DE1905721A1 - Thickened aqueous latices and process for their manufacture - Google Patents

Description

The invention relates to 'thickened aqueous' Latices and a process for the production of thickened aqueous latices with unusual flow properties.

It has already been proposed to increase the viscosity of aqueous latices by making them water-soluble polymeric materials, commonly referred to as thickeners. To a useful one To maintain viscosity at acceptable concentrations of thickener, the polymeric materials are typically of colloidal dimensions with immoral

009835/0 964

Oral · Abradan, intbtsondar «by Taltfbn, btdürtan echrlftllehar BtUStlgung PrMdntr Bank Munich Account 109104 · Pc «t« htekkonto Mönchen 11 »74

■:. ■; ■; ■ :: ■ -. ■ * ■ ■ -. ■■■. · ■■ -

. Molecular weights, as measured by "their" solution viscosities, on the order of 100,000 or more.

For example, if the latex is an aqueous latex paint it is desirable to thicken the paint, i.e. to increase its plastic viscosity, about the ease with which it can be applied when applying, e.g. by brushing on a. Substrate, spreads, to limit, where it is known to be dried Low-strength films can form if the paint spreads too easily «It is also desirable that the applied mim has good educational properties possesses flat surfaces. I.e. the moist film should have sufficient flow before it dries, so that defects left behind by the application process, e.g. strokes, flow out and such Even surface is formed «if, however, usual thickeners to a latex in sufficient concentrations to generate an appropriate plastic visual viscosity to be admitted, what with the limitation of the Speed of propagation, are those Properties for the formation of flat surfaces often not satisfactory. - · _

It has now been found that good pleating properties can be achieved in a thickened aqueous latex

009835/0984

by thickening the latex in such a way that the thickened latex has a "pilling coefficient" of greater than 1.5, where, the Pliesscoefficient as plastic Viscosity of the latex in centipoise divided by, its

The limit value is defined in dynes per cm. When the egg thickening using conventional thickening agents, "for example soluble cellulose derivatives, "is the flow coefficient usually 1 or less, what with bad properties for the formation of flat surfaces related.

Surprisingly, it has now been discovered that not only certain mixed polymers of vinyl alcohol are unusual low molecular weight used as a thickener at normal concentrations in aqueous latices can be, but that even if this is in appropriately selected, so thickened latices have a 3? let coefficient of greater than 1.5 can.

According to the invention, thickened aqueous latiees are made with a Pliess coefficient greater than 1.5 and a plastic viscosity of at least 0.3 poise at 25 ° ® provided, the'Latex in an aqueous liquid dispersed disperse polymer particles with an average diameter of 0.04

: ■ -. W130S721

to 2.0 microns, preferably 0.05 msec 0.4 microns -and 0.1 to 10% by weight of one in the. aqueous latex soluble polymeric thickening agent based on the weight of the resin particles, the thickening agent; \. of a chain-like mixed polymer of vinyl alcohol with · at least one mixed monomer, "containing 4 to: ■ -_ ■ '■' 18 carbon atoms, the homopolymer of which is essentially insoluble in the aqueous latex, and wherein the mixed polymer has a molecular weight of 2: 000 to 10 OQO and the proportion of the mixed monomer units therein "is related to the number of carbon atoms' in the mixed monomers according to the following table:

C atoms in the mixed MdI mixed monomer units as percent polymer set of total monomer units

minimum maximum 1 preferred area 4th .. 10.0 " 50 1 15 to 30 VJl 6.0 35 - •1 8 to 22 6th 3.0- 28 0 5 to 15 7th ^: ■ 1.5: 25th 0 2 to 12 8th ■ 1.0 ;:; 21 0 ,5 to 10 9 0.8 18th »2 to 9 10 0.7 ^: 15th , 0 to. 8th 11 · · 0.6 ' 12th , 9 to 7 12th 0.5; 10 , 8 to 6 13-18 - 0.2 8th , 3 to 5

009835/8964

Furthermore, according to the invention, a method for producing a thickened aqueous latex with a flow coefficient of greater than 1.5 and a plastic viscosity of at least 0.3 poise at 25 ⁰ G is created by adding Hn "in a latex which has a flow coefficient of greater than 3 and having dispersed polymer particles dispersed in an aqueous liquid with an average diameter of 0.04 to 2.0 microns, preferably 0.05 "to 0.4 microns, 0.1 to 10.0 wt $., based on the weight of the synthetic resin particles, dissolves a soluble polymeric thickener g, as described below, selected from chain-like .Mischpolmeren of vinyl alcohol with at least one mixed monomer containing 4 to 10 carbon atoms, the homopolymer of which is essentially in the aqueous latex is insoluble, the copolymer having a molecular weight of 2,000 to 10,000 and the proportion of the mixed monomer units therein with the number of the carbon atoms in the mixed monomers is related according to the following table:

C atoms in the mixed mole of mixed monomer units as percent monomers set of total monomer units

• Minimum maximum "- preferred area '" until 30. '"■"; ·. ■ ■ 4 10.0 ' .50 .15 until 22; .. "; .- 5 '"6.0 35 ν ³ until 15; . -; ■■ " 6th • 3.0 28 5- until 12th: 7th . ; -1.5 25th; 2 · until ΙΟ '/. ν 8th 1, 'OV 21 - 1.5 until i 9 ^V. 9 0.8 18th 1.2 until 8th ■ ίο ' 0.7 ' 15th 1.0 until 7th 11: 0.6 12; 0.9 until ■; 6 .. '' 12th .- .0.5. 10 0.8 until 5. 13 ■ - 18 0.2 . 8th- 0.3

Lower limit value and plastic viscosity values are zu'verstehen that from the section on the "abscissa and the inclination of a graph of shear rate / shear force curve of the paint at 25 ⁰ C, is applied to einem'Quadratwuraelkoordinaten chart calculated net became. The extrapolation of the graph should be from the results in the shear rate range of 40

1 - 1

Be done up to 300 sec7. This diagram is obtained from measurements that were carried out with a suitable rheometer or viscometer ₉ with which the shear force and the -, eutspEöohende vision © SQb, windiness with small increments, or continuously over a

OQ883S / 0SS4

-r-

wide. Area can be measured.

One such diagram, sometimes called the Casson representation, is by Asbeck, for example in Official Digest of the Federation of Societies for Paint Technology 33, (1961), page 69 explained.

