R ''') -C (0) - are new and are also the subject of the present invention.
- X 1 and X 4 either form a group of the general formula V as defined above (dyes purple) or a group of the formula -C (0) -N (R "') -C (0) - (Dyes Illb).
- the remaining groups X 2 and X 3 preferably preferably have a meaning different from -XSP and are in particular selected independently of one another from hydrogen, linear or branched C ⁇ -C ⁇ 2 alkyl, which may be one or more, not adjacent Oxygen- atoms, sulfur atoms or interrupted by (alkyl) imino groups and / or substituted by halogen, alkyloxy, optionally substituted aryl or aryloxy or halogen.
- Y 1 to Y 4 have one of the abovementioned meanings different from XSP in the dyes purple.
- one of the groups X 2 or X 3 preferably represents a group -XSP.
- the remaining group X 2 or X 3 then has one of the abovementioned meanings which differ from XSP.
- X 1 , X 3 and X 4 are independently selected from hydrogen, linear or branched C ⁇ -C ⁇ 2 alkyl, which may be interrupted by one or more non-adjacent oxygen atoms, sulfur atoms or by (alkyl) imino groups and / or by OH and / or can be substituted by halogen, alkyloxy, cycloalkyl, cycloalkyloxy, C 2 -C 6 alkynyl,
- Y 1 to Y 4 have the meanings given above, different from -XSP (dyes IIIc).
- a fourth class of dyes of the general formula III relates to those dyes in which both X 1 with X 4 and X 2 with X 3 represent a group of the general formula V as defined above (dyes Illd).
- the known perylene derivatives are usually converted into conventional methods, for example by esterification or amino
- R f stands for a functional group which can be converted into a polymerizable group P or for the formation of a chemical bond with an ethylenically unsaturated compound W which has a reactive complement to R f
- aprotic solvent eg. B. in an aliphatic or cycloaliphatic ether, an aromatic hydrocarbon or in a nitrogen-containing solvent such as pyridine, quinoline or N-methylpyrrolidone.
- the reaction of the acid chlorides is preferably carried out in the presence of a base.
- bases are trialkylamines, such as triethylamine, tripropylamine, tributylamine, and also diazabi- cyclooctane and diazabicycloundecene.
- the ratio of base to acid chloride is usually chosen to be equimolar.
- Compounds of the general formula VI can also be subjected to an asymmetric aryl / aryl coupling with aryl boronic esters in the presence of palladium (O) compounds.
- the arylboronic acids can advantageously already contain a copolymerizable double bond, since this is not attacked under coupling conditions. Examples of suitable arylboronic acids with copolymerizable double bonds are o-, m- and para-styrene boronic acids.
- the arylboronic acids can of course also have functionalities R f which, if appropriate after chemical modification, can be reacted with an ethylenically unsaturated compound W to give the desired end product of the general formula III.
- Suitable bases are alkali metal hydroxides and carbonates.
- Suitable organic solvents are alkyl aromatics such as toluene or xylenes.
- X 2 , X 3 and Y 1 to Y 4 have the abovementioned meanings different from -XSP, with a primary amine which carries an ethylenically unsaturated double bond, for. B. allylamine, or with a primary amine, which has a further reactive group R f (see above), and then the reactive
- the average size of the droplets of the disperse phase of the aqueous emulsion E 1 to be used according to the invention can be determined according to the principle of quasi-elastic dynamic light scattering (the so-called z-average droplet diameter d z of the unimodal analysis of the autocorrelation function).
- a Coulter N4 Plus Particle Analyzer from Coulter Scientific Instruments was used (1 bar, 25 ° C.). The measurements were carried out on dilute aqueous emulsions E1, the content of non-aqueous components of which was 0.01% by weight.
- the dilution was carried out using water which had previously been contained in the aqueous emulsion monomers had been saturated. The latter measure is intended to prevent the droplet diameter from changing as a result of the dilution.
- the values for d 2 thus determined for the emulsions E1 are normally 500 500 nm, frequently hearing 400 nm.
- the d z range from 100 nm to 300 nm or from 100 nm to 200 nm is favorable.
- d 2 of the aqueous emulsion El 40 40 nm to be used according to the invention are normally 500 500 nm, frequently cord 400 nm.
- the macroemulsion is then converted into emulsion El (hereinafter also referred to as mini-emulsion) by known processes (cf. PL Tang, ED Sudol, CA. Silebi and MS El-Aasser in Journal of Applied Polymer Science, Vol. 43, pp. 1059-1066 [1991]).
- High-pressure homogenizers for example, can be used for this purpose.
- the fine distribution of the components in these machines is achieved through a high local energy input.
- Two variants have proven particularly useful in this regard.
- the aqueous macroemulsion is compressed to over 1000 bar using a piston pump and then expanded through a narrow gap.
- the effect here is based on the interplay of high shear and pressure gradients and cavitation in the gap.
- An example of a high-pressure homogenizer that works on this principle is the Niro-Soavi high-pressure homogenizer type NS1001L Panda.
- the compressed aqueous macroemulsion is expanded into a mixing chamber via two opposing nozzles.
- the fine distribution effect depends primarily on the hydrodynamic conditions in the mixing chamber.
- An example of this type of homogenizer is the M 120 E microfluidizer from Microfluidics Corp.
- the aqueous macroemulsion is compressed to a pressure of up to 1200 atm by means of a pneumatically operated piston pump and expanded via a so-called "interaction chamber”.
- the emulsion jet is divided into two jets in a microchannel system, which are brought together at an angle of 180 °.
- Another example of a homogenizer working according to this type of homogenization is the Nanojet type Expo from Nanojet Engineering GmbH. However, instead of a fixed duct system, the Nanojet has two homogenizing valves that can be mechanically adjusted.
- homogenization can, for. B. also by using ultrasound (z. B. Branson Sonifier II 450).
- the fine distribution here is based on cavitation mechanisms.
- the devices described in GB 22 50 930 A and US Pat. No. 5,108,654 are also suitable for homogenization by means of ultrasound.
- the quality of the aqueous emulsion El produced in the sound field depends not only on the sound power introduced, but also on other factors, such as. B. the intensity distribution of ultrasound in the mixing chamber, the residence time, the temperature and the physical properties of the substances to be emulsified, for example on the toughness, the interfacial tension and the vapor pressure.
- the resulting droplet size depends, among other things. from the concentration of the emulsifier and from the energy introduced during the homogenization and is therefore z.
