WO2000053641A1

WO2000053641A1 - Novel polymer thickening agents and uses thereof particularly in printing pastes for textiles and in cosmetics

Info

Publication number: WO2000053641A1
Application number: PCT/FR2000/000532
Authority: WO
Inventors: Mehrdad Beheshti; Emmanuel Villard; Lionel Champagnon; René Hund
Original assignee: Snf S.A.
Priority date: 1999-03-11
Filing date: 2000-03-02
Publication date: 2000-09-14
Also published as: AU3171100A; FR2790759A1; FR2790759B1

Abstract

The invention concerns compositions containing vinyl synthetic polymers or copolymers with dry particle size ranging between about 0.2 and 0.6 microns, preferably between 0.2 and 0.4 or 0.3 microns, in the form of an invert emulsion obtained by oil emulsion polymerisation, or a dispersion in an aqueous medium, generally water. The quality of the thickening agent (in particular, resolution in the application of printing paste while preserving a high colour yield) is improved. The invention is useful as thickeners, and more particularly as bodying agents for printing pastes, in particular for textiles, specially in pigmentary printing processes but also for printing processes using the so-called fixed-and-washed technique in particular, in cosmetics and other uses of thickening agents.

Description

New polymeric thickening agents and their applications in particular in printing pastes on textiles, and in cosmetics.

The present invention relates to the technical sector of synthetic thickening polymers and their applications in the usual fields of such polymers, in particular in printing pastes for textiles, in cosmetics, and other known applications.

The use of such polymers in the field of textile printing is now very common, in particular for so-called “pigmentary” printing, that is to say carried out using dyes of the pigment type.

Crosslinked polymers which swell with water and which are in the form of a “reverse” water-in-oil emulsion or in the form of a dispersion of dry polymer in an organic medium are used.

In the case of a polymer prepared in reverse emulsion, it is used, at the site of use, in a known manner after its "inversion" with water.

Reverse emulsions have been described by Vanderhoff, USP 3,284,393.

Reverse emulsions, their general properties, and their mode of use, in particular the step of inversion with water before use, are now well known to those skilled in the art.

There are also synthetic thickeners in other forms that can be used as synthetic thickeners in the printing paste composition, but they have significant drawbacks compared to reverse emulsions and organic dispersions. In the patents (GOODRICH) US 3,940,351, EP 0,128,237, US 2,923,692, Fr 2,277,109, are described the preparations of crosslinked polymers, swelling in water obtained by polymerization by precipitation in an organic solvent. A very fine and very pulverulent is obtained by evaporation of the organic solvent. These powders are very difficult to use given their pulverence and the difficulty of dispersing them in an aqueous medium while avoiding the formation of agglomerates.

In the patents EP 0,216,479 (ACL) and EP 0,013,836 (R&H), the syntheses of associative polymers are described in the form of an aqueous emulsion which can be used as a thickener or especially as a co-thickener of printing paste (examples 8,9 & 10 of patent EP 0,216,479). However, it is necessary to use several products, the user prefers to use only one thickener. The fuselage is generally improved by this type of co-thickener but the color yield is reduced.

Patent USP 4,059,552 (Zweigle et al., DOW CHEMICAL), describes crosslinked polymers of monomers such as acrylamide and sodium acrylate, in the form of suspensions or water-in-oil emulsions, and of dimension 0.2 to 4 micron particle size. A low HLB surfactant is used. The patent describes the application as thickeners. The likely particle size range of this patent is 1 to 3 - 4 microns

Patent USP 4,077,930 (Lim et al., Calgon) describes self-reversible emulsions of monomers of the acrylamide and AMPS type or of acrylamide and sodium acrylate, and of analogous monomers, prepared using around 10% by weight of surfactant, the lipophilic-hydrophilic balance (HLB) can be around 9. The products obtained are therefore, due to the reaction parameters, polymer emulsions, not crosslinked, and whose particle size is very small, of the order of 0.2 microns.

The industry considered has also become accustomed to calling "emulsions" emulsions whose particle size is less than 0.1 micron. In particular, the work of Candau et al. (FR 2 565 623, 2 567 525) have highlighted these “microemulsions”, as well as their characteristics of thermodynamic stability and transparency, and have established the importance of a few parameters, such as in particular the proportion of surfactant and the HLB of the surfactant or of the mixture of surfactants, to obtain a microemulsion whose particle size is around 0.1 to 0.2 micron, or below 0.1 micron.

The work of Candau et al. have established the advantage of combining a high proportion of surfactant (of the order of 9 to 25%) with an HLB of between values of the order of 8 to 11.

Patent USP 4,443,576 (Bhattacharyya et al., Nalco) describes thickening polymers in the form of reverse water-in-oil emulsions of monomers such as acrylamide, acrylic acid and hydroxyethyl methacrylate, and which are qualified as very stable if the particle size is between 0.1 and 5 microns, preferably 0.2 to 3 microns, preferably 0.2 to 2 microns. The HLB used is located between 4 and 9 by reference to patent USP 3,997,492 (HLB 7 to 9).

We will also cite the patents USP 4, 196, 272, 4, 143,222 and the patent (NALCO) USP 3,997, 492 which describes the choice of an HLB between 7 and 9, in order to obtain a stable emulsion with particle size less than 1 micron, no application being described.

Patent EP 0 161 038 (Allied Colloids) describes thickeners for printing paste which consist of crosslinked polymer compositions, prepared in reverse emulsion, of particle size between 0.2 and 3 microns. The starting monomers are for example acrylamide and acrylic acid or analogous monomers. It is indicated that the properties of the polymer can be modified by an appropriate choice of the proportion of crosslinking agent and of the molecular weight. The prior art relating to textile printing pastes therefore generally establishes the advantage of reverse emulsions of acrylamide and of acrylic acid or acrylate, or similar monomers, preferably crosslinked, and of dry particle size included. between 0.2 and 3 to 5 microns.

No prior art mentions or suggests the interest, in this particular sector of industry, of selecting the particle size of the polymer. Only patent EP 0 161 038 (Allied Colloids) directs towards smaller particle sizes than those of the prior art, but it notes that the dimensions of the prior art are already "very small", and it does not direct towards the lower range of the 0.2 - 3 micron sector that it recommends.

It has now been discovered that the properties of the thickeners are significantly improved by selecting particle sizes included in the lower range of the prior art of conventional emulsions, that is to say approximately 0.2 to 0.6 microns, preferably 0.2 to 0.4 or 0.3 microns.