The composition of the synthetic resin parts of the aqueous Latex is not critical and it has been found that the invention applies to all polymers or copolymers is applicable, which is commonly used in latex paints will. Such polymers are, for example, homopolymers or copolymers of the following types of Monomers:

Vinyl esters and ethers, alkyl acrylates and methaery . ■ latex, alkyl fumarates and maleates, halogenated oils Vinyle, Arylvinyle und Olefins *

Suitable · monomers are for example vinyl acetate, vinyl propionate, vinyl caprate, vinyl stearate, Vinylester of saturated tertiary monocarboxylic acids "Viny-lsiloxan and the saturated monovalent Alkoholester of ^acrylic: acid, methacrylic acid, maleic acid and" fumaric acid, including those »of methanol, ethanol, n- Propaetiol, isopropanol, n * butanol, isobutenol, secondary butanol, tertiary butanol, C ^ rßlohexanol, 2-ithylhexanol,

Dodecanol, hexadecanol and octadecanol are derived. * Other suitable monomers are vinyl chloride, Vihylldeh-, Chloride, vinylidene fluoride, styrene, alpha-methylstyr oil, the technical mixed isomers known as "vinyl toluene", Ethylene, propylene and isobutylene. Pie polymers can be mixed polymers of two or more of the be the foregoing monomers, and particularly useful blends are interpolymers of vinyl acetate in major molar proportion with vinyl caproate, 2-ethylhexyl acrylate, Ethyl acrylate, n-3utyl methacrylate, dibutyl maleate or Dib'utyl fumarate in a smaller molar proportion or mixed polymers from methyl methacrylate with ethyl acrylate, butyl acrylate, Butyl methacrylate or 2-ethylhexyl acrylate * It is known that lower (usually less than 3 G-ev .- $ of the polymer) proportions of other monomers, ■ e.g., the unsaturated acids of the above Esters are sometimes used to modify such interpolymers, and these modifications are included in the ■ - ■ - ■■; Definition of suitable copolymers according to the invention included. On the other hand, the synthetic resin particles can be substantially linear polymers or interpolymers be of isoprene, chloroprene and butadiene. .

The aqueous liquid forms the continuous. borrowed phase of the latex, and they can V /;:. sser alone or Contain water, up to su 4ö G-ew .-? I water-soluble

'009835/0364

or water-insoluble organic liquids added -. have been, for example, to increase the solubility of the thickener in the liquid, for regulation the evaporation properties of the continuous phase - or the freeze-thaw stability or coagulation properties- • ten of the latex. The. organic liquids can be present alone or in combination.

The organic liquids can, for example, alkyl alcohols, alkylene glycols, alkyl glycol ether alcohols, Be alkyl ketones and some alkyl ethers. It has been found that ethyl alcohol, propyl alcohol, ethylene glycol, Propylene glycols, butylene glycols, hexylene glycols, diethylene glycol, 2-Ketho.xyäth.anol, 2-Ethoxyethanol, 2-Propoxyäthanol, 2-butoxyethanol, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, Diacetone alcohol and 1: 4-dioxolane are satisfactory Liquids are.

The preferred organic liquids are ethylene glycol, Propylene glycols, butylene glycols, 2'-ethoxyethanol, 2-butoxyethanol and diacetone alcohol, whose volatility is particularly suitable for regulating the drying properties of made from the thickened latices Coatings are. ,. '

BATH ORIGINAL

The non-thickened latices typically contain ' 20 "to 50% of the disperse polymer particles, based on" the weight of the dispersed polymer together. _ with the aqueous liquid, which an area on. . Base usual technical implementation is; However, provided that the latex is stable, the mixture is for carrying out the invention is not so limited.

The latex must be prior to thickening according to the invention not only consist of disperse polymers and water and usually consists not only of that, but optionally also contains water-soluble organic liquids.

It is known that nonionic surfactants can also be present in a latex, for example suspending agents used during latex manufacture. Accordingly, the continuous phase of the latex, both anionic and non- Ionic surface-active agents contain, but it is preferred to limit the seed concentration of such agents to a maximum of Ton 4 £ ew _e - $ y Soaked "on the total weight of the thickened latexysu.

'Typical surface active agents are bsisplels »wise complex phosphates, ζ.B * iafriuaMxamethapiioaphat _s

BATHROOM LOCATION

M -

Saphthalene sulphate, alkylaryl poly (oxyethylene) sulphate dialkylsulphosuccinate, triallcylajmorxlumbase, PolyCsxyäthy- ■■ len) ethanol fatty acid esters, alkyl (oxyethoxy) amide, alkylaryl ρ ο Iy (oxyethylene polymers and propylene oxyethylene or block ethoxyls of alcohol and irregular polymers)

The aqueous latex, especially if it is a latex paint, can contain other materials, for example pigments, fillers, preservatives, defoamers and plasticizers, such additional materials are included in the definition of an aqueous latex according to the invention »

Of course, the latex must not contain any materials that are known * to have thickened aqueous latex react unfavorably. For example, certain pigments, e.g. lead chromates, are for it known to have an unfavorable effect on latex coatings due to their high concentration of soluble metal ions, and unpleasant materials like these should be avoided. Other materials known to be they react with polyvinyl alcohol, or which on the Combination of latex and thickener can act, obviously! ^ Compatibility and gelation of the Paint, and in thickened aqueous Latices found to react

009835/0964 BADOHlStNAL

Jl -

■ .190572-

nuts such. Materials excluded from the / meat ζ ^ v / earth. '

^; For the description of the thickeners to be used according to the invention as hischpolyraere of vinyl alcohol, reference should be made to the fact that vinyl alcohol is not. exists as a stable monomer, and the "thickeners" must be made from suitable copolymerizable monomers. ·. by indirect methods. However, the finished copolymeric thickener has the structure of a vinyl alcohol polymer, which "must be taken into account in the definition according to the invention.

The polymeric thickener is thus produced from at least one monomer which, after it has been copolymerized therein, can then be modified into the molecule to produce a vinyl alcohol unit. For example, a suitable mohawk is an ester of; an alpha, / beta-ethylenically unsaturated alcohol which hydrolyzes to produce a vinyl alcohol unit. Suitable monomers of this type are, for example, hydrolyzable esters of vinyl alcohol, for example vinyl acetate and vinyl propionate. ,. . '·

The mixed monomer of the thickening agent must, in Porm of a homopolymer, essentially in the aqueous la-

_B g 3 5/0 9 6 A. BM)

λ% ■■■■■

tex to be insoluble. This requirement is met when a homopolymer of the mixed monomer, which has been polymerized to a molecular weight of not less than 10,000, has a solubility of less than 1 Gevi.-fo in the continuous phase of the latex to be thickened, while for example vinyl pivalate , which forms a homopolymer which is substantially insoluble in an aqueous latex, is a suitable mixed monomer. Acrylamide, the homopolymer of which may be soluble in the aqueous latex, is not suitable.