- the device described in the older German patent application DE 197 56 874.2 has proven particularly useful for producing the emulsion E1 from conventional emulsions by means of ultrasound.
- This is a device which has a reaction space or a flow-through reaction channel and at least one means for transmitting ultrasound waves to the reaction space or the flow-through reaction channel, the means for transmitting ultrasound waves being designed in such a way that the entire reaction space or the flow-through reaction channel can be irradiated uniformly with ultrasonic waves in one section.
- the radiation surface of the means for transmitting ultrasound waves is designed such that it essentially corresponds to the surface of the reaction space or, if the reaction space is a partial section of a flow-through reaction channel, extends essentially over the entire width of the channel, and that the depth of the reaction space, which is essentially perpendicular to the radiation surface is less than the maximum depth of action of the ultrasound transmission means.
- depth of the reaction space essentially means the distance between the radiation surface of the ultrasound transmission means and the floor of the reaction space.
- Reaction chamber depths of up to 100 mm are preferred.
- the depth of the reaction space should advantageously not be more than 70 mm and particularly advantageously not more than 50 mm.
- the reaction spaces can also have a very small depth, but in view of the lowest possible risk of clogging and easy cleaning and a high product throughput, reaction space depths are preferred which are considerably larger than, for example, the usual gap heights in high-pressure homogenizers and are usually over 10 mm .
- the depth of the reaction space can advantageously be changed, for example by means of ultrasound transmission means which are immersed at different depths in the housing.
- the radiation surface of the means for transmitting ultrasound corresponds essentially to the surface of the reaction space.
- This embodiment is used for batch production of emulsions El.
- ultrasound can act on the entire reaction space.
- a turbulent flow is generated in the reaction chamber by the axial sound radiation pressure, which causes intensive cross-mixing.
- such a device has a flow cell.
- the housing is designed as a flow-through reaction channel which has an inflow and an outflow, the reaction space being a partial section of the flow-through reaction channel.
- the width of the channel is the channel extension which is essentially perpendicular to the direction of flow.
- the radiation area covers the entire width of the flow channel transverse to the flow direction.
- the length of the radiation surface perpendicular to this width that is to say the length of the radiation surface in the flow direction, defines the effective range of the ultrasound.
- the flow-through reaction channel has an essentially rectangular cross section. If a likewise rectangular ultrasound transmission medium with corresponding dimensions is installed in one side of the rectangle, a particularly effective and uniform sound system is guaranteed.
- Transmission means can be used without disadvantages.
- a single ultrasound transmission means instead of a single ultrasound transmission means, several separate transmission means can be arranged, which are connected in series as seen in the direction of flow. Both the radiation surfaces and the depth of the reaction space, that is to say the distance between the radiation surface and the bottom of the flow channel, can vary.
- the means for transmitting ultra-sound waves is particularly advantageously designed as a sonotrode, whose end facing away from the free radiation surface is coupled to an ultrasonic transducer.
- the ultrasonic waves can be generated, for example, by using the reverse piezoelectric effect.
- generators high-frequency electrical vibrations (usually in the range from 10 to 100 kHz, preferably between 20 and 40 kHz) are generated, converted into mechanical vibrations of the same frequency via a piezoelectric transducer, and coupled into the medium to be sonicated using the sonotrode as a transmission element .
- baffles are provided in the reaction space to improve the flow and mixing behavior.
- These internals can be, for example, simple baffles or a wide variety of porous bodies.
- the mixing can also be further intensified by an additional agitator.
- the reaction space can advantageously be temperature-controlled.
- all water-soluble emulsifiers customary for free-radical aqueous macroemulsion polymerization can be used to carry out the process according to the invention. These are both anionic, cationic and nonionic emulsifiers. Anionic and / or nonionic emulsifiers are preferably used.
- Suitable neutral emulsifiers are ethoxylated mono-, di- and tri-alkylphenols (EO grade: 3 to 50, alkyl radical: C 4 to C 9 ), ethoxylated fatty alcohols (EO degree: 3 to 50, alkyl radical: C 8 to C 36 ) and ethoxylated oxo alcohols (EO grade: 3 to 50, alkyl radical: Cg to C 36 ).
- anionic emulsifiers are the alkali metal and ammonium salts of di-C 4 -C 2 o-alkyl esters of sulfosuccinic acid, in particular the di-n-octyl esters and the di-2-ethylhexyl esters.
- anionic emulsifiers are the salts of bis (phenylsulfonyl) ethers which have a C 4 -C 24 -alkyl group on at least one phenylsulfonyl group.
- the alkyl group which can be linear or branched, preferably has 6 to 18 carbon atoms and in particular 6, 12 or 16 carbon atoms.
- the sodium salts are particularly preferred.
- the sodium salts are particularly advantageous if they have at least one alkyl group with 12 C atoms and are branched.
- Technical mixtures are frequently used which have a proportion of 50 to 90% by weight of the monoalkylated product, for example Dowfax® 2A1 (trademark of the Dow Chemical Company).
- the compounds mentioned are generally known, for. B. from US-A 4,269,749, and commercially available.
- emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg-Thieme Verlag, Stuttgart, 1961, pages 192 to 208 and in Ulimann's Encyclopedia of Industrial Chemistry, 5th ed., VCH Weinheim 1987, Vol. 9a, pp. 313-318.
- the emulsifiers mentioned can of course also be used in a mixture with protective colloids.
- Protective colloids are water-soluble, organic polymers. These are able to barely reduce the voltage of water and, in contrast to emulsifiers, generally have relative molecular weights above 1000, preferably above 2000.
- anionic protective colloids are, for example, homopolymers and copolymers of the aforementioned monoethylenically unsaturated monomers A ', which have at least one acid group, and the salts, in particular the alkali metal and ammonium salts, of such homopolymers and copolymers.
- Homo- and copolymers of acrylic acid, methacrylic acid, maleic acid, styrene sulfonic acid and / or 2-acrylamido-2-methylpropanesulfonic acid are preferred, optionally with neutral comonomers, which are selected, for example, from olefins such as ethylene, propene, 1-butene , Isobutene and diisobutene, vinyl aromatics such as styrene, esters of acrylic acid or methacrylic acid, hydroxyalkyl esters of acrylic acid or methacrylic acid, acrylamide, methacrylamide, vinyl acetate and acrylonitrile, and their salts.