In particular, certain properties of printing pastes for textiles are improved by selecting particle sizes included in the lower area of the prior art of conventional emulsions, that is to say approximately 0.2 to 0.6 microns, of preferably 0.2 to 0.4 or 0.3 microns.

In particular, the quality of the thickener is improved (the fusing is improved) while retaining a good color yield.

The term “polymers” is used here to denote homopolymers and copolymers, terpolymers, etc., monomers considered with copolymerizable monomers well known to those skilled in the art.

it is surprising to obtain such a set of interesting properties, especially in a field which is not that of "microemulsions", highlighted by Candau et al. and which have focused the subject of numerous researches since then. Improvements are also observed during the use of these new thickeners in cosmetic applications with regard to the physical characteristics of the formulations obtained, as well as in the other applications of thickeners, well known to those skilled in the art.

The polymers thus selected are useful as thickeners in themselves, and also as a co-thickener in combination with a conventional emulsion (that is to say with a particle size of the order of 0.9 - 1 to 3 - 4 or 5 microns) of thickening polymer. This property is advantageous for reducing the cost of the operation and is particularly effective for printing certain textiles such as cotton polyesters.

The polymers according to the invention can be used directly in the form of the reverse emulsion (which results from polymerization under the conditions known as reverse emulsion) which is itself inverted with water before use.

It is known that these polymers can also be used in the form of the product obtained by dehydration (generally by distillation or spray-drying or "spray-drying") of the reverse emulsion obtained during the polymerization.

When it is desired to carry out such a dehydration, a light oil and a heavy oil are combined to form the non-aqueous or organic phase. During dehydration, the light oil is eliminated, as well as the water and an organic dispersion of “dry” polymer is obtained in the rest of the heavy oil.

If heavy oil is not used, dehydration results in a powder which can also be used.

Dehydration or drying is known to those skilled in the art, and is carried out by distillation, in particular azeotropic distillation, or spray drying or “spray-drying”. As mentioned above, the polymers can also be used in the form of a dispersion. These particles swell in the aqueous dispersion medium and form a latex which is used as a thickener.

The invention also relates to mixtures and combinations of these different forms of presentation with other thickeners of the prior art, in a suitable form (for example mixture of two emulsions, or mixture of an inverted emulsion with a solution, etc. ....).

The invention will be more particularly described in what follows with regard to textile applications, but this without any limitation being implied, the skilled person will be able to extrapolate to other applications, cosmetics and others, the advantages obtained according to the invention and found more particularly in the textile sector.

The polymers of the invention are, in the technical sector of textile printing, generally of the anionic type, as will be understood by a person skilled in the art. However, this rule is waived when the dyes or printing reagents are cationic.

The present invention therefore achieves for the first time a good compromise between the particle size and the cost of the polymer, while unexpectedly improving certain properties or set of properties of the thickening compositions.

Other characteristics and advantages of the invention will appear better on reading the description which follows, and with reference to the appended drawing, in which:

FIG. 1 represents the fusing on a polyester (PE) - cotton type fabric with 65% PE and 35% cotton treated with a composition of the prior art.

FIG. 2 represents the fusing of test No. 23 of Table II according to the invention on a PE cotton / polyester fabric; FIG. 3 represents the fusing of test No. 24 of Table II according to the invention on a cotton / polyester PE fabric;

FIG. 4 represents the fusing of test No. 25 of Table I I according to the invention on a cotton / polyester PE fabric;

- Figure 5 shows the fusing of test No. 4 of Table I according to the invention on a cotton / polyester PE fabric.

The present invention therefore relates to compositions containing at least one or more synthetic vinyl polymers (or copolymers or terpolymers, etc.) with a dry particle size of between approximately 0.2 and 0.6 microns, preferably 0.2 and 0, 4 or 0.3 microns, in the form of the reverse emulsion obtained by polymerization in reverse emulsion, or of organic dispersion of “dry” polymer, or of powder, or of solution in an aqueous medium, such as water, of this powder, or any other form accessible to those skilled in the art.

In a preferred embodiment, the invention relates to compositions containing at least one or more synthetic polymers or copolymers totally or partially insoluble in water, swellable or swollen with water, with a dry particle size of between approximately 0, 2 and 0.6 microns, preferably 0.2 and 0.4 or 0.3 microns, obtained by reverse phase polymerization of a mixture of copolymerizable monomers which comprises

(a) at least one ethylenically unsaturated acid having free acid groups,

(b) at least one ethylenically unsaturated acid having neutralized (or salified) groups chosen from ammonium, amine, and alkali or alkaline earth metal salts and

(c) at least one crosslinking agent containing ethylenic unsaturation. Preferably, the proportions of said free acid groups to said salified groups during the polymerization is from 80/20 to 10/90.

Although difunctional acids can be used, it is preferred according to the invention that acids (a) and (b) are monofunctional acids, preferably monocarboxylic or monosulfonic.

Monocarboxylic acids are still more preferred.

Typical but nonlimiting examples of acids which can be used are the following:

vinyl sulfonic acids, (meth) sulfopropyl acrylate, itaconic, crotonic, maleic, fumaric,

preferably AMPS

more preferably (meth) acrylic acids.

The partial neutralization of the acid groups, mentioned above, can be carried out by partial neutralization of the monomer or else by mixing monomers, identical or different, one with free acid groups and the other with acid groups salified at least in part, and all known analogous methods.

Likewise, the monomers (a) and / or (b) can be used alone or in various mixtures in each category.

As salts, the sodium, or potassium, or amine, preferably aliphatic amine, salts will be preferred.

These amines can be primary or secondary, such as, for example, those described in patent EP 0 161 038.

Cross-linking agents are known (cf. EP 0 161 038) and include MBA (methylene bis acrylamide), allyl methacrylate, diallyl phthalate or glycol diacrylates, MBA being often preferred. The invention also relates to vinyl synthetic polymers with a dry particle size of between approximately 0.2 and 0.6 microns, preferably 0.2 and 0.4 or 0.3 microns, in the form of the reverse emulsion obtained. at the end of the synthesis, or of the product obtained by drying, generally by distillation, in particular known azeotropic distillation, or by spray-drying or “spray-drying”, of the reverse emulsion obtained by polymerization, or in powder, or the solution of this powder in an aqueous medium such as typically water, as described above.