The mixed monomer can be an olefin which is derived from the monomer as described above is copolymerized for the vinyl alcohol units. It can, for example, be 1-butene, 1-hexene or 1-decene or an aromatic substituted olefin, ζ.Β * styrene, alpha-methylstyrene or the technical mixed isomers known as "vinyl toluene".

The mixed monomer may be a diolefin such as 1,3-butadiene, 2-methyl-1,3-butadiene, and 2-chloro-1,3-butadiene be, although this. because of the practical difficulties, v / elche in the production of the copolymers in the desired molar proportions are less preferred. .

190572

Suitable mixed monomers .can be made from alkyl esters of . alpha, beta-ethylene-ish unsaturated mono-, and; DicarbOn- ■ acids must be selected. The liischmonomere can "for example an ester of acrylic, methacrylic, .Malein- ·; ■ ;. or fumaric acid with a saturated alcohol., e.g. Methanol, ethanol, n-propanol, isopropanol, - n-butanol, ^ Isobutanol, sec, -Butanol, Cyclohexanol, 2 ~ Ethylhexanol and dodecahol, be. The limited solubility of the mixed monomer is usually, but not necessarily

• wise, 'the use of acidic hardesters of dicarboxylic acids and polyhydric "alcohols, such as the ester alcohols,

-. exclude.

'Another type of Jiischmonomer and: such a j that because of the lightness _? with which it is in a: wide range of molar proportions with the monomers. copolymerized, which is the source of the vinyl alcohol units _s "is particularly preferred,.; is the group of unsaturated tertiary acid esters of."

• Vinyl alcohol, which is particularly resistant to; Ver ™ 'soapmg are. Under saturated tertiary monocarboxylic acids acids are understood by ^ ungösättigten _g versweig-tkettigen hydrocarbons containing a tertiary alpha-carbon atom. Me esters can consist of,

BATH

individual acids or mixed esters composed of one the several acids are derived. The esters can for example, a technical mixture of esters of tertiary acids with 9 to Ή carbon atoms.

The mixed monomer can be an ether of vinyl alcohol. Suitable mixed monomers are, for example, diethyl, n-propyl, isopropyl, η-butyl, isobutyl, sec-butyl, tert-butyl-Z-chloroethyl, 2-methoxyethanol, Cyclohexyl and benzyl ethers of vinyl alcohol. Preferred mixed monomers are the η-butyl and cyclohexyl ethers.

On the other hand, the mixed monomer may be a unit of the polymer chain of the molecule of the thickener which, although it may be incorporated therein by copolymerization of a suitable monomer, is convenient due to the in situ modification of adjacent pairs of mixed monomer units that are already in the. Molecule are present, is formed. For example, suitable mixed monomers are certain acetals, which Monomer units of the formula:

- GE - ■ GH - R OH ₂
i -.CH -

00083.57 09 6

190572

"form, wherein -R, which is within a thickening agent iXe- · Mils same or different "can be, up to 8 KoIiIeast off atoms, preferably 4 to 8 carbon atoms ■ and Alkyly. Alkylene, aryl, ■ alkaryl, aralkyl or Can be aralkenyl. . . . -; _

Particularly valuable mixed monomers are those monomers which contain phenyl groups, i.e. benzals, from adjacent vinyl alcohol units.

Furthermore, in some cases, as below. described, certain "residues introduced into the thickener during its production by the action of polymerisation initiation and / or chain terminators are regarded as mixed monomer units - which are involved in the composition of the polymeric thickener ^.: ■ - ■" ■ "■ ·. ;.;;

The 'thickeners can get through. Interpolymerization, a monomer as a source of vinyl alcohol units and of a mixed monomer in the desired proportions using conventional techniques of addition polymerization initiated by free radicals, including the use of chain terminators, / with subsequent conversion of the units of the former Monomers in the polymer

009835/0964 ■ ^{BAD 0RtölNAI} -

Αϊ, -

see below vinyl alcohol units. For example, a mixed polymer of vinyl alcohol "and" vinyl pivalate can result the mixed polymerization of vinyl acetate and vinyl pivalate are produced, with the vinyl acetate units then under alkaline conditions-to generate hydrolyzed by vinyl alcohol units in the .mischpolymeren will. Similarly, a thickening agent consisting of polyvinyl alcohol / vinyl n-butyl ether can be used by Dutch copolymerization and hydrolysis of vinyl acetate and vinyl n-butyl ether. If for a certain selected mixed polymer composition, the reactivity proportions of the monomer and mixed monomers h are disadvantageous in that they are, for example, uneven feed operations require to get the correct interpolymer composition the polymerization becomes more convenient usually carried out by "emulsion polymerization".

The mixed monomer can with the monomer as a source be identical for vinyl alcohol units, only the proportion of the primary units subsequently hydrolyzing v / ird. The thickening agent can be, for example, a partially hydrolyzed polyvinyl acetate.

009S35 / 09S4

'It can be both the vinyl alcohol as αμοΐι:' the mixed monomer units in the molecule of the thickening. "- introduced by indirect methods. For example, e.in ^: 'Pp ^" (vinyl alcohol / vinyl butyral)' -. "can be produced by first partially hydrolyzing polyvinyl acetate, for example to produce an" .. irregular mixed polymer of vinyl alcohol and vinyl acetate, containing about 20 (? ew .- $ vinyl acetate units, and then · reacting the mixed polymer with butyraldehyde,. ■ the same time the acetate to vinyl _alcohol: hydrolyzed initiate.

If the molar proportions of the mixed monomer units' in the molecule, the 'thickening agent according to the above Table can be chosen; atoms in the mixed monomer have a value in which such; covalently bonded adjacent carbon atoms of the Mi s chmonomers, which are part of the. Carbon «-ICoh- \ Liner backbone chain of the polymeric detergent. form, are included ,. It can do more than one. His chmonomer it must be present in every thickener. and if this is a PaI ^, the number of carbon atoms according to the table is given as © in gev / pgener average value ^ .referred to the number of carbon atoms, in jadem Mixed monomers and etie molar proportions in which the

BATH ORIGINAL

Mixed mono-monomers are present in the mixed polymer, • "calculated, 'ti & nn is the average number of carbon atoms Ice an integer, V / earth the corresponding limits for the percentage of the Hischnonoia units-interpolated from the table above.