- Anionic protective colloids are also anionically modified starches and lignin sulfonates.
- cationic protective colloids are the homopolymers and copolymers of monoethylenically unsaturated cationic monomers, for example homopolymers and copolymers of quaternized N-vinylimidazoles or of quaternized dialkylaminoalkyl acrylates and methacrylates with, for example, N-vinylpyrrolidone and / or N-vinylcaprolactam. This also includes cationically modified starches.
- Neutral protective colloids are, for example, polyvinyl alcohols, partially saponified homo- and copolymers of vinyl acetate, ethylene oxide-propylene oxide block copolymers, modified starches, cellulose derivatives, polyvinylpyrrolidone and copolymers of vinylpyrrolidone with neutral monomers, for. B. with vinyl caprolactam, vinyl acetate, acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-butyl acrylate or with methyl methacrylate.
- a preferred embodiment of the process according to the invention consists in placing the total amount of emulsion E1 in the polymerization vessel.
- the polymerization is started, for example, by adding at least part of the initiator and then heating to the polymerization temperature.
- the remaining amount of initiator is then added continuously, in portions or all at once to the polymerization reaction.
- the mixture is first heated to the polymerization temperature and then the initiator is added in the manner described above.
- Water-soluble initiators which comprise at least one nonionic peroxide, in particular hydrogen peroxide, have proven to be particularly advantageous. Such initiators are often used together with at least one of the aforementioned reducing agents (redox initiators). Examples of such combinations are e.g. B. hydrogen peroxide / sodium salt of hydroxymethanesulfinic acid, tert-butyl hydroperoxide / sodium salt of hydroxymethanesulfinic acid and hydrogen peroxide / ascorbic acid.
- the aforementioned nonionic initiators can also be used without a reducing agent. In this case, one of the aforementioned water-soluble, redox-active metal compounds is preferably added to the polymerization medium.
- the actual polymerization reaction is carried out in such a way that at least part of the aqueous emulsion E1 is fed continuously as feed I and the conventional emulsion E2, in parallel or in portions, during feed I of the polymerization reaction.
- the conventional emulsion E2 preferably contains no compounds whose water solubility is ⁇ 0.01 g / 1 and, in particular, no dye.
- the dye-containing, aqueous polymer dispersions obtainable according to the invention are in particular superior to the known dye-containing polymer dispersions when the polymer matrix is selected from at least one monoethylenically unsaturated monomer A with a water solubility> 0.01 g / 1 and at least one further monomer
- Dye-containing, aqueous polymer dispersions with superior properties are also obtained if, according to the process of the invention, the above-mentioned monomers A with a water solubility> 0.01 g / 1 and, if appropriate, the monomers B, C and D together with an oil-soluble, organic color Polymerized material that has at least one copolymerizable functional group that does not belong to the chromophore of the dye.
- Such polymer dispersions are also the subject of the present invention.
- the polymer matrix is preferably made of 50 to 99.5% by weight, in particular 80 to 99% by weight and very particularly preferably 90 to 98% by weight of monomers A, 0.5 to 50% by weight, in particular 1 to 20% by weight and very particularly preferably 2 to 10% by weight of monomers B, 0 to 30% by weight, in particular 0.5 to 20% by weight and very particularly preferably 1 to 10% by weight of monomers C, and up to 30 % By weight, preferably up to 20% by weight and in particular up to 10% by weight of monomers D
- the total amount of monomers C and D preferably not exceeding 30% by weight and in particular 10% by weight, based on the total amount of monomers. If the oil-soluble dye used does not have a copolymerizable, functional group, one will preferably choose a polymer matrix which contains the monomers C and / or D in amounts of at least
- the polymer matrix has 0.5 to 20% by weight, particularly preferably 1 to 15% by weight, of monomers C, and among these particularly preferably divinylbenzene, butanediol diacrylate, butanediol dimethacrylate, hexanediol diacrylate, hexanediol dimethacrylate, triethylene glycol diacrylate and triethylene glycol, glycol dimethyl and no monomers D.
- a preferred embodiment of the dye-containing polymer dispersions according to the invention are those polymer dispersions which have a copolymerizable dye, and among them those whose polymer matrix in copolymerized form also has monomers C and / or D.
- the dye-containing, aqueous polymer dispersions according to the invention can be designed such that the polymer matrix of the dye-containing polymer does not contain copolymerized monomers A '.
- Such dispersions are particularly suitable for obtaining dye-containing polymers that are to be incorporated into non-polar media, for example as a color-imparting component in printing inks, alkyd resin lacquers, eg. B. melamine-alkyd resin stoving lacquers, or staining of plastic fibers or plastic compositions.
- the monomers A copolymerized in the polymer matrix of the polymer particles comprise: 0.5 to 30% by weight, in particular 1 to 20% by weight and especially 2 to 15% by weight, of at least one monomer Al with a water solubility> 60 g / 1 (in each case at 25 ° C. and 1 atm) and,
- the monomers AI also include the hydroxyalkyl esters of ethylenically unsaturated carboxylic acids, in particular acrylic acid and methacrylic acid, such as hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxybutyl acrylate, and the N-alkylolamides of ethylenically unsaturated carboxylic acids.
- hydroxyalkyl esters of ethylenically unsaturated carboxylic acids in particular acrylic acid and methacrylic acid, such as hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxybutyl acrylate, and the N-alkylolamides of ethylenically unsaturated carboxylic acids.
- the monomers AI preferably comprise either at least one of the monoethylenically unsaturated cationic monomers listed under A 'or at least one of the monoethylenically unsaturated monomers listed under A' with at least one acid group, optionally in deprotonated form, the latter being preferred.
- the monomers AI are acrylic acid, methacrylic acid and acrylamido-2-methylpropane sulfonate, for. B. preferred as ammonium or sodium salt.
- the dye-containing polymer particles of the dispersion have a monomodal distribution of their particle sizes.
- the distribution of the polymer particle sizes in the dispersion such as results, for example, from light scattering experiments or from determination of the polymer particle size by means of an ultracentrifuge, has a pronounced maximum with a particle size. As a rule, this maximum will be at a value ⁇ 1000 nm.
- the polymer particles have z-average particle diameters d 2 (determined by quasi-elastic, dynamic light scattering, see above) in the range from 100 to 400 nm, in particular 100 to 300 nm and very particularly preferably 100 to 200 nm.