The invention also relates to vinyl synthetic polymers with a dry particle size of between approximately 0.2 and 0.6 microns, preferably 0.2, and 0.4 or 0.3 microns, in the form of the product obtained by redispersion. or dissolving a powder in an aqueous medium.

The invention also relates to compositions containing synthetic vinyl polymers or copolymers with a dry particle size of between approximately 0.2 and 0.6 microns, preferably 0.2 and 0.4 or 0.3 microns, in the form of the emulsion obtained by inversion with water of the reverse emulsion obtained by reverse emulsion polymerization.

Preferably, the monomers used for the synthesis of the (co) polymers according to the invention will be chosen from the following:

anionic: ethylenically unsaturated monomers having

a carboxylic acid function, as an acrylic acid or methacrylic acid monomer,

a sulfonic acid function as a 2 - acrylamido - 2 - methylpropane sulfonic acid or AMPS monomer,

cationic: ethylenically unsaturated monomers such as chloromethylated MADAME, chloromethylated ADAME, DADMAC (diallyldimethyl ammonium chloride) non-ionic: monomers with ethylenic unsaturation and having no ionic function, such as acrylamide, methacrylamide, vinylpyrrolidone.

and generally the monomers described in patent EP 0 161 938 or patent EP 0 186 361 which are incorporated here by reference.

The monomers will be used in the following proportions: (% moles)

cationic: from 0 to 100%, preferably from 0 to 95%, more preferably from 0 to 90%

anionic: 0 to 100% preferably 30 - 50 to 100%

non-ionic: 0 to 100%, preferably 25 to 80%%, preferably

70 to 30%.

Mention will in particular be made of polymers containing from 5 to 100% of cationic monomers, the possible non-cationic balance consisting of nonionic monomers.

An amphoteric copolymer composed of

15 - 60 mole% of cationic monomer (s)

25 - 80 mole% of nonionic monomer (s) (ACM)

2 - 30 mole% of anionic monomer (s)

The cationic thickeners can in particular be used in cosmetics, although all of them can be used.

The (co) polymers according to the invention will preferably be obtained from acrylamide and acrylic acid or sodium acrylate.

It is also possible to replace the sodium acrylate with a reaction mixture containing acrylic acid and an appropriate proportion of sodium hydroxide.

Other salts than that of sodium may be used, such as the potassium, ammonium salt or other well-known equivalent salts. The ammonium salt or any other volatile base will preferably be used for so-called “pigmentary” applications.

For the other textile applications, in particular said “fixed-washed”, one can use the same salts, in particular the sodium salt.

Those skilled in the art will understand that different degrees of salification can be chosen.

The invention relates generally to the synthetic vinyl polymers defined above, obtained by reverse emulsion polymerization, and characterized in that the continuous oily phase consists of one or more oils chosen from the following:

mineral oils, vegetable oils, synthetic oils

non-organic solvents

halogenated hydrocarbons.

According to an advantageous embodiment, the acrylamide may represent of the order of 0% by weight to 90% by weight, preferably from 0% by weight to 50% by weight.

According to an advantageous embodiment, the acrylic acid or the sodium acrylate may represent of the order of 10% by weight to 100% by weight, preferably from 50% by weight to 100% by weight.

The polymer is found, at the end of the preparation, in dispersion in a medium immiscible with water such as kerosene, mineral oils, or generally a hydrocarbon or a halogenated hydrocarbon. If consideration is given to dehydration of the reverse emulsion thus obtained, an oil will be used which will be a hydrocarbon, optionally halogen, of volatile nature, which can be removed for example by azeotropic distillation, all in a known manner.

Most preferably, the (co) polymers according to the invention will be crosslinked. Preferably, the crosslinking agent will be chosen from crosslinking agents containing ethylenic unsaturations, such as methylene bis acrylamide (MBA), which will be generally preferred, allyl methacrylate, diallyl phthalate, and glycol diacrylates.

As regards the MBA, the proportion will be between approximately 50 and 5000 ppm, preferably 50 and 2000 ppm, or between 200 and 800 ppm, expressed in dry weight of all the monomers used.

The (co) polymers which are not crosslinked but branched (that is to say obtained by mixing a crosslinking agent with a known chain transfer agent) will also be usable according to the usual criteria of those skilled in the art.

It is also possible to use, according to the invention, mixtures of crosslinked and / or branched and / or linear (co) polymers.

It will also be possible to use chain transfer agents or chain length limiters, optionally in combination with crosslinking or branching agents, in order to control the structure of the final polymer. Reference will be made, for example, to patent EP 202,780 B1, at the top of page 6, incorporated here by reference.

The emulsions according to the invention generally have a non-transparent translucent appearance.

They are stable with an onset of phase shift beyond 5 to 7 weeks approximately, in a settling tube at 50 ° C.

The invention also relates to the application or use of the compositions containing synthetic vinyl polymers or copolymers with a dry particle size of between approximately 0.2 and 0.6 microns, preferably 0.2 and 0.4 or 0.3 microns. , in one of the forms described above, as thickening agents, and more particularly as thickening agents for printing pastes, in particular for textiles, in particular for pigment printing processes, but also for printing processes "fixed-washed" type printing (the fixing being different) which group together the techniques known as dispersed dyes, reactive dyes, etc.

To prepare a thickening composition according to the invention, the reverse emulsion obtained by polymerization can be used as it is, without isolating the polymer from the water-immiscible liquid. This reverse emulsion is then added to an aqueous liquid, which "reverses" said reverse emulsion and gives by swelling (by hydration with water) a gel or latex. The operation can be promoted by adding an emulsifier which promotes wetting of the polymer with water, in proportions of 0.05% to 5% by weight of aqueous medium, preferably 0.1 to 1%.

It is also possible, as indicated above, to isolate the polymer in the form of a “dry organic” dispersion by dehydration of the reverse emulsion obtained by polymerization, or in the form of a powder, or even a solution of this powder in an aqueous medium such as 'water.

The polymer according to the invention can also be isolated by any other technique, and the particles redispersed in an aqueous medium.

Finally, also as indicated above, the reverse emulsion can be inverted with water, and the resulting oil-in-water emulsion can be used.

Also as indicated above, the invention also relates, as new thickening compositions or new thickening agents, to mixtures of the polymers according to the invention, in any one of the above forms, with one or more thickeners or printing bases of the prior art, in a compatible form.