When performing this calculation, chain end groups must also be given due consideration. It is for the pachmann it is evident that this is not with accuracy can happen and daio "be st innate assumptions and approximations must be accepted, which method is also used for this -. will. It is-required that this is done in the following way, on which the table above is based.

If from the knowledge of the procedure, the is selected for the preparation of the thickener. "It is known that .terminal groups of the polymer chains, which were obtained as residues of the polymerization initiator and / or the chain terminator, essentially contain less than 4 carbon atoms they are neglected. If, on the other hand, the predictable residues have a greater number of carbon atoms contain, they are regularly treated as those that form substituents, which are covalently attached to terminal Monomer units of the chains of the polymeric thickening s-. , -. ft-t, · ·

009835/0964 BAO original

are bound by means. For the purpose of relating "the composition" of the thickening agent to the table above, a reasonable approximation has been found to be the assumption that the. Terminal monomer units., units that carry the "" above radicals., are always vinyl alcohol units from the outset. Thus, the addition of the terminal groups to these units has the effect of decreasing the apparent number of "vinyl monomeric units" in the thickener and increasing the apparent number of mixed monomer units therein. hend'e-Angle ic hung the theioretis.ch.en composition ,, of the thickener in, Bez ie - ,, .- 'hung to the table above "made. In the practice of a ---- ■ -Dickungsmittels a particular composition from knowledge of the reaction components and the Reaktionskinetik- ,, the probable molare' concentration and type is used in the preparation of the production of the terminal residues that occurring in the thickener , estimated and this estimate verified by analyzing the end product.- From these. Data is estimated the "average molar" composition of the starch, with each mole of a residue assigned to a "vinyl alcohol" unit, as described above. The number of carbon atoms assigned to these presumed mixed monomers is calculated by adding the number of Carbon atoms: the terminal radicals determined to be that of vinyl alcohol It is assumed, for example, - ".

00 ^ 835/0964; ■ - '· v

that by means of an ÄzOdiisobutyrOnitril-Polynerisa- tion initiator. mixed monomers obtained 7 carbon atoms and that from the chain abort by means of a dode- mixed monosers obtained from cyluer-captan chain terminators T4 contains carbon atoms. It can be seen. that the so "described average composition is an artificial assumption in that the polymeric thickener is a heterogeneous mixture of polymer species different compositions and weights however, it would be impractical yet as found became »necessary to try its« to the last detailed composition to be specified »

■ "Thickening is carried out by stirring the thickening agent into the latex in the selected concentration, expediently» but not necessarily pre-dissolved in an aqueous liquid », whereby the usual precautionary measures are taken to prevent the bath from being ventilated Addition of the thickener to a latex normally worsens its pour coefficient, and in order to ensure that the latex according to the invention has a plastic viscosity of at least 0.3 poise and a pour coefficient of greater than 1. 5 can be thickened, it is required that the non-thickened .Latex has a lichtkoeffIsienten greater than 3;

J $$ & ii \ 'Tir \ t% +. * <- - - RAD ORIGINAL

owns. Some common latices have low measured viscosities and it can be difficult to determine their pour coefficients with accuracy, so it is more useful and convenient to use a newly suitable latex by discarding those latices which have a pour coefficient From 3 or less be-Jp. sit »to select. The "'is allowed coefficient determined on the non-thickened latex, have been added to the all Eomponenten except the thickening agent. The' thickening agent may be added for example to a pigmented latex paint or provided with 5 ⁸ UIlStOffen ■ adhesive can be '

Ideally, any thickener would, according to the above table soluble in the selected latex

fe be and thicken it according to the invention, * This ideal can be achieved with certain latices, it is ever-. - but usually required., a selection of dykes from the above. -Susainmens © tziingen ^ based on their solubility in the selected latex. meet * A thickener becomes .as soluble. viewed »if *; ' , after being selected in one at Ijatex- at the desired ten Ko & ze & ir & tiöit -beinge-stirred-in ^, no_ Seiloiien or.; Agglo3 | ®J? At® insoluble-! Eeilcaen of the thickening agent

- ' _r ■ _' "Examination of this Gemisohes with a microscope" ge * »

ringer achievement, s · !, at §G-faob, © r enlargementj are visible. Observations hsb # ß. Gö ^ eigt that when working ■ - ^: ^ u-ivs ^ Ü09835. / QU4 "- bad

With many latiees all the addition of essentially any lietteia so selected. Thickener a thickened latex with a Pließkoeff icient greater than 1.5 generated..

However, as is believed, it may be a result of side effects between certain existing components among each other In your non-thickened latex, e.g. 3. of stabilizers and dispersants, this result is not always achieved, »The Pliess coefficient is noticeably unpredictable and therefore lcanns the basis on which the required thickener is to be selected, not clearly defined if, as is often the case in practice, a technical latex, the exact composition of which is not known, but there is a group of laxatives which within the above, compositional limits which make it possible to create any special Thicken latex according to the requirements of the invention.,

"If the selected latex is thickened as described above and the flow coefficient drops to a value below 1.5, the existence of these unpredictable factors means that the selection of thickeners must be narrowed down as follows ^:

CONSTRUCTION ORIGINAL ΌΟ9835 / 096Α '. "

A soluble thickener with a molar appearance. part of mixed monomers near- the lower limit-,, the .; according to the "number of carbon atoms in the mixed granulation is allowed" is added to the latex in the allowed ... weight concentration on the basis of the weight of the polymer particles and checked for the flow coefficient. The latex thickened in this way would have the desired flow coefficient. If the flow coefficient is too low, a similar thickener with a higher molar proportion of mixed monomer is selected and a latex sample thickened in this way is tested again. The procedure is repeated, taking into account the allowable variables for the selection of the mixed monomers and the molecular weight: until a thickener or group of thickeners has the desired flow properties and ^; Solubility properties has been selected. As a general guide, it has been found that the flow coefficient is usually increased by decreasing the molecular weight of the thickener /. The less hydrophilic the mixed monomer, the better the flow. For example, the flow coefficient of the thickened latex is usually improved by replacing mixed ethyl acrylate units in a thickener with dodecyl methacrylate units.