- the particle sizes of the polymer particles are narrowly distributed, ie the ratio of the full width at half maximum of the distribution curve of the polymer particle sizes as determined by dynamic light scattering to the average particle diameter d z generally has values of ⁇ 1, preferably ⁇ 0.75 and in particular ⁇ 0 , 5 on.
- the glass transition temperature of the polymer matrix T G is at least 60 ° C.
- the glass transition temperature here and below is the "mid-point temperature" determined according to ASTM-D 3418-82 by means of DTA.
- polymer dispersions according to the invention can be converted into polymer powder in a customary manner by conventional drying methods, for example by freeze drying or preferably by spray drying. Such polymer powders are also the subject of the present invention.
- Spray drying for example, is carried out by spraying the polymer dispersions to be dried in a conventional drying tower in a stream of warm air.
- the inlet temperature of the warm air flow is in the range from 100 to 200 ° C., preferably 120 to 160 ° C.
- the outlet temperature of the warm air flow is in the range from 30 to 90 ° C. and preferably 60 to 80 ° C.
- the aqueous polymer dispersion can be sprayed in a hot air stream, for example by means of single or multi-substance nozzles or via a rotating disk.
- the polymer powders are normally separated off using cyclones or filter separators.
- the sprayed, aqueous polymer dispersion and the hot air stream are preferably conducted in parallel.
- the polymer dispersions according to the invention are preferably dried in the presence of customary drying aids.
- customary drying aids are: polyvinyl alcohols (see, for example, EP-A-56 622, EP-A-680 993, DE-A-22 14 410 and DE-A-26 14 261), polyvinylpyrrolidones (see, for example, DE 22 38 903 and EP 576 844), phenolsulfonic acid-formaldehyde condensates (see, for example, EP-A 407 889, WO 98/03576), naphthalenesulfonic acid-formaldehyde condensates (see, for example, WO 98/03577), homopolymers and copolymers 2-acrylamido-2-methylpropanesulfonic acid (see, for example, EP-A 629 650, EP-A 671 435 and DE-A 195 39 460), copolymers of ethylenically unsaturated carb
- EP 467 103) or olefins see, for example, EP 9 169) or with hydroxyalkyl esters (see, for example, JP 59 162 161).
- the water-soluble polymers PW mentioned below can also be used as drying aids.
- Anti-caking agents, such as highly disperse silica, can also be used.
- the dye-containing, aqueous polymer dispersions according to the invention and the polymer powders obtainable therefrom by drying are particularly suitable as a coloring component in aqueous dye-containing preparations, for example for inks, in particular in inks for paper and textile inkjet printing.
- the dye-containing polymer particles serve as a replacement for pigment particles in conventional, aqueous pigment-containing preparations.
- the present invention also relates to aqueous, dye-containing preparations comprising:
- At least one dye-containing polymer according to the invention which is present in the preparation in the form of dispersed polymer particles and which is selected from the polymers contained in the aqueous, dye-containing polymer dispersions according to the invention and the polymer powders prepared therefrom, and
- aqueous, dye-containing preparations in particular on the inks used in the ink jet process (ink jet printing processes such as thermal ink jet, piezo ink jet, continuous ink jet, valve jet)
- Printing has a suitable viscosity and surface tension, it must be stable in storage, ie it should not coagulate or flocculate and the dispersed, undissolved colorant should not settle, it must not clog the printer nozzle, which is the case with pigment-containing, ie dispersed colorant particles containing inks can be problematic.
- the continuous ink jet they have to be stable against the addition of conductive salts and have no tendency to increase when the ion content is increased Show flakes.
- the prints obtained must meet the color requirements, ie show high brilliance and depth of color, and good fastness properties, e.g. B. Rub fastness, light fastness, water fastness and wet rub fastness, even on uncoated papers.
- Water-soluble polymers PW are to be understood in principle as those polymers which are completely soluble in the chosen amount in the aqueous dispersion medium of the aqueous, dye-containing preparation according to the invention. In principle, all polymers which are already mentioned as protective colloids or as drying aids are suitable as water-soluble polymers PW. Ionic polymers PW are preferred.
- the preferred ionic polymers PW either have cationic functional groups, in particular quaternary ammonium groups or imonium groups, or acidic functional groups, preferably in deprotonated form (i.e. anionic groups).
- Preferred polymers PW with cationic functional groups are copolymers which are composed of at least one monoethylenically unsaturated, cationic monomer, in particular a monomer with at least one quaternary ammonium group or imonium group and at least one further neutral comonomer.
- Suitable cationic monomers are all of the monoethylenically unsaturated cationic monomers mentioned in A ', for example quaternized N-vinylimidazoles such as 1-vinyl-3-methylimidazolium chloride or methosulfate, or quaternized dialkylaminoalkyl acrylates and methacrylates, e.g. B.
- Particularly noteworthy cationic polymers PW are: copolymers of 1-vinylpyrrolidone with 1-vinyl-3-alkylimidazolinium salts, in particular with 1-vinyl-3-alkylimidazolinium chloride or methosulfate; Copolymers of 1-vinylpyrrolidone with methacryloyloxyethyltrialkylamonium salts, in particular with methacryloyloxyethyltrialkylamonium chloride or methosulfate; Terpolymers of vinylpyrrolidone and vinylcaprolactam with 1-vinyl-3-alkylimidazolinium salts, in particular with 1-vinyl-3-alkylimidazolinium chloride or methosulfate.
- Such polymers PW are known in principle to the person skilled in the art, for example from EP-A 246 580, EP-A 544148, US 4,859,756 and EP-A 715 843, the content of which is hereby expressly incorporated by reference.
- the polymers are also commercially available, for example as LUVIQUAT® FC 370, LUVIQUAT® FC 550, LUVIQUAT® HM 552, LUVIQUAT® FC 905, LUVIQUAT® MS 370, LUVIQUAT® PQ 11 and, LUVIQUAT® Hold from BASF AG (Ludwigshafen) .
- Suitable anionic polymers PW are, for example, homopolymers and copolymers which are composed of at least one monoethylenically unsaturated monomer with at least one acid group, for example one of the monomers listed under A ', in particular in particular a monomer with at least one COOH or S ⁇ 3 H group, and optionally at least one further neutral comonomer or a monoethylenically unsaturated comonomer with an acid group.
- Monomers with an acid group to be mentioned specifically are acrylic acid, methacrylic acid, maleic acid and 2-acrylamido-2-methylpropanesulfonic acid.