The invention therefore relates to a base for textile printing paste, characterized in that it comprises at least one vinyl synthetic polymer or copolymer with a dry particle size of between approximately 0.2 and 0.6 microns, preferably 0 , 2 and 0.4 microns, preferably 0.2 and 0.3 microns, in the form of the reverse emulsion obtained by polymerization in reverse emulsion, or of this emulsion itself reversed with water, or " dry organic dispersion ”, or powder, or polymer isolated and the particles of which are redispersed in an aqueous medium. The invention also relates to a base for textile printing paste, characterized in that it comprises at least one vinyl synthetic polymer or copolymer with a dry particle size of between approximately 0.2 and 0.6 microns, preferably 0 , 2 and 0.4 microns, preferably 0.2 and 0.3 microns, in the form of the reverse emulsion obtained directly by polymerization in reverse emulsion, or of this emulsion itself reversed with water, or of "Dry organic dispersion", or powder, or polymer isolated and the particles of which are redispersed in an aqueous medium.

Said other thickening polymers which can advantageously be mixed with the bases according to the invention are conventional thickening polymers whose particle size is greater than 0.6 microns, and is typically situated in the range of approximately 1 to 3 microns or 5 microns, as described in the aforementioned patent EP 0 161 038.

The invention also relates to textile printing pastes characterized in that they contain at least one base as described above.

The invention also relates to printing pastes comprising as thickener at least one polymer or thickening composition according to the invention, as well as textiles the printing of which has been carried out at least in part by such a polymer or thickening composition.

The invention also relates to printing pastes comprising as thickener at least one polymer or thickening composition according to the invention and at least one dyestuff (pigments and dyes) of all types used in the textile industry.

Examples of pigments that may be mentioned include the unisperse blue BE (TM) from Ciba-Geigy; Printofix H 3BD Red (TM) or H BFC blue (TM) from Clariant; or the yellow K 4 G Imperon (TM) or red K GC from Hoechst. Examples of dispersed dyes that may be mentioned include Dianix (TM) yellow S 6G from Dystar, and the entire Dianix (TM) range, or Foron (TM) yellow SE.FL or red RD-BR from Clariant.

As examples of reactive dyes, the Drimarene (TM) yellow R3GL series, R3GN red or R2RL blue from Clariant, or the Levafix (TM) PN series, PN 5GN yellow, PN FB red, or PN 3R blue from Dystar.

Examples of acid dyes that may be mentioned include the Nyiosane (TM) yellow N 7GL or Sandolane (TM) blue E HRL series from Sandoz.

Ciba-Geigy, Clariant, Dystar, Hoechst, Sandoz are registered trademarks.

As examples of textiles which can be treated with a printing paste according to the invention, the following are non-limiting examples:

cotton, polyester-cotton fabrics, polyester,

- terry fabrics, nonwovens,

natural, modified natural or synthetic fabrics,

or their mixtures,

or textiles made of mixed fibers of all kinds.

The invention also relates, according to a second option, in general:

a base for textile printing paste, characterized in that it comprises at least one synthetic vinyl polymer or copolymer with a dry particle size of between approximately 0.2 and 0.6 microns, preferably 0.2 and 0, 4 microns, preferably 0.2 and 0.3 microns, in the form of the reverse emulsion obtained directly by polymerization in reverse emulsion, or of this emulsion itself reversed with water, or of “dry organic dispersion”, or of powder, or of isolated polymer and the particles are redispersed in an aqueous medium, mixed with at least one other thickening polymer.

- a base for printing paste for textiles, characterized in that said other thickening polymers are thickening polymers whose particle size is greater than 0.6 microns, and is typically in the range of about 1 to 3 microns or 5 microns or more.

- A base for textile printing paste, characterized in that said other thickening polymers are thickening polymers whose particle size is in the range of about 1 to 3 microns or 5 microns.

a base for printing paste for textiles, characterized in that said other thickening polymers are thickening polymers chosen from those described in the aforementioned patent EP 0 161 038, in particular:

those obtained by reverse emulsion polymerization of copolymerizable monomers which comprise at least one ethylenically unsaturated acid and at least one crosslinking agent with ethylenic unsaturation, said acid comprising (a) at least one unsaturated acid comprising free carboxy groups and (b) at at least one unsaturated acid containing acid groups salified with a sodium, ammonium or similar ion, such as:

acrylic acid / sodium acrylate

ammonium acrylate / acrylamide

acrylic acid / sodium acrylate / acrylamide textile printing pastes characterized in that they contain at least one base as described above.

textile printing pastes characterized in that they contain at least one coloring material as described above.

- the above textile printing pastes, characterized in that they contain at least one reactive dye.

the above textile printing pastes, characterized in that they contain at least one pigment dye.

the above textile printing pastes, characterized in that they contain at least one acid dye.

the above textile printing pastes, characterized in that they contain at least one dispersed dye.

the above textile printing pastes, for pigmentary applications, characterized in that they additionally contain at least one binder;

- This binder is preferably chosen from standard binders of the acrylic or butadiene-styrene type.

printing pastes for applications using dyes, of the reactive dye, dispersed dye type, “fixed-washed” technique, characterized in that they do not contain a binder.

the above textile printing pastes for pigment applications, characterized in that they additionally contain at least one fixing agent and other conventional additives; the above textile printing pastes, characterized in that the reactive dye is chosen from the following: Drimarene (TM) series yellow R3GL, red R3GN, or blue R2RL from Clariant, or the Levafix (TM) PN series , PN 5GN yellow, PN FB red, or PN 3R blue from Dystar.

- the printing pastes for textile above, characterized in that the pigment dye is chosen from the following: the unisperse blue BE (TM) from Ciba-Geigy; Printofix H 3BD Red (TM) or H BFC blue (TM) from Clariant; or the yellow K 4 G Imperon (TM) or red K GC from Hoechst.

- the above textile printing pastes, characterized in that the dispersed dye is chosen from the following: Dianix (TM) yellow S 6G from Dystar, and the entire Dianix (TM) range, or Foron (TM ) yellow SE.FL or red RD-BR from Clariant.

the above textile printing pastes, characterized in that the dispersed dye is chosen from the following: series Nyiosane (TM) yellow N 7GL or Sandolane (TM) blue E HRL from Sandoz.

The invention also relates to textiles or similar products characterized in that they have been printed using a printing base or a printing paste according to the present invention.

As textile and similar products, there may be mentioned in particular:

cotton, natural or modified natural,

polyester,

mixed fibers such as:

cotton / polyester,

- "Lycra" (TM)

polyamides, silk, wool,

acrylic fabrics,

and their mixtures,

and other fibers and fiber mixtures.