^s * '"009 83 5/0 9 84 BAD original

is ■■ · .-. ^eT '-

Available compositions which are suitable for a particular latex must also be taken into account that the plastic viscosity obtained for a given concentration by weight of the thickener in the latex increases as the molecular weight of the thickener increases is increased. Therefore it iat j when the amount of dicenter is to be limited, for example by the ITot- ■ agility to keep water-soluble polymeric components of the latex to a minimum, preferably with the high molecular weight thickeners to work which are both soluble in the latex and also achieve the required ply coefficient. It will be natural It may also be necessary to discard thickeners which add the thickened latex at the maximum allowable (Jewiohtskonzentration according to the invention not a Provide a viscosity of at least 0.3Poise. G-ewöhnl.icli However, it is found that such a thickener to settle for peace is if it was made with a higher average molecular weight.

■ ■ - '- ι ■ - - ■■■ - "· ■ - ■'

. The invention is not limited thereto, taken ■ ßatieea produce I ¹ XIeßkoeffizienten greater than \ alsi. 3 Through the pre- ']) esökriö _: "beiae ■■ allgömeiwe method, a thickened latex can be produced with a Pliesskocefficient higher than 3, whereby it must be noted that

this usually requires that the non-thickened latex has a flow coefficient of at least 2 units -..- higher than the thickened latex. It has been found when working with certain technical latexes of unknown composition that the actually achieved IPLoss coefficient when thickening according to the invention is lower than predicted. This appears to be due to the use of an unusually low concentration of surfactant in the latex. Under these circumstances the addition of something non-ionic -. . "Shem surface-active agent, eg * a ■! Tony! phenyl / ethylene oxide-ICondensate restores the normal state! -." -.- · ";: ■ len.". - '/ "" ■ ,. " ---. ..'. ■ -."""".-·."'■"-■'"..;

It can be seen that once there is a suitable range of thickeners for a particular latex was selected, the thickener should not then be added in exactly the manner described above but may be added to the latex at any convenient earlier stage in its manufacture.

Certain materials (branded items) that were used in the \ examples are identified as follows:

partially hydrolysed polyvinyl acetate! by.-SQhnifctlibftes Holekulategewiofct about 3000> 75 $ hydro

BATH ORIGINAL

3 *

tertiary vinyl ester: a tertiary vinyl alcohol ester branched chain monocarboxylic acids containing 9 Ms 11 "carbon atoms;

Pigment grade titanium dioxide: surface treated Quality of Eutil titanium dioxide ("Austiox" R-CB.6-. "Austiox:" is a trademark of Australian Titan Products Pty *, Ltd.);

technical defoamer: a technical defoamer not "known composition (" ITopco " ITXZ - "Uopco" is a visa oak from ITopco Chenica.1 Co., USA); -: ■.

Latex A: an acrylic copolymer latex of 46.0-G-ew .- ^ Pesticides and a medium-sized lily knife from 0.06 microns; .

Latex B: an acrylic copolymer latex with 4o, 5, G.ev; .- ^ solids and an average particle diameter of 0.1 micron. '. -

The invention is illustrated by the following examples, in which all parts are expressed by weight are.

Preparation of a solution from a partMl hydrolyte 00983B / 0 964 g ^ _0RlaiNA

. "- ■ ^-;.. - ■■■■■ '' - ^'': 1J0E721

sierte Polywinylaeetat-ISieloingsiEittei pil; one ICpie-τ-failargeiriicht of approximately 3000 and one retained τοη "aa.geaab.ert 25- Tinylacetateialieifeii.je 1OG I-Ionosereiniiei-- - · th. -.." ■■ ". '- ^; '

-A G-esisch. sit a "salary of 30 ropes-" one _; .

-partially bydrolized Polyvinylaeetats von teenniseaer, ■ -,

Quality, dispersed in 70 parts of water, became "in". ■ -

a hit a stirrer and a HückflußkondensatöJE ¹ - - -_ ". Eollaen equipped to an operation of 80 ⁰ C - -

aitzt and "with" this teaperätur two stnoses long "g ■ - th. The tlare, Tistose solution obtained is nacasteiiend -.-. "as Bictungsöittel 1 ljeseiefa.net .. It -wurden ireine final-" gen S-ruppen ax 4 or aear Eolalenstofiatoaen durcfa. analysis des- DicjEungsiaittels found. '. . - - -.-. ■ - - - ..- -. "■ '

ψ Bas BielöingsEittel-was used for the indentation of watery ■ "■. · '""

latiees in Examples 12 and 13 ■ verv / enöei; .. "■■ - '■■ - _; .- .."

■■ "■" Example 2 ....; ■ ■ "■.

Production of a solution of a partial acetal '-_ - won Poiy ¥ i.nylaXfcob.ol as BiclningsBiittel with a colo ... tulargewielit won approximately 3000. - "

A suspension of 5 ropes of a "partially hydro- ...

lysed polj ^ injlaeetats' technical -quality ia 25O- ^; "'"' * ■ "'■ Ό098357096Λ. ^: ,."^;

BAD ORiQlNAL

.. ■■ - ■ & -

Metbanal "ropes have been converted into one with a reflux condenser, A flask equipped with a stirrer and thermometer was brought. A solution was added to this suspension prepared by dissolving 0.5 part of sodium hydroxide in 50 parts of methanol. The contents of the flask was refluxed for 8 hours. The precipitate obtained after this time was filtered off, washed with methanol and placed in a vacuum oven at 60 ° -G dried. A 20% (w / w) aqueous solution of the Polymers were prepared by the procedure given in Example 1.

The partial benzaldehyde derivative of polyvinyl alcohol, Now containing less than $ 2 (w / w) remaining Vinyl acetate units were then made. A mixture of 10 parts of the aqueous polymer solution, 1.8 Parts of propane-1: 2-diol, 0.71 parts of benzaldehyde and 0.086 Divide 89% (Gev /./Wt.) Phosphoric acid into one Brought a flask equipped with a reflux condenser, a stirrer and a thermometer. The content of the The flask was held at reflux for two hours, after which the position of the condenser was changed and one hour slow removal of volatile components from the Mass of the solution was started by distillation. Select. ■ During this process, the water solubility of the

BATH ORIGINAL

■■■■ ' .v * 00983570964

. . . : · ■ .. ■. 190572t

Polymers tested. Small samples of the polymer solution were removed from the flask and taken to 25 times the sample weight. diluted with 0.01 molar ammonia solution.; -, The temperature above which the polymer formed a precipitate in this dilute sample rose, and when this temperature reached about 100 ° C., the mass of the solution in the flask became with - ^ minonia from · P specific gravity 0.580 neutralized. There was a _-: conducted further Entferung of the volatile components in the Hasse the solution by distillation, was until the Peststoffgehalt the solution is about 40 ^.