- the neutral comonomers mentioned in the present case are, in particular, C ⁇ -C ⁇ 0 - and in particular C ⁇ -C 4 -alkyl esters of acrylic acid or methacrylic acid, hydroxyalkyl esters of acrylic acid or methacrylic acid, vinylaromatic monomers, olefins, acrylamide and methacrylamide as neutral comonomers in the present case .
- Polymers with copolymerized maleic acid can also be produced from maleic anhydride copolymers by hydrolysis.
- Anionic polymers PW which are composed of at least one monoethylenically unsaturated monomer with an acid group and at least one neutral comonomer are preferred.
- the salts especially the alkali metal and ammonium salts of the aforementioned anionic homopolymers and copolymers.
- the anionic polymers have carboxyl groups, they can be partially esterified with polyalkylene oxides or their monoalkyl ethers (see, for example, EP-A 367 049).
- Suitable anionic polymers PW are, for example, the homo- and copolymers of acrylic acid, methacrylic acid, maleic acid and 2-acrylamido-2-methylpropanesulfonic acid and their salts. Such polymers are well known to the person skilled in the art.
- anionic polymers PW are: homo- and copolymers of 2-acrylamido-2-methylpropanesulfonic acid; Copolymers of acrylic acid and / or methacrylic acid with styrene; Copolymers of acrylic acid and / or methacrylic acid with C ⁇ -C 4 alkyl esters of acrylic acid and / or methacrylic acid; Copolymers of maleic acid or of maleic anhydride with olefins, in particular with diisobutene; Formaldehyde condensation products of an arylsulfonic acid; and the salts, preferably the alkali metal or ammonium salts and in particular the sodium salts of the aforementioned anionic polymers PW.
- Suitable homo- and copolymers of 2-acrylamido-2-methylpropanesulfonic acid are known, for example, from DE 195 39 460, EP 671 435 and EP 629 650. Reference is hereby made in full to the content of the cited documents. Such polymers are preferably used in the form of their sodium salts or their ammonium salts.
- Preferred styrene / acrylic acid copolymers and styrene / methacrylic acid copolymers have a styrene content of about 20 to 60% by weight, in particular 35 to 50% by weight and an acid number of 130 to 250.
- Their average molecular weight M w is preferred - Wise 1000 to 15000.
- the glass transition temperature of the copolymers is preferably 60 to 90 ° C.
- the carboxyl groups of these copolymers can be partially esterified, e.g. B. ethoxylated or propoxylated.
- the ammonium and especially the sodium salts of such polymers are preferred.
- Such polymers are known (z. B. EP-A-68 024, 96 901 and 467 103) and commercially z. B. available under the name Joncryl ® , Carboset ® , Morez ® or Glascol ® .
- Preferred copolymers of maleic acid (or of maleic anhydride after hydrolysis) with olefins preferably C 4 -C 2 -01efins, in particular isobutene and diisobutene, and processes for their preparation are known, for example, from EP-A 9169, EP-A 9170 and EP-A 367049 known.
- the molar ratio of polymerized maleic acid to polymerized olefin is preferably in the range from 5: 1 to 1: 5.
- the carboxyl groups in these polymers are preferably at least partially neutralized. The ammonium and especially the sodium salts of such polymers are preferred.
- the carboxyl groups of these copolymers can also be partially esterified, e.g.
- the K value of the polymers in the acidic, ie non-neutralized form is generally in the range from 5 to 100, preferably 10 to 60 (determined according to Fikentscher as a 1% strength by weight solution, Cellulose-Chemie 13, 1932 , Pp. 58 - 64 and 71 to 74).
- Such polymers are commercially available, for example, under the name Sokalan® CP9 from BASF AG.
- Formaldehyde condensation products of aromatic sulfonic acids are known to the person skilled in the art as spraying aids, for example from DE-A 24 45 813, EP-A 78 449, EP-A 407 889, WO 98/03576 and WO 98/03577 .
- Spray aids are hereby expressly referred to.
- Suitable formaldehyde condensation products are also commercially available, for example as TAMOL® NN 4501 and as TAMOL® NN 9104 from BASF AG.
- exercises can be incorporated. They can also be added in the preparation of the dye-containing polymer dispersion according to the invention, for example as protective colloids. They can also be used as drying aids when drying the dye-containing polymer dispersion according to the invention, and thus into that
- the weight fraction of the polymers PW, based on the dye-containing polymer in the preparation, is generally in the range from 0.5 to 100% by weight, preferably in the range from 1 to 25 60% by weight and in particular in the range from 2 up to 30% by weight.
- polymer dispersions to reduce coagulum formation and to increase the storage stability of the dye-containing polymer dispersions, which is particularly important when polymer dispersions with a higher dye content, for. B. above 2 wt .-%, especially above 5 wt .-%, based on the
- polymer dispersions containing no polymer PW can be dispersed by treatment with aqueous solutions of the polymer PW. This applies in particular if the glass transition temperature of the polymer matrix of the dye-containing polymers is at least 60 ° C.
- a good redispersibility of the dye-containing polymer according to the invention can also be achieved if a monomer mixture is used in the preparation of the dye-containing polymer dispersions according to the invention which comprises 0.5 to 30% by weight, preferably 1 to 20% by weight and especially 2 to 15
- the dye-containing, aqueous preparations according to the invention frequently additionally comprise at least one inorganic or organic base as auxiliaries.
- Suitable bases are, for example, alkali metal hydroxides, ammonia and basic ammonium salts such as ammonium carbonate, aliphatic amines such as mono-, di- and trialkylamines with generally up to four carbon atoms, hetero-cyclic amines such as morpholine and piperazine and alkanolamines such as mono-, di- and trialkanolamines and mono- and dialkanolalkylamines, usually with up to four carbon atoms. Volatile bases are preferably used. As a particularly preferred base (D) z. B. called ammonia.
- the proportion of agents with a water-retaining effect in the dye-containing preparations according to the invention is generally 0.1 to 35% by weight, in particular 5 to 25% by weight.
- the polymer matrix of the dye-containing polymers used for this purpose has a glass transition temperature T G above 60 ° C.
- the ink jet process the usually aqueous inks are sprayed directly onto the substrate in small droplets.
- driving is either applied via a piezoelectric crystal or a heated cannula (bubble or thermo-jet process) pressure on the ink system and thus an ink drop is thrown out.