EXAMPLE PLES

The following examples illustrate the invention without, however, limiting its scope.

Examples of synthesis:

A chain transfer agent or chain limiter was used, as well as a crosslinking agent, under the conditions indicated at the bottom of Table I or of Table I I. The aim is to obtain a control of the polymer structure as is generally known to those skilled in the art.

Pure product

Thickener # 3 in Table I

An aqueous phase of monomers is prepared in a one-liter beaker by mixing 133 g of 50% acrylamide, 157 g of acrylic acid, 150 ppm of methylene-bis-acrylamide / weight of active material, 150 ppm of bis-acrylamido-acetic acid / weight of active material, 0.09% of a 40% aqueous solution, of pentasodium salt of diethylenetriaminepentacetic acid / weight of the aqueous phase, 150 ppm of potassium bromate / weight of material active, 200 ppm of sodium hypophosphite / weight of active ingredient, an ammonia solution 28 ° B to obtain a pH of 4.8, as well as the water supplement to obtain 670 g. Simultaneously, an organic phase is prepared in a one liter reactor by mixing 110 g of mineral oil, 150 g of a hydrocarbon solvent distillation fraction between 175 and 225 ° C, 7.9% of sorbitan monoisostearate / weight of organic phase, 13.3% of polyethoxylene sorbitan trioleate 20 / weight of organic phase, as well as 440 mg of azobisisobutyronitrile.

The aqueous phase is poured into the reactor and mechanically emulsified to obtain the desired particle sizes. The emulsion thus formed is deoxygenated by bubbling nitrogen through for a sufficient time. The polymerization is initiated by injection of sulfur dioxide. After polymerization, the emulsion can be used as it is or can be dehydrated by azeotropic distillation, alone or in mixture with another emulsion as described in patent EP 0 161 038, in particular those obtained by reverse emulsion polymerization of copolymerizable monomers which comprise at least one ethylenically unsaturated acid and at least one ethylenically unsaturated crosslinking agent, said acid comprising (a) at least one unsaturated acid comprising free carboxy groups and (b) at least one unsaturated acid comprising acid groups salified with a sodium ion, ammonium or the like, such as:

acrylic acid / sodium acrylate

ammonium acrylate / acrylamide

acrylic acid / sodium acrylate / acrylamide

Without dehydration 1, 8% of polyethoxylated nonyl phenol 9 (polyethoxylated 9 times) are added to the emulsion described. Thickener No. 3 is obtained. The particle size is measured using a Horiba LA 900 laser granulometer from the company HORIBA (TM) France. The average particle size measured for this example is 0.2 microns after polymerization. After concentration (distillation) of the emulsion described at 60% of active material, the average particle size measured is 0.13 micron, 3.0 g of polyethoxylated nonyl phenol 9 are added to the concentrated emulsion.

Product mixed with other thickeners of the prior art

Thickener No. 13 of Table II (test 20)

A reverse emulsion is prepared by mixing 12.7% of the emulsion described with 87.3% of a reverse emulsion as described in patent EP 0 161 038, then dehydrated by azeotropic distillation (example No. 1c) . 3.0% of polyethoxylated nonyl phenol 9 are added to the concentrated emulsion thus prepared.

Thickener No. 20 of Table II (test 28) (prior art)

The reverse emulsion is used as described in patent EP 0 161 038. After dehydration and concentration at 60%, 3.0% of polyethoxylated nonyl phenol 9 are added to this concentrated reverse emulsion.

Examples of applications:

a) Pigment dye:

Printing pastes are prepared using for 1 kg, X g (see column of Table I) of thickener, 120 g of binder PL6226 (TM) conc from the company CLARIANT, 12 g of blue pigment Printofix H-BFC (TM) from CLARIANT. The pH of the paste is adjusted to 8.5 with a 28 ° B ammonia solution.

The amount of thickener is adjusted to obtain a viscosity of 6.5 Pa.s (Brookfield RVT (TM) viscometer - Speed 50). Prints are made on bleached cotton, 372 g / m2, as well as on polyester / cotton blend (65/35), 118 g / m2, using a FAM-R (TM) type printing machine from the STORK company. Drying and fixing are carried out in a UL-50 (TM) type study from the company Memmert. The printing conditions for each test are grouped in Tables I and II (Pressure, speed, temperature and drying time).

The printing results with the different thickeners used are also grouped in Tables I and II. The fusing phenomenon is evaluated from 1 to 5 corresponding to the fineness observed on 5 lines of different thickness. The drop in viscosity observed corresponds to the drop in viscosity when the binder is added to the paste composed of water and the thickener (pH adjusted to 8.5). The color is evaluated from 1 to 5 by comparison with reference samples.

The synthesis conditions as well as the results of application of the pure polymer are collated in Table I.

In this Table, the right-hand side Summary includes the following abbreviations:

M.A. / Théo. = active ingredients / theoretical calculation

HLB = hydrophilic-lypophilic balance

Ret. / Lim. = crosslinking / transfer agent ratio

(ppm / active ingredient) / (ppm / active ingredient)

Anio. = anionicity

G is a component of the organic phase of the emulsion and designates a light hydrocarbon solvent, distillation fraction 230 - 270 ° C. H is a component of the organic phase of the emulsion and denotes a light hydrocarbon solvent, distillation fraction 175 - 225 (° C).

K is a component of the organic phase of the emulsion and denotes a mineral oil.

These solvents and oils are very well known to those skilled in the art who will be able to select them according to the application envisaged, in particular heavy oil / light oil, cf. above) and routine testing.

AA = acrylic acid monomer

Dry ACM = acrylamide monomer measured in the dry state

Inverter = known agent NP9 (TM) (polyethoxylated nomylphenol 9)

"Tween 85" (TM) and "Arlacel 987" (TM) are surfactants well known to those skilled in the art, which form the surfactant system of this example; the HLB of the system is indicated in the “HLB” column.

As can be seen in Table I, tests 1 to 12 make it possible to vary the anionicity, the crosslinking / transfer agent ratio, the nature of the oil forming the continuous phase of the reverse emulsion resulting from the synthesis , the proportion of acrylic acid and acrylamide.

On the other hand, the surfactant system was adjusted to an HLB of 8.5 for a total of 7% of surfactants.