The percentage of acetal mixed monomer units in the mixed polymer was determined based on the infrared spectrum valued at about $ 3. Ea were not terminal Groups with 4 or more carbon atoms by analysis of the thickener found. . ; · ■

The viscous solution obtained, which gelled on cooling, is hereinafter referred to as thickener 2, '■ "■■ -'■■■" -.- '"..-.- ■.;. ■ - ■

■■ - .. The thickener was used in Example 14 to thicken an aqueous latex. ". · -. ■ .- _......- ^

mmä ilÄ | Ö983 5/0984

- " Example 3

Production of a mixed polymer from vinyl alcohol and a saturated tertiary ester of vinyl alcohol as dicing agent by bead polymerization of vinyl acetate and tertiary vinyl ester with subsequent drying of the mixed polymer thus formed, removal of the acetate groups and production. of aqueous solutions from it. ' . ■

The general method for making the mixed 'polyaeren is as follows

A mixture of O ₃ OI parts of a partially hydrolyzed polyvinyl acetate with a holeloil weight. of 12,5,000 iind a content of residual polyvinyl acetate * of about $ 20 (w / w) in 230 parts of water was placed in a flask equipped with an ax, a reflux condenser, a stirrer and a thermometer. The contents of the flask was heated to 70 ⁰ C and held for 30 Hinuten at this temperature. The clear solution obtained was cooled to 40 ° C., and a mixture of 99 parts of vinyl acetate, 1 part of tertiary vinyl ester, 5 parts of benzoyl peroxide and 3.3 parts of tertiary dodecyllaercaptan were added. The contents of the flask were then held at mild reflux for 3 hours during which time

; 19Q57.Z-1 ---

Time the "temperature rose slowly from about 7D ⁰ G. ■. = -" -. .-.

After cooling, the water was separated from the viscous, coalesced polymer phase by decanting. "A solution of 5 parts of the polymer in 200 parts of methanol was poured into a condenser with a reflux" and a stirrer Fitted flask, and _ .- "Fe to this were added 0.2 parts of sodium hydroxide, dissolved in ... ^{: j.} 20 parts of methanol. The contents of the flask -." held at reflux for 4 hours; during this . Time a cloudy precipitate was formed, ITa c la addition ".." of 200 parts of acetone, the mixture was filtered off, washed with methanol and added in a vacuum oven. 60 ^ C getroclc-. net.

The interpolymer thus obtained was

. in water under. Use of that described in Example 1. Procedure solved. The viscous solution obtained, which. gelled on cooling and having a solids content "van ..- ■■ '":. "- about $ 30 (w / w), is hereinafter referred to as thickener .3 · The molecular weight of the. Misc.hpoly- ^: On the basis of its viscosity in a (weight / weight) aqueous solution at 20 ° C., the molar percentage of the mixed monomer, based on the total monomer units in the Diclamg- ■ means was calculated to a value between '5.0 and 6.0, whereby the terminal residues present therein are' ·

₍ . »F ^ OO.9835 / 0964

. . BATH

were taken into account. ' :

The thickener was used to thicken aqueous Latices used in Examples 15 and 16.

■ Example 4

Production of a further mixed polymer from vinyl alcohol and a saturated tertiary ester of vinyl alcohol as a thickener "and the preparation of an aqueous solution therefrom.

In the process of making this thickener the method given in Example 3 was followed, except that the weight of the monomers used was 95 parts of vinyl acetate and 4 parts of tertiary vinyl esters.

The copolymer finally obtained was in Water using the procedure described in Example 1 dissolved, being a viscous solution with 'a content of about $ 25 w / w of the interpolymer was obtained. This solution, which has a tendency to gel when Cooling is hereinafter referred to as thickener 4. The percentage molar fraction of the mixed monomer, based on the total monomer units in the

00983 5/0 984

■ 31,; ■■ - ■ '

■ ·. ! '9 ÖS

Thickener, was calculated as 5 "to SfS", where -.-..- the existing terminal estates were retained therein. The molecular weight of the "detergent" became ". As determined in Example 3 to be about JOOO. /

The thickener became more aqueous to thicken Latices used in Example 17. ·. , '. .. ■ / ■ -.

Examples 5 "to- 8.""- / ■ - .. ^; .

Manufacture of a string of dietetic solutions partial acetals from vinyl alcohol, produced by. Reaction of polyvinyl alcohol with a molecular weight, weight of about 7,000 with benzaldehyde.

A solution of 25 ₉ 65 'parts of polyvinyl alcohol with an average molecular weight of. about 14 and a salary of about $ 1. remaining. Vinylacetatei'nheiten in 95 $ 40 parts of water in a with a · Rückflußkondensatorj a stirrer and: made a thermometer equipped reaction vessel "specialist to heating the solution to reflux 'were O ₁ 40 parts of ammonia with a specific gravity" of .0,88 and 0.55 parts of 130 vol. of hydrogen peroxide were added, and the reaction was then refluxed for 2 hours

heated, whereupon the average molecular weight des polyvinyl alcohol, estimated on the basis of the viscosity of a 4% solution of the polymer, is reduced to about 7000 had been. ·. -

(. C-ew./G-ew): To the solution of polyvinyl alcohol 30 parts propane-1 were then 2-diol, 1,5 O5 $ strength by weight phosphoric acid and 10.0 parts of benzaldehyde was added. Heating under reflux was continued for three hours, during which time the solution became cloudy. The position of the capacitor was changed and it became a slow distance of the. volatile .Komponenten au :: the mass of the solution started by distillation. Samples of 13 parts each were removed from the flasks at time intervals and neutralized with ammonia with a specific gravity of 0.80 after each amount of 3 ₅ 2, 8.5, .13.8, 19.0, 23.3, 28.3 or 34.6 parts of volatile components had been distilled from the batch.

The samples of the solution obtained after distilling 19.0, 23.3, 28.5 and 34.0 parts of volatile components are referred to below as thickeners 5, 6, 7 and 8, respectively. ·

'The percentages of. Acetal-M-ischmonone units in the mixed polymer were based on 'the infrared spectra

009835/0964

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BATH

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The procedure for making these thickeners followed the general method given in Examples 5 "through 8" except that benzaldehyde was used. 15 ropes of propionaldehyde was replaced. An additional 20 parts propane-1: 2-diol were added after 24 parts of volatile components had been distilled warm from the cash register of the mixture, and samples of 13 parts each were taken after total amounts of 55.2 and "60.1 Parts of volatile components had been distilled off.