- Such procedures are in text. Chem. Color, volume 19 (8), pages 23 to 29, 1987, and volume 21 (6), pages 27 to 32, 1989.
- cellulose-containing materials such as paper, cardboard, cardboard, wood and wood-based materials, which can also be lacquered or otherwise coated,
- the substrate material can be flat or three-dimensional and can be printed with the aqueous, dye-containing preparations according to the invention both over the entire surface and in images.
- the 0.001 to 5% by weight, preferably 0.01 to 2% by weight and in particular 0.05 to 1% by weight of optical brightener, based on the weight of the polymer matrix of the polymer contain.
- the aqueous pigment-containing preparations according to the invention usually contain 0.5 to 30% by weight, preferably 0.1 to 20% by weight, in particular 2 to 15% by weight and especially 3 to 10% by weight, based on the solids content of the Pigment-containing preparation according to the invention, at least one dye-containing polymer which contains at least one optical brightener as the dye. 5
- the film-forming, water-insoluble polymer is essentially composed of the aforementioned ethylenically unsaturated monomers A2.
- Customary monomers A2 in this case are vinyl acetate, vinyl propionate, optionally with ethylene as a copolymer, vinyl aromatic monomers, in particular styrene, C ⁇ -C ⁇ o-alkyl esters of acrylic acid or methacrylic acid, in particular methyl methacrylate 0 lat, n-butyl acrylate and 2- Ethyl hexyl acrylate and butadiene.
- the film-forming polymer In order to ensure film formation, the film-forming polymer generally has a glass transition temperature (according to ASTM-D 45 3418-82) below 50 ° C. and preferably below 40 ° C., in particular below 30 ° C. In general, however, it is above -80 ° C.
- the glass transition temperature of the film-forming polymer naturally depends on the specific purpose. For binders for emulsion paints, it is often above -20 ° C. If the emulsion paints are solvent-free, the glass transition temperature is often below 15 ° C.
- the glass transition temperature of the film-forming polymer is preferably in the range from -30 to -10 ° C. and in particular in the range from -25 to -20 ° C, in the case of paper coating slips for the offset range, preferably in the range from 0 to 40 ° C., in particular in the range from 0 to 25 ° C.
- T g n are the glass transition temperatures of the polymers built up in each case from one of the monomers 1, 2, ..., n in degrees Kelvin.
- the latter are e.g. B. from Ullmann's Encyclopedia of Industrial Chemistry, VCH, Weinheim, Vol. A 21 (1992) p. 169 or from
- the glass transition temperature can be any glass transition temperature.
- Choice of monomers can be adjusted in a known manner.
- film-forming polymers are generally carried out in a manner known to the person skilled in the art by radical aqueous emulsion polymerization of the monomers in the presence of at least one polymerization initiator and at least one surface-active substance which is selected from the abovementioned emulsifiers and the protective colloids.
- the dispersions of the dye-free film-forming polymer obtainable in this way generally have weight-average particle sizes in the range from 20 to 1000 nm, in particular 50 to 800 nm.
- the average particle size is particularly preferably in the range from 50 to 200 nm, very particularly preferably 100 to 160 nm. Bimodal and multimodal particle size distributions can also be advantageous.
- the dye-free, film-forming polymer is a binder component for the inorganic white pigment and the fillers.
- Such accessories Rittungen contain the film-forming polymer as a binder, preferably in amounts of 1 to 50 wt .-%, in particular 2 to 40 wt .-%, based on the total solids content of the preparation.
- the paper coating slips contain the film-forming polymers in particular in an amount of 3 to 30% by weight, based on the total solids content of the paper coating slips (information relates to polymer as such, not to the dispersion).
- the amount of binder depends on the printing ink used, the type of paper and the type of printing.
- the proportion of binder in the gravure printing range is 3 to 6% by weight when using solvent-containing printing inks, 15 to 20% by weight in aqueous printing inks and 8 to 20% by weight in the offset range.
- the polymer matrix of the polymers containing the optical brightener also acts as a binder, provided that it has a glass transition temperature suitable for film formation.
- Suitable film-forming polymers for paper coating slips are known, for example, from EP-A 307 816 and EP-A 833 752.
- the total amount of polymer with brightener and dye-free polymer will preferably not exceed 50% by weight, in particular 40% by weight and particularly preferably 30% by weight, based on the total solids content of the preparation.
- Inorganic white pigments and inorganic fillers are usually the main component of the pigment-containing preparations according to the invention. Their proportion, based on the total solids content of the preparations, is generally in the range from 50 to 98% by weight and in particular in the range from 60 to 90% by weight. .
- Frequently used pigments and fillers are feldspar, silicates, kaolin, talc, mica, magnesite, dolomite, alkaline earth sulfates such as calcium sulfate and barium sulfate, silicon dioxide, calcium sulfoaluminate, titanium dioxide, zinc oxide, chalk or coating clay.
- the pigment-containing preparations according to the invention can furthermore contain conventional dispersants as auxiliaries.
- Suitable dispersants are polyanions, for example of polyphosphoric acids or of polyacrylic acids, which are usually present in amounts of 0.1 to 3% by weight, based on the amount of pigment / filler.
- the pigment-containing preparations according to the invention can contain so-called “co-binders” and thickeners as auxiliaries.
- Co-binders Starches, casein, gelatin and alginates may be mentioned as natural cobinders and thickeners, hydroxyethyl cellulose, methyl cellulose and carboxymethyl cellulose and cationically modified starch may be mentioned as modified natural products.
- synthetic cobinder and thickener e.g. B. based on vinyl acetate or acrylate. These can be contained in amounts of 0.1 to 10% by weight, based on the amount of pigment.
- auxiliaries are defoamers, preservatives or water repellents, biocides, dyes and / or fibers.
- the polymer preparations for adjusting the film-forming properties of the polymers A can also contain solvents or plasticizers.
- the constituents are mixed in a known manner, the dye-free polymer generally being used in the form of the aqueous dispersion.
- the pigment-containing preparations according to the invention are particularly suitable for use as a paper coating slip.
- Paper coating slips are used for coating paper, especially for papers used in printing processes, e.g. B. offset printing or gravure printing, are to be used.
- the pH of the dispersions was determined using a glass electrode.
- the LD value was determined by comparing the light transmittance of a 0.01% by weight sample (layer thickness 2.5 cm) of the respective polymer dispersions against water.