In this Table, the left side Printing includes the following abbreviations:

The column g / Kg (1) represents the amount of thickener X in grams per kilogram of printing paste to obtain a viscosity of the paste of 6500 cps +/- 300 cps. It is therefore noted that this Table corresponds to the use of the thickener according to the invention in the form of the pure product (that is to say not mixed with other thickeners).

In this technical sector, it is obviously interesting that the amount of thickener is as small as possible, because it partly determines the cost of the printing paste.

The printing conditions are indicated above, and specified in the notes at the bottom of Table I. Those skilled in the art know these conditions. The speed and the pressure correspond to machine settings, as well as the frame which we know determines the opening of the meshes.

The visco drop column. represents the drop in viscosity observed, in%, when adding the binder to the paste. The most interesting product will naturally be that corresponding to the lowest drop in viscosity.

Those skilled in the art know that fusing is an essential parameter characteristic of printing paste. Fusing can be described as the ability of the dough to lead or not to a good resolution between the printed areas and the unprinted areas. In other words, the fusing reflects the migration or the absence of migration of the dough from the printed area to an adjacent unprinted area, or printed differently. It is obviously essential that migration is as low as possible.

In the test used, strips are printed as shown in the figures, with a thin unprinted strip between each printed strip, and the area for which the resolution is poor is identified on a scale of 1 to 5, ie for which the white strip is invaded by the print.

A value of 1 means that the first band is invaded, and such an index is therefore bad. Index 5 shows, on the contrary, excellent behavior in fuselage. FIG. 1 represents a test on a 65% PE / 35% cotton fabric with a thickener in accordance with the teaching of the prior art, test 28 of Table II (thickener No. 20).

The fuselage index is equal to 1.

FIG. 5 represents a test on the same fabric with a polymer corresponding to test No. 3 of Table I.

The fusing index is equal to 5. It can be seen that the resolution of the bands is much better, which guarantees very good printing precision.

In general, in Table I, it can be seen that all the fusing values are equal to 4 or 5 depending on the nature of the fabric, which is an excellent result.

The last column of the "Color" table corresponds to a subjective visual test aimed at evaluating the color yield, or intensity of the color.

An index of 1 corresponds to a mediocre result at just acceptable, while an index 5 corresponds to a very good perception of the color obtained.

According to Table I, it can be seen that the best embodiment of the present invention corresponds to test 12 which offers the best combination of excellent properties, ie a fusing of 5 for both cotton and polyester -cotton and a color index of 4 for both fabrics. This product is all the more advantageous since it can be used in a quantity barely greater (in polymer reduced to the active materials) than the polymers of the prior art. As for the drop in viscosity, it remains entirely acceptable. As a guide, a typical example of the application of a polymer corresponding to patent EP 0 161 038 (Figure 1, test 28, thickener No. 20) and which leads in the industry to excellent results, would be 12 g / kg for a fusing of 1 on cotton / PE and for a color index of 5 on all types of fabric;

The synthesis conditions as well as the results of application of the polymer in admixture with thickeners of the prior art are collated in Table I I.

In this Table I I. the right side Synthesis includes abbreviations identical to those in Table I. with the exception of the following:

Ratio: this column designates the mixing ratio in% by weight of a printing base of the pure product according to the invention (TR) with a printing base of the prior art (AA).

The objective of this example is to show that the products according to the invention are also capable of greatly improving the properties of conventional printing bases. This can reduce the cost of printing, which is essential in this industry, without significantly penalizing the properties.

In this Table I I, the left part Printing includes abbreviations identical to those of Table I.

We see that the total amount of thickeners is lower in active ingredients / kg of dough, compared to the same calculation made in Table I.

It is also noted that all of the four essential parameters are in a very good register, in particular for tests 20, 23, 24, 25 of Table II.

It is therefore advantageous to use the polymer according to the invention in admixture with thickeners of the prior art, and in particular at the rate of: 5 to 30% by weight of polymer according to the invention for

95 to 70% of thickener (s) of the prior art, such as those described in patent EP 0 161 038.

The invention therefore therefore also relates to bases for textile printing paste comprising at least one thickener according to the invention and at least one other thickener, characterized in that said other thickening polymers are thickening polymers with a dry particle size> 0, 6 microns, and often between 1 and 3 or 5 microns or more, chosen from those described in the aforementioned patent EP 0 161 038.

b) Dispersed dye:

Dispersed dye printing pastes are prepared using the following formulation:

Thickener according to the invention X g

Ammonia NH3 28 ° B Y g

water qs 1000 g

The viscosity is measured using a Brookfield (TM) RVT viscometer of geometry 6 - speed 20.

To this white paste, 1% of dispersed dye of the red Terasil (TM) X - GSA L type from Ciba is added.

The viscosity is measured again. The percentage drop in viscosity is calculated by adding dye.

X is chosen so that the viscosity after addition of dye is 10,000 cPs and Y so that the pH is slightly acidic (around 6). Thickener # 12 is used in this formulation at a dosage of 34 g. The drop in viscosity observed by adding dye is 24%.

Next, a polyester type fabric is printed with this paste.

The results show good resistance to electrolytes as well as a very good print quality by avoiding any fusing phenomenon and by maintaining a good color yield.

Other printing tests of the same type are carried out with different thickeners prepared according to the invention, in particular thickener No. 10. These tests confirm the excellent results obtained with thickener No. 12.

The invention also generally relates to:

The use of polymers, mixtures of polymers as described above according to the invention as thickeners.

The use of polymers, mixtures of polymers as described above according to the invention as thickeners for the textile industry, in particular printing on textiles.

The use of polymers, mixtures of polymers as described above according to the invention as thickeners for the field of the cosmetic industry.

The use of these polymers or mixtures of polymers as described above, in admixture with at least one other thickener of the prior art.

The use of polymers, mixtures of polymers as described above, in admixture with at least one other thickener of the prior art such as: those obtained by reverse polymerization of copolymerizable monomers which comprise at least one ethylenically unsaturated acid and at least one crosslinking agent with ethylenic unsaturation, said acid comprising (a) at least one unsaturated acid comprising free carboxy groups and (b) at least one unsaturated acid containing acid groups salified with a sodium, ammonium or similar ion, such as:

acrylic acid / sodium acrylate

ammonium acrylate / acrylamide

acrylic acid / sodium acrylate / acrylamide.