After reacting with propionaldehyde, the mixture had separated into two phases, but it became again homogeneous after 45 »0 parts of volatile components through the distillation had been removed. '

The samples of the solution obtained after distillation of 55.2 and 60.1 parts of volatile components are hereinafter referred to as thickeners 9 and 10, respectively. ■ ·. ·

The percentage of acetal mixed monaural units in the copolymers was due to the infrared spectra and the scores obtained are summarized in Table I. with the estimated values of the solids content ■ Larweights given. There were no final results

009 835/0 964 BAOORlQtNAL

18 ■■■. - ■■ - .- '.' ■ 190.572-

Gen groups with 4 or more carbon atoms found by analysis of the detergent, *,. \

Example 11

. Production of a thickening agent, 'testing-aiis'. a mixed polymer of vinyl alcohol in which the mixed monomer units at the end of the polymer chains, sit and prepare aqueous solutions from them. The mixed monomer units \ 7 earth obtained from chain end groups, introduced during the polymerization reaction. The general procedure for. Manufacture of the Mixed polymers is as follows * ■■ _ ■■ '.

Am Gremisch aua 15 parts of vinyl acetate, 0.5 parts of azodiisobutyronitrile and. 3.0 .Teilen n-octyl mercaptan was' in a fitted with a reflux condenser, a stirrer, a thermometer and a dropping funnel reaction vessel gebracht.-Der was used: heated to about 7O ⁰ C, at which temperature an exothermic polymerization took place. The contents of the Seaktionsgefäßes was "kept at reflux funnel" at about 76 ⁰ C under Susata methanol from .dem drip ITachdeia had decreased the exothermic V / ärmeentwicklung which was Rückfiußtenperatur while-further 60 minutes by

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190572 ^

"■"'"'" .. Examples 12 to 26 .. · V

Making a strain of thickened aqueous; -. ' Latices by the method according to the invention and with the incorporation of thickeners T. to If from ". Examples 1--11. The thickened latices were pigmented and formed latex paints. . .- ■

Each coat of paint is made from a mill base material produced according to the following approach, won: .. ".

A mixture of "-. ■ ■. ■ ^:

. Pigment grade titanium dioxide 10.0 parts technical defoamer; . ' .0.08 parts of 25% (w / v) aqueous solution

of sodium hexamethaphosphate 0.24 part

Water - ' . .2.7 parts

was ground for 16 hours in a laboratory ball mill •. ' _: _:

- - The ICahl Grunamateriä produced in this way. was, under; v; Stir added to 26.0 parts of the latex to be tested. · Two mixtures based on Latex A bsw. Latex, .3, the WUR prepared as described above. All Kisch products had flow coefficients greater than 6.

-. '. ■■' ^{ί! Ί% &% <} ^ 00983 5/0 96 4 · BADORlGfNAL

In Examples 18 to 21, 0.2 parts became one non-ionic surface-active agent (¥ onylphenol, Ethylene oxide conaensate) added.

Thickeners according to Table II were turned into partitions. ien of these mixtures are added with stirring, the thickeners if necessary to increase their flowability have been heated to facilitate handling. .

It has the flow property of each .This thus formed thickened aqueous latices at 25 ⁰ C by means of a "Epprechf'-Rheomats," 15 "using the" B "-shell measured. The plastic viscosities and flow coefficient, as defined above, and determined vmrden The flow coefficients were all above 2, v / as indicates good flow. Bss was found when these paints were painted on glass plates, with paint marks flowing out to an extent that was unusual for conventional latex paints.

The improvement of the flow, which usually goes through Increasing the amount of the mixed monomer in the thickener is obtained, is demon- strated in Examples 16 and 17

- BAD ORIGINAL

009835/0964.

striert. It can be seen that a larger weight percentage of thickening agent "4 was required , in order to achieve the same plastic viscosity as that obtained by Diclomgs.- '--- agent 3 to achieve given, however, the valley coefficient increased from. 2.4 to 5 »7 an« The increase in _: flowing ^; Coefficient with increase in the proportion of _Mischaonq-: Neren-in the Dickungsmittel'ist .also, from a comparison. V - _: same as examples 22 and 23 'can be seen, example' - '. 20 shows in connection with Examples 18 and 19, as \ a thickened aqueous latex with satisfactory JPließkoeffizienten by re-selection of the Dickunga- - _ ^ means on the basis of Mschmonomerenlconzentrationj. > - _; ^; can be achieved if the first selected ■ - "■" - "■ -." ■ Thickener (Example 20) has a low Pließkoeffisienten. This is again explained in comparative examples 24 and 25. :,

BATH ORIGINAL Table II

Example "Plic ^ cigensciiafi; der medium JTr. Parts of Dili paints

1 A. medium
solvable Plastic,
■ YisliOsi- " c) ^Z oeffi- 1 Λ
.η. did in - ■
Poise (25 O ient 12th 2 *
B. ., 1.3 0.9 5 , 5 13 ' 3 *
B. 2.6 1.8 12th , 2 14th 3 A. 1.3 0.8 2 15th 4th A. 1.5. 0.8 2 , 3 16 6th B. 1.4 0.8 5 , 4 17th 7th 'B 2.6 0.8 A.
« , 7 18th • 8th B. 4.0
(+ 1.0 parts
Water) 0.60 .. 2 , 3 19th 10 B. 4.6
(+ 0.6 parts'
V / water) 0.81 0 , 2 20th 5 A. • 5.6 O., 82 3 , 7 21 6th A. 4.6 0.65 2 , 0 22nd 9 A. 3.5 0.84 1 , S. 23 10 A. 3.5 0.67 9 , 5 24 11th A. 2.5 ^# * - 0.59 1 , 5 25th 3.6 0.49 5 ,1 26th "· 2.3 0.63 , 7

* Weiehgeinacht with $ 2 1/2 (w / w) tri-n-butyl phosphate.
^fr * On the verge of indescribability.