- Dye 4 Lumogen ® F Violett 570 (from BASF; naphthalimide
- Dye 7a Neopen® Blue 807 (from BASF; reaction product of a mixture of Cu-phthalocyanine trisulfochloride and tetrasulfochloride with 3- (2-ethylhexoxy) propylamine);
- Dye 9 Ultraphor® SF-00 (from BASF; o, o-dicyanodistyrylbenzene); Dye 10: N- (n-nonyl) perylene-3,4-dicarboximide;
- Dye 11 N- (2,6-diisopropylphenyl) -1,6,9-tris (p-tert-butylphenoxy) perylene-3,4-dicarboximide
- Example 9 Preparation of N- (2,6-diisopropylphenyl) -9- (p-styryl) perylene-3,4-dicarboximide (dye 16) A mixture of 5 g (9 mmol) 9-bromo-N- (2,6-diisopropylphenyl) perylene-3,4-dicarboximide (prepared analogously to Example 6a of WO 96/22 332 with N- (2,6-diisopropylphenyl) perylene-3,4-dicarboximide from Example 28 or WO 97/22 607 as starting material), 1.6 g (10.8 mmol) of p-styrene boronic acid, 0.9 g of Pd (PPh 3 ) 4 , 100 ml of a 2N potassium carbonate solution and 500 ml of toluene were stirred and refluxed in an argon atmosphere for 12 h (115 -120 ° C) heated, after
- UV / VIS (CH 2 C1 2 ): ⁇ max ( ⁇ ) 404 (8312), 515 (38122), 550
- UV / VIS (CH 2 C1 2 ): ⁇ max ( ⁇ ) 403 (8111), 514 (37001), 549
- aqueous emulsifier solution was placed in a reaction vessel with a stirrer (template).
- the components of this solution are given in Table 1.
- a solution of the respective dye in the monomers to be polymerized (monomer / dye solution) was added within 2 minutes.
- the components of this solution are given in Table 1.
- the mixture was then stirred for a further 10 minutes.
- the resulting conventional, dye-containing monomer emulsions were then homogenized as follows to form an aqueous monomer microemulsion using ultrasound:
- a Branson Sonifier II 450 was used as the ultrasound source. With stirring, 1 liter of the aqueous macroemulsion was sonicated for 5 minutes with the duty cycle 25%, Output control 10, and 10 minutes with duty cycle 100% and Output control 10. Here, aqueous, farbstoffhal- 0 term mini emulsions were obtained. The droplet sizes of these mini-emulsions (d z values) are given in Table 2.
- Emulsifier A 15% by weight aqueous sodium lauryl sulfate solution
- Emulsifier B 2-sulfosuccinic acid bis (2'-ethylhexyl) ester sodium salt (50% by weight aqueous solution)
- C l: l-mixture of emulsifier B (DOW Fa, 45 wt .-% pure.) (50 wt .-%) and Dowfax ® 2A1
- aqueous emulsifier solution was placed in a reaction vessel with a stirrer (template). The components of this solution are shown in Table 3.
- a solution of the respective dye in the monomers to be polymerized (monomer / dye solution) was added within 2 minutes. The components of this solution are shown in Table 3.
- the mixture was then stirred for a further 10 minutes.
- the resulting, conventional, dye-containing monomer emulsions were then homogenized using ultrasound as follows to form an aqueous monomer microemulsion:
- the device described in FIG. 4 of DE 197 56 874 was used as the ultrasound source, equipped with a flow cell with a vessel diameter of 42 mm and a height of 25 mm.
- the sonotrode had a diameter of 40 mm and an output of 1,000 W.
- With stirring about 0.5 liter of the aqueous macroemulsion was sonicated at a flow rate of 30 l / h with an output of 1,000 W.
- Aqueous, dye-containing mini-emulsions were obtained.
- the droplet sizes of these mini-emulsions (d z values) are given in Table 5.
- the miniemulsion thus obtained was placed in a polymerization vessel and heated to 85 ° C. Then the initiator solution (see Table 3) was added in one portion with stirring, the mixture was left to react at 80 to 85 ° C. for 2.5 h and then cooled to 25 ° C.
- the properties of the polymer dispersion thus obtained are given in Table 5.
- a mini-emulsion was prepared from template 1 and a monomer / dye solution in the manner described under V 1.1. Their composition is shown in Table 4.
- the mini-emulsion thus obtained was transferred to an inlet vessel. Water and part of the initiator solution (IL) were placed in a polymerization vessel (template 2; see Table 4).
- the template 2 was heated to 85 ° C. and the dye-containing mini-emulsion and the aqueous initiator solution were then added to the polymerization vessel at the same time, starting within 3 hours, while maintaining the 85 ° C.
- the properties of the dye-containing polymer dispersions are given in Table 5.
- L370 Luviquat® FC 370
- LA Lauryl acrylate
- LH Luviquat® Hold
- NaPS sodium peroxodisulfate
- Luviquat® FC 370 is an approximately 40% by weight aqueous solution of a copolymer of vinylpyrrolidone and l-vinyl-3-methylimidzolium chloride in a weight ratio of 7: 3, with a K value (according to Fikentscher; determined based on to DIN 53726 as a 1% by weight solution in 3% by weight aqueous NaCl solution in the range from 41 to 49 (manufacturer: BASF AG, Ludwigshafen).
- Luviquat® Hold is an approximately 20% by weight aqueous solution of a terpolymer made of vinyl caprolactam, vinyl pyrrolidone and 1-vinyl-3-methylimidzolium methyl sulfonate in a weight ratio of 5: 4: 1, with a viscosity (determined according to Brookfield LV; as 1% by weight solution? based on DIN 53018 in the range from 1.5 to 4 (manufacturer: BASF AG, Ludwigshafen).
- Tamol® NN 4501 is the powdery sodium salt of a low molecular weight formaldehyde condensation product of an isomer mixture of ⁇ - and ⁇ -naphthalenesulfonic acid, whose 45% by weight aqueous solution has an average viscosity (according to Brookfield) of about 70 mPa-s (determined at 23 ° C) (manufacturer: BASF AG, Ludwigshafen).
- the emulsifier used was the bis-2-ethylhexyl ester of sulfosuccinic acid (as the sodium salt in the form of a 60% by weight aqueous solution) (LUMITEN® IRA from BASF AG).