3 (0 Û)

XI a h-

TABLE II

m c m σ m

33 m

TJ r- m

Ξ m

33 m Limiter: sodium hypophosphite M.A. = active ingredients Ω Crosslinker: 50% MBA / 50% ABAA m

1 → quantity of thickener required in g per kg of dough to obtain 6500 cps ± 300 cps Printing conditions

2 → drop in viscosity observed in% when adding Vitesse 100 binder

3 → C = cotton - PIC = Polyester / cotton Pressure 3 TR = thickener according to the invention Frame 77T

AA = thickener of the prior art before distillation Doctor blade diameter 10 mm (*) = thickener of the prior art after distillation Drying / Fixing 4 min. - 150 ° C

Claims

1 Synthetic vinyl polymers characterized in that they have a dry particle size of between approximately 0.2 and 0.6 microns, in the form of the reverse emulsion obtained directly by polymerization in reverse emulsion, or of this emulsion itself even reversed with water, or of “dry organic dispersion”, or of powder, or of polymer isolated in particular in powder and whose particles are redispersed in an aqueous medium.

2 vinyl synthetic polymers according to claim 1, characterized in that they have a dry particle size of between approximately 0.2 and 0.4 microns, in the form of the reverse emulsion obtained directly by reverse emulsion polymerization, or of this emulsion itself inverted with water, or of "dry organic dispersion", or of powder, or of polymer isolated in particular in powder and whose particles are redispersed in an aqueous medium.

3 vinyl synthetic polymers according to claim 1, characterized in that they have a dry particle size of between approximately 0.2 and 0.3 microns, in the form of the reverse emulsion obtained directly by reverse emulsion polymerization, or of this emulsion itself inverted with water, or of "dry organic dispersion", or of powder, or of polymer isolated in particular in powder and whose particles are redispersed in an aqueous medium.

4 vinyl synthetic polymers according to any one of claims 1 to 3, characterized in that they are in the form of the product obtained by redispersion, in particular of a powder, in an aqueous medium, generally water.

5 vinyl synthetic polymers according to any one of claims 1 to 4, characterized in that the oily continuous phase of emulsion synthesis consists of one or more oils chosen from the following:

mineral oils, vegetable oils, synthetic oils non-organic solvents

halogenated hydrocarbons.

6 vinyl synthetic polymers according to any one of claims 1 to 5, characterized in that the monomers used for the synthesis of the (co) polymers according to the invention will be chosen from the following:

anionic: ethylenically unsaturated monomers having

a carboxylic acid function, as an acrylic acid or methacrylic acid monomer,

a sulfonic acid function as a 2- acrylamido-2-methylpropane sulfonic acid or AMPS monomer,

cationic: ethylenically unsaturated monomers such as chloromethylated MADAME, chloromethylated ADAME, DADMAC (diallyldimethyl ammonium chloride)

non-ionic: monomers with ethylenic unsaturation and having no ionic function, such as acrylamide, methacrylamide, vinylpyrrolidone,

and generally the monomers, in particular copolymerizable monomers which comprise at least one ethylenically unsaturated acid and at least one crosslinking agent with ethylenic unsaturation, said acid comprising (a) at least one unsaturated acid comprising free carboxy groups and (b) at least an unsaturated acid comprising acid groups salified with a sodium, ammonium ion or the like, and also, preferably, the proportions of said free acid groups to said salified groups during the polymerization being from 80/20 to 10/90, and said acids ( a) and (b) being difunctional or preferably monofunctional acids, preferably monocarboxylic or monosulfonic, preferably monocarboxylic acids, and in particular the following acids:

- preferably AMPS

more preferably (meth) acrylic acids,

the partial neutralization of the acid groups, mentioned above, which can be carried out by partial neutralization of the monomer or else by mixing monomers, identical or different, one with free acid groups and the other with acid groups salified at least in part, and the monomers (a) and / or (b) which can be used alone or in various mixtures in each category.

7 vinyl synthetic polymers according to any one of claims 1 to 6, characterized in that the monomers are used in the following proportions: (% by moles):

anionic: 0 to 100% preferably 30 - 50 to 100%

non-ionic: 0 to 100%, preferably 25 to 80%%, preferably

70 to 30%.

8 vinyl synthetic polymers according to any one of claims 1 to 7, characterized in that they consist of polymers containing from 5 to 100% of cationic monomers, the possible non-cationic balance consisting of nonionic monomers.

9 vinyl synthetic polymers according to any one of claims 1 to 8, characterized in that they consist of amphoteric copolymers composed of 15 - 60 mole% of cationic monomer (s)

25 - 80 mole% of non-ionic monomer (s) (such as ACM or acrylamide)

2 - 30 mole% of anionic mohomer (s)

1 0 synthetic vinyl polymers according to any one of claims 1 to 9, characterized in that they consist of polymers containing from 5 to 100% of cationic monomers, the possible non-cationic balance consisting of nonionic monomers.

1 1 vinyl synthetic polymers according to any one of claims 1 to 10, characterized in that the (co) polymers are preferably obtained from acrylamide and acrylic acid or sodium acrylate.

1 2 vinyl synthetic polymers according to any one of claims 1 to 11, characterized in that the sodium acrylate is replaced by a reaction mixture containing acrylic acid and an appropriate proportion of sodium hydroxide.

1 3 vinyl synthetic polymers according to any one of claims 1 to 12, characterized in that other salts than that of sodium are used, such as potassium salt, ammonium or other equivalent salts.

1 4 vinyl synthetic polymers according to any one of claims 1 to 3, characterized in that they are crosslinked.

1 5 vinyl synthetic polymers according to claim 14, characterized in that the crosslinking agent will be chosen from crosslinking agents with ethylenic unsaturations, such as methylene bis acrylamide (MBA), which will be generally preferred, allyl methacrylate, diallyl phthalate, and glycol diacrylates.

1 6 vinyl synthetic polymers according to any one of claims 14 and 15, characterized in that the proportion of MBA is between approximately 50 and 5000 ppm, preferably 50 and 2000 ppm, or between 200 and 800 ppm, expressed as dry weight of all the monomers used.

1 7 Synthetic vinyl polymers according to any one of claims 1 to 14, characterized in that they are branched (that is to say obtained by mixing a crosslinking agent with a chain transfer agent).

1 8 vinyl synthetic polymers according to any one of claims 1 to 17, characterized in that they consist of mixtures of (co) polymers crosslinked and / or linear and / or branched.

1 9 Synthetic vinyl polymers according to any one of claims 1 to 18, characterized in that they also comprise chain transfer agents or chain length limiters, optionally in combination with crosslinking or branching agents.

20 Base for textile printing paste, characterized in that it comprises at least one vinyl synthetic polymer (or copolymer or terpolymer, etc.) with a dry particle size of between approximately 0.2 and 0.6 microns, under the form of the reverse emulsion obtained directly by polymerization in reverse emulsion, or of this emulsion itself reversed with water, or of “dry organic dispersion”, or of powder, or of polymer isolated in particular in powder and whose particles are redispersed in an aqueous medium.

21. Base for textile printing paste, according to claim 20, characterized in that it comprises at least one synthetic vinyl polymer or copolymer with a dry particle size of between approximately 0.2 and 0.4 microns, in the form of the reverse emulsion obtained directly by polymerization in reverse emulsion, or of this emulsion itself reversed with water, or of “dry organic dispersion”, or of powder, or of polymer isolated in particular in powder and whose particles are redispersed in an aqueous medium.

22. Base for textile printing paste, according to claim 20 or 21, characterized in that it comprises at least one vinyl synthetic polymer or copolymer with a dry particle size of between approximately 0.2 and 0.3 microns, in the form of the reverse emulsion obtained directly by polymerization in reverse emulsion, or of this emulsion itself reversed with water, or of “dry organic dispersion”, or of powder, or of polymer isolated in particular in powder and of which the particles are redispersed in an aqueous medium.

23 A base for textile printing paste, according to any one of claims 20 to 22, characterized in that it comprises at least one synthetic vinyl polymer or copolymer with a dry particle size of between approximately 0.2 and 0, 6 microns, preferably 0.2 and 0.4 microns, preferably 0.2 and 0.3 microns, in the form of the reverse emulsion obtained directly by polymerization in reverse emulsion, or of this emulsion itself reversed at water, or of “dry organic dispersion”, or of powder, or of polymer isolated in particular in powder and whose particles are redispersed in an aqueous medium, in mixture with at least one other thickening polymer in a compatible form.

24 Base for textile printing paste according to claim

23, characterized in that said other thickening polymers are thickening polymers whose particle size is greater than 0.6 microns, and is typically in the range of about 1 to 3 microns or 5 microns or more.

25 Base for textile printing paste, according to claim 23, characterized in that said other thickening polymers are thickening polymers whose particle size is in the range of about 1 to 3 microns or 5 microns.

26 Base for textile printing paste, according to claim 23, characterized in that said other thickening polymers are thickening polymers chosen from those described in patent EP 0 161 038, in particular: those obtained by reverse polymerization of copolymerizable monomers which comprise at least one ethylenically unsaturated acid and at least one crosslinking agent with ethylenic unsaturation, said acid comprising (a) at least one unsaturated acid comprising free carboxy groups and (b) at least one unsaturated acid containing acid groups salified with a sodium, ammonium or similar ion, such as:

acrylic acid / sodium acrylate

ammonium acrylate / acrylamide

acrylic acid / sodium acrylate / acrylamide

27 Base for textile printing paste, according to claim 20, characterized in that it contains at least one (co) polymer according to any one of claims 1 to 19

28 Base for textile printing paste, according to claim 20, characterized in that it contains at least one mixture of (co) polymer according to any one of claims 1 to 19 with at least one other thickening polymer.

29 Printing pastes for textiles, characterized in that they contain at least one base according to any one of claims 20 to 28.

30 Textile printing pastes according to claim 29, characterized in that they additionally contain at least one dyestuff (pigments and dyes) of all types used in the textile industry.

31 Textile printing pastes according to any one of claims 29 or 30, characterized in that they additionally contain at least one pigment, such as the unisperse blue BE (TM) from Ciba- Geigy; Printofix H 3BD Red (TM) or H BFC blue (TM) from Clariant; or the yellow K 4 G Imperon (TM) or red K GC from Hoechst. 32 Textile printing pastes according to any one of Claims 29 to 31, characterized in that they additionally contain at least one dispersed dye, such as Dianix (TM) yellow S 6G from Dystar, and the entire Dianix range (TM), or the Foron (TM) yellow SE.FL or red RD-BR from Clariant.

33 Textile printing pastes according to any one of Claims 29 to 32, characterized in that they additionally contain at least one reactive dye, such as the series of Drimarene (TM) yellow R3GL, red R3GN, or blue R2RL from Clariant, or the Levafix (TM) PN series, yellow PN 5GN, red PN FB, or blue PN 3R from Dystar.

34 Textile printing pastes according to any one of claims 29 to 33, characterized in that they additionally contain at least one acid dye, such as the Nyiosane (TM) yellow N 7GL or Sandolane (TM) blue E series. HRL of Sandoz.

35 Textile printing pastes according to any one of Claims 29 to 34, characterized in that they additionally contain at least one binder.

36 Textile printing pastes according to claim 35, characterized in that the binder is chosen from the following:

- acrylic type

butadiene-styrene type

37 Textiles or similar products characterized in that they have been printed using a printing base or a printing paste according to any one of claims 1 to 36.

38 Textiles or similar products according to claim 37, characterized in that they are chosen from the following:

cotton, natural or modified natural polyester,

mixed fibers such as:

cotton / polyester

"Lycra" (TM)

polyamides

silk, wool,

acrylic fabrics

and their mixtures,

and other fibers and fiber mixtures.

39 Use of polymers, polymer blends as described in any one of claims 1 to 19 as thickeners.

40 Use of polymers, polymer blends as described in any one of claims 1 to 19 as thickeners for the textile industry, in particular printing on textiles.

41 Use of polymers, mixtures of polymers as described in any one of claims 1 to 19 as thickeners for the field of the cosmetic industry.

42 Use of the polymers, polymer blends according to any one of claims 39 to 41, the polymers or polymer blends as described in any one of claims 1 to 19 being in admixture with at least one other thickener. 43 Use of the polymers, polymer blends according to any one of claims 39 to 42, the polymers or polymer blends as described in any one of claims 1 to 19 being in admixture with at least one other thickener such as:

those obtained by reverse polymerization of copolymerizable monomers which comprise at least one ethylenically unsaturated acid and at least one ethylenically unsaturated crosslinking agent, said acid comprising (a) at least one unsaturated acid comprising free carboxy groups and (b) at least one unsaturated acid containing acid groups salified with a sodium, ammonium or similar ion, such as:

acrylic acid / sodium acrylate

ammonium acrylate / acrylamide

acrylic acid / sodium acrylate / acrylamide.