009835/0964

Claims (2)

190572 Patent claims ■ - ■ '"-, ■ - ■ ·'. Thickened aqueous latex with a ratio: 3I-zceificients greater than 1.5 and a plastic viscosity of at least 0.3 poise" at 25 C, characterized in that of latex disperse polymer particles ■ with an average diameter of 0.04 to. 2 ', 0 microns, dispersed in an aqueous .liquid,. ■ P. ■ and 0.1 "to 10.0 G-ev /.- ^., Dezogen on the .GFev / icta.t of the polymer particles, a polymeric di'ckungsraittels soluble in the aqueous latex _ contains, where'Dei -das . " Thickening agent consists of a chain-like copolymer of vinyl alcohol with at least one mixed monomer. Containing 4 to 13 carbon atoms, the homopolymer of which is essentially in the .aqueous; latex is insoluble and the mixture polymer has a molecular weight of 2,000 to 10 '. 000 has and the proportion of. =, / _``_. k mixed monomer units therein with the number of carbon .. carbon atoms in the mixed monomer according to the following table, is related: ·. ■. ■: '-_ :; C-Atoms in the mixed-Hol mixed monomer units as prosent monomers ". Set of the total monomer units Minimum. '■'. Maximum 4 10.0 '".' "■■ 50 5 '■■■■■. 6.0 ■ ■" " 35 6 3.0 2Ö 009835/0964 BADOR1GIMAt C-Atoms in the mixed.- Get milk mononic units as a percentage of the total monomer units set of the total monomer units, minimum maximum. 6120.515 - 180.2 25 21 18 15 12 10 2) Thickened aqueous latex according to claim 1, characterized in that it contains dispersed polymer particles with an average diameter of 0.05 "to 0.4 microns. 5) Thickened "aqueous latex according to one of the preceding claims, characterized in that the proportion of the mixed monomer units in the thickener is related to the number of carbon atoms in the mixed monomers of the following lamella: BADORIQfNAL 009835/0964 CA-tome in the mixed mole of mixed monomer units as Proaent monomers.: Set of the total monomer units - ._ 4 15 Ms 30 '._ ■ "" - ■■ - ■; ■ \' .5 Q to 22 "- .V; : 6. 5 to 15 - "Ζ" V 7. 2 to 12 ':. 8 - ■ 1.5 to 10 '·.; '9 1, 2 to 9' 10 '. 1.0 to 8. : / ■■■■ -; /. 11 - "0.9 to 7 .- ■■■■" "; -; '12.' 0.8 to - 6 ■ \; _ T3 - 18, 0.3 to 5. ' 4) Thickened aqueous latex according to one of the preceding claims, characterized in that the continuous phase of the latex contains up to 40% by weight of water-soluble or water-miscible organic liquids. "5) Thickened Aqueous latex according to one of the preceding claims, characterized in that it contains, as organic liquid, ethylene glycol, propylene glycols, butylene glycols, 2 ~ ethoxyethanol 2V-butoxyethanol and / '.- ■■■ ". or diacetone alcohol." "Mi -« r- ■ β) Thickened aqueous latex according to one of the preceding claims, characterized in that it contains a polymeric di ersion emit tel mit-minaestraß a luisötinonoxaereneinheit selected from the group of olefins, aromatic substituted olefins, "- alkyl esters of alpha , "bet a-ät hy leni cally unsaturated I-iono- and dicarboxylic acids, vinyl alcohol esters of eonocar-donic acids of saturated, branched-chain hydrocarbons with a tertiary alpha-liohlenstoffa tom, ethers of vinyl alcohol and ethers, the monofunctional units of the formula. CH0 - CH - R - CH2 - CH - QT "form, where R, the inner hallD of a thickening element: can be the same or different, contains up to 8 carbon atoms and can be alkyl, alkylene, aryl, alkaryl or arallcenyl. 7 ) Process for the production of a thickened aqueous latex with a pour coefficient of greater than 1.5 and a plastic viscosity of at least 0.3 poise · "at 25DC, characterized in that a latex with a pour coefficient of greater than 5 and which is dispersed Polymer particles have an average diameter of 0.04 "to 2.0 microns, which 0 0.9835 / 0 96 A BA & ORIGINAL ■ are dispersed in an aqueous liquid, 0.1" to 10.0 wt on- the weight of the polymer part-. Chen, a soluble polymeric detergent, selected from chain-like copolymers of vinyl alcohol - "-. with at least one mixed monomer with 4" to 10 carbon atoms, the homopolymer of which is essentially insoluble in the aqueous latex , solves., The mixed polymer has a molecular weight of 2,000 to 10,000 and the proportion of the mixed monomer units therein is related to the number of carbon atoms in the mixed monomers according to the following table: C atoms in the mixed mole of mixed monomer units as pros / demonomer .. set of the entire. Monomer units ■■■ .4 ■ 1O5O5-. 6.0β: .7 -8V 1.0. 90.810Ζ 0.7.11; "- ■ 0.612 -" .- V 0.513 ..- 18-; 0.2 minimum:. .Maximum "50 .25 18" 12 10 '8 009835./0964 8) .Method according to spoke 7S, characterized in that a latex with dispersed polymer particles is used, the average diameter of which is 0.05 to 0.4 microns. 9) Method according to one of the preceding claims. characterized in that a thickening agent is used with a proportion of mixed monomer units which is related to the number of carbon atoms in the mixed monomer according to the following table: C atoms in the mixed - mole of mixed monomer units as percentage of the total monomer units .4 4 15 to 30; 5 8 to 22. : 6 5 to 15 · ■ -. ■ 7 2 to 12 ■ 8 · '1.5. to '10 9 / 1.2 to 9 10 .1.0 to 8 11 "0.9 to 7.: • 12' ■ 0.8 to 6 - 18 0.3 to 5 10) Procedure, according to one of the above -herent claims, characterized in that a latex is used with a BAD ORIGIN / ". 009835/0964. continuous phase which contains up to 40% water-soluble or water-miscible organic liquids." . - 11). Process according to one of the preceding claims, characterized in that the organic liquid used is ethylene glycol, propylene glycols, eutylene glycols, 2-ethoxyethanol, 2-butoxyethanol and / or diacetone alcohol. 1. 2) Method according to e .nem of the preceding claims, characterized in that the 'polymeric thickener one such is used, the at least one mixed monomer unit from the group of olefins, aronate o-substituted Olefins, alkyl esters of alpha, oetaäthylenisch unsaturated mono- and dicarboxylic acids, Vinyl alcohol esters of monocarboxylic acids are saturated, branched chain Hydrocarbons with tertiary alpha carbon atoms, ethers of vinyl alcohol or acetals »■ the monaural units. the formula. ^BATH Q098M / Ö964 "Form where R, the" within a thickener molecule can be the same or different, contains up to 8 carbon atoms and alkyl, alley le n, aryl, alkaryl, May be aralkyl or aralkenyl. 009835/0964