- the ink formulations according to the invention according to 2.1 were in a commercially available ink jet printer from Epson (Stylus Color 500) both on commercial paper for laser printers (80 g / m2; intercopy) and on special paper for high-resolution inkjet printing (Paper for 720 dpi printing; Epson).
- Epson Stylus Color 500
- a checkerboard pattern full color / unprinted: 11 cm served as the test print sample.
- the mini-emulsions thus obtained were placed in a polymerization vessel and heated to 85 ° C.
- 10 parts by weight, based on 100 parts by weight of monomers, of a 10% by weight solution of sodium peroxodisulfate in water (initiator solution) were added all at once. After the initiator had been added, the mixture was left to react for 3.5 hours at 80-85 ° C. with stirring and then cooled to 25 ° C.
- the properties of the aqueous polymer dispersions thus obtained are summarized in Table 7.
- Type A is the ammonium salt of a copolymer of maleic acid and 2,4,4 '-trimethylpent-1-ene, which by ammoniacal hydrolysis of a copolymer of maleic anhydride and
- Example 3 of EP-A 9169 is available according to Example 3 of EP-A 9169.
- 325 parts of water are added to the suspension and excess disobutene is distilled off by steam distillation (bath temperature 80 ° C.). After an internal temperature of 98 ° C. has been reached, it is still 1 h Steam introduced. After adding a further 200 parts of water and 170 parts of 25% by weight ammonia, the mixture is stirred at 60 ° C. until an almost clear aqueous solution is obtained (approx. 1 h). The solids content is then adjusted to 22% with water. The pH of the solution is 9.
- the K value of the copolymer (determined according to Fikentscher as a 1% strength by weight solution in dimethylformamide) is in the range from 30-40.
- Type B is the sodium salt of a copolymer of maleic acid and 2, 4,4'-trimethylpent-1-ene, which is obtained by hydrolysis of a copolymer of maleic anhydride and 2, 4, 4'-trimethylpent-1-ene.
- the latter copolymer is obtainable according to Example 3 of EP-A 9169.
- 325 parts of water are added to the suspension and excess disobutene is distilled off by steam distillation (bath temperature 80 ° C.). After an internal temperature of 98 ° C has been reached, steam is introduced for a further 1 h.
- the K value of the copolymer (determined according to Fikentscher as a 1% strength by weight solution in dimethylformamide) is in the range from 30-40.
- Type C is a 44% by weight aqueous solution of a reaction product, obtainable by reacting 420% by weight.
- the pH of the solution is about 7.5.
- the K value of the copolymer (determined as a 1% by weight solution of the polymer in cyclohexanone according to Fikentscher) is in the range from 14 to 18.
- Table 6 Feedstocks
- Table 8 Redispersibility of polymer dispersions which were prepared in the absence of a polymer PW (tests Rl to Rll)
- Dye was dissolved in the monomers together with 1 part by weight of oleic acid (based on 100 parts by weight of dye).
- AI 1 wt .-% hydrogen peroxide, 0.15 wt .-%, based. to 100% by weight of main monomers, hydroxymethanesulfinate sodium salt.
- A2 0.3% by weight hydrogen peroxide, 0.3% by weight, based on to 100% by weight of main monomers, hydroxymethanesulfinate sodium salt.
- A3 0.3% by weight hydrogen peroxide, 0.3% by weight, based on to 100% by weight of main monomers, ascorbic acid.
- the coating slip was applied on both sides with 6 g / m 2 each on a technical coater (application method: roller, dosing method: blade) at a speed of 1000 m / min.
- the paper web was adjusted to a paper moisture of 5.0% by means of an IR drying unit and air drying.
- the coated papers were exposed to light in the range from 300-800 nm (. X 450 nm) and a power density of 250 W / m 2 using an Atlas xenon lamp Suntest XLS Plus and then measured.
- the values are given in Table 15.
Abstract
Description
Claims
Priority Applications (6)
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DE59909181T DE59909181D1 (de) | 1998-02-09 | 1999-01-13 | Verfahren zur herstellung farbstoffenthaltender, wässriger polymerisatdispersionen |
JP2000530550A JP4383657B2 (ja) | 1998-02-09 | 1999-01-13 | 染料含有水性ポリマー分散液の製法 |
CA002320244A CA2320244C (en) | 1998-02-09 | 1999-01-13 | Method for producing aqueous polymer dispersions containing colorants |
EP99906122A EP1054907B1 (de) | 1998-02-09 | 1999-01-13 | Verfahren zur herstellung farbstoffenthaltender, wässriger polymerisatdispersionen |
US09/600,868 US6727318B1 (en) | 1998-02-09 | 1999-01-13 | Method for producing aqueous polymer dispersions containing colorants |
US10/629,552 US7176255B2 (en) | 1998-02-09 | 2003-07-30 | Method for producing aqueous polymer dispersions containing colorants |
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DE19805121.2 | 1998-02-09 | ||
DE19805121A DE19805121A1 (de) | 1998-02-09 | 1998-02-09 | Verfahren zur Herstellung farbstoffenthaltender, wässriger Polymerisatdispersionen |
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US10/629,552 Division US7176255B2 (en) | 1998-02-09 | 2003-07-30 | Method for producing aqueous polymer dispersions containing colorants |
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EP (1) | EP1054907B1 (de) |
JP (1) | JP4383657B2 (de) |
KR (1) | KR20010040768A (de) |
CN (1) | CN100357326C (de) |
CA (1) | CA2320244C (de) |
DE (2) | DE19805121A1 (de) |
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Also Published As
Publication number | Publication date |
---|---|
EP1054907A2 (de) | 2000-11-29 |
US20050075453A1 (en) | 2005-04-07 |
US6727318B1 (en) | 2004-04-27 |
CN100357326C (zh) | 2007-12-26 |
CA2320244A1 (en) | 1999-08-12 |
CN1293680A (zh) | 2001-05-02 |
JP2002502893A (ja) | 2002-01-29 |
CA2320244C (en) | 2009-11-10 |
KR20010040768A (ko) | 2001-05-15 |
WO1999040123A3 (de) | 1999-10-28 |
ES2220045T3 (es) | 2004-12-01 |
EP1054907B1 (de) | 2004-04-14 |
JP4383657B2 (ja) | 2009-12-16 |
DE59909181D1 (de) | 2004-05-19 |
DE19805121A1 (de) | 1999-08-12 |
US7176255B2 (en) | 2007-02-13 |
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