DE2617243A1 - Aq. polyacrylate dispersions - contg. itaconic or (meth)acrylic acid, a (meth)acrylamide, alkyl (meth)acrylates and acrylonitrile, used as foam coatings for textiles - Google Patents

Abstract

An aq. dispersion contains an emulsion copolymer of (A) 0.5-3 wt.% itaconic acid (I) and/or (meth)acrylic acid, (B) 1-5 wt.% n-methylol acrylamide (II) and/or (meth) acrylamide, (C) 0-86 wt.% Bu acrylate (III), (D) 0-95 wt.% Et-, Pr-and/or Me acrylate and (E) 0-10 wt.% acrylonitrile (IV) with the proviso that (C) + (D) comprises 85-95 wt.% and the ratio of Bu acrylate to acrylonitrile if present is 4.5-8.6:1. The copolymer has excellent low temp. softness and flexibility and may be used as decorative foam laminates esp. with textiles. The foam is resistant to detergents and dry cleaning chemicals.

Description

Polymer mass

The invention relates to copolymers which are produced by addition cotolmerization are formed by four different types of monomers: (a) 0.5 to 3% by weight methacrylic acid, Acrylic acid, itaconic acid or a mixture thereof, (b) 1 to 5% by weight of acrylamide, Methacrylamide, N-methylolacrylamide or a mixture thereof, (c) 0 to 86 wt Butyl acrylate, (d) 0 to 95 weight percent methyl acrylate, ethyl acrylate, or propyl acrylate and (e) 0 to 10 weight percent acrylonitrile.

The various components used to make the copolymer must are present in certain proportions so that the copolymer obtained is added is suitable to meet the numerous intended uses. Important Properties are softness and flexibility at low temperatures, such as -23 ° C (100F) or below, even with a reaction with small amounts an aminoplast resin. The copolymer can be with or without an aminoplast crosslinking agent used, but contains groups that easily react with the aminoplast. Such groups help ensure that the finished copolymer is not tacky and becomes blocking-resistant, whereby under "blocking" the sticking of folds together of a coated substrate and work with other components of the copolymer in that coatings as well as other forms of the copolymer are resistant become capable of washing and organic solvents, in particular Solvents used for chemical cleaningjThe hydrophilic components of the Copolymers are limited in such a way that the viscosity of an aqueous system that it contains, can be controlled.

To achieve these goals, the amount of acidic component (a) be at least 0.5% and can constitute up to 3.0% of the total composition. It has been found that this amount of acid is necessary to make the final products non-tacky close. This amount of acid also contributes to good wash resistance of the finished product, with excessive thickening and consequent difficulties avoided when applied from aqueous media even under alkaline conditions will.

The acrylamide, methacrylamide or N-methylolacrylamide or mixtures of which (b) are present in amounts between 1 and 5%. This amount of amide ensures a rapid reaction with an aminoplast, if such with the copolymer is used.

Either acrylamide or an equimolar mixture of acrylamide and N-methylolacrylamide are preferred as these compounds Tissues, which are covered with scaled-down foams from the masses, an excellent one Give resistance to dry cleaning.

The amount of butyl acrylate (c), if any, should be such be that no thickening problems arise in the neutralization of the acidic Component occur. The butyl acrylate can be selected from n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate or mixtures thereof, but n-butyl acrylate is preferred in question. The amount of butyl acrylate can be up to 86%.

The sum of butyl acrylate (c) and the methyl acrylate, ethyl acrylate, n-propyl acrylate or isopropyl acrylate or mixtures thereof of component (d) must Make up from 85 to 95% by weight of the monomer mixture or of the copolymer. Ethyl acrylate is preferred because it is readily available. The ester components described above (c) or mixtures of (c) and (d) are necessary to achieve softness and Flexibility at low temperatures as well as to control the inclination of the acidic Component to thicken the mass when applied in alkaline aqueous media will.

Acrylonitrile is only required in the monomer mixture, albeit Butyl acrylate is present. The amount of acrylonitrile is directly related to the amount of butyl acrylate in the copolymer. For flexibility when cold and durability against solvents used in dry cleaning to achieve, the ratio of butyl acrylate to acrylonitrile must be between 4.5: 1 and 8.6: 1 and preferably varies between about 5.7: 1 and 7.5: 1. Quantities of acrylonitrile in the monomer mixture of up to 10% by weight result in these ratios.

The polymerization is carried out using a free radical donor Initiator or catalyst carried out, for example an organic or inorganic peroxide catalyst, like a persulfate (ammonium persulfate or alkali persulfate).

0.05 to 1% of the initiator or catalyst can be used based on the total weight of the monomers.

If butyl acrylate and acrylonitrile are present in the monomer mixture, then "one shot" polymerization is used.

When carrying out an emulsion polymerization, a redox system is used extremely effective. Again, an organic peroxide, ammonium persulfate or Potassium persulphate in the same amounts as indicated above, used. The peroxide catalyst is effectively combined with a reducing agent, such as an alkali sulfite, bisulfite, metabisulfite or hydrosulfite or hydrazine coupled in approximately equivalent amounts.

In the polymerization, a chain transfer agent or a Regulators are used, for example mercaptoethanol or another mercaptan, to control molecular weight.

A significant amount of the emulsifier for the polymerization must be be anionic, on the order of at least 50% by weight of the emulsifier. Compared to foams made from emulsions, the anionic Containing emulsifiers, nonionic systems produce foams that have a strong Cause blocking both when dry and when wet (after washing). Nonionic emulsifiers that can be used are, for example higher alkylphenoxypolyethoxyethanols in which the alkyl group has 6 to 18 carbon atoms has, for example octyl, dodecyl or octadecyl, with 8 to 50 or more Oxyethylene units can be present.

Examples of anionic emulsifiers are the higher fatty alcohol sulfates, such as sodium lauryl sulfate. One can also use cationic emulsifiers, these however, are less preferable. Mention may be made of higher alkylpyridinium salts, such as Laurylpyridinium chloride, Octlbenzyltrimethylammoniumchlorid or the like.

It was found that polymer compositions without butyl acrylate and acrylonitrile can be made using a "two shot" polymerization method. When performing this method, a first part (25 to 75 wt. Of the total amount) the monomer mixture in the presence of a customary emulsifier and catalyst emulsifies and polymerizes. After the reaction mixture has reached its exothermic maximum reached, the pH is adjusted by adding aqueous ammonia, whereupon the mixture is allowed to cool. Then the remainder of the monomer emulsion becomes and the catalyst are added to the reaction mixture, whereupon the entire batch is polymerized.

If cellular foams are to be produced, foam stabilizers must be used use. These foam stabilizers are, for example, alkali, ammonium or amine salts such as mono-, di- or triethanolamines of aliphatic carboxylic acids with 16 to 20 carbon atoms, of which oleic acid, stearic acid or the like may be mentioned. Examples include sodium, potassium or ammonium stearate, sodium, potassium or ammonium oleate or the like ammonium stearate is the preferred foam stabilizer.

The foam formulation usually contains about 3 to 10 parts by weight and preferably 2 to 6 parts by weight of the foam stabilizer based on the weight of the copolymer.

A more detailed description of suitable conventional foaming methods as well as other foam stabilizers and foaming agents that can be used, can be found in "Latex Foam Rubber" by E. W. Magee, John Wiley and Sons, New York (1962).

The cellular foam compositions can also contain pigments (fillers). Examples of pigments that can be used are clays, especially of the kaolin type, calcium carbonate, blanc fixe, talc, titanium dioxide, colored lacquers and toners, ocher, soot, graphite, aluminum powder or flakes, chrome yellow, molybdate orange, toluidine red, copper phthalocyanines, such as "Monastral" blue and green lakes. The term 'mineral' should include all pigment materials be understood regardless of whether they are strictly mineral Have character or are partially or wholly organic.

According to a preferred embodiment of the invention, foamed Articles made from copolymers according to the invention, wherein 1 to 10 wt .-%, based on the weight of the copolymer, are used as aminoplasts, for example of a water-soluble formaldehyde condensate with urea, melamine or N, N'-ethylene urea. In this case too, according to a preferred embodiment, 3 to 5 wt. of a melamine / formaldehyde resin-forming precondensate, based on weight the polymer solids. In general, molded according to the invention Articles by formulating an aqueous dispersion of the emulsion polymer of the invention with the mentioned amount of aminoplasts to set a mass with a solids concentration from about 35 to 60 weight percent. The mass can be in several ways a foamed product can be transferred, however, there is a preferred method in introducing suitable foaming agents with or without pigments and then the mass Beat to develop a foam structure in the mass. The beaten mass is then placed in a heated mold to harden and solidify the foam structure brought in. The whipped mass can also be coated on a suitable substrate on which it is first dried without noticeable hardening or heat hardening, which is then followed by heating for an appropriate period of time elevated temperatures is cured, these temperatures generally in the upper part or above the temperature range that is maintained for drying will lie. This method is particularly suitable when you are using a laminate wants to produce a foam layer. For example, they are used to produce decorative fabrics these with a foamed mass in a thickness between 254 and 2540 ß or more overdrawn. The coated fabric is then, for example, for a period of time dried from 1 to 10 minutes at a temperature of 93 to 1430C (200 to 2900F). The length of time is inversely proportional to the temperature. It is often convenient to crush the foam on the fabric. After this is done the fabric and foam laminate is fed through a calender or a pair of nip rollers pressed, with the rollers Z or slightly elevated temperatures of up to 50 "C. The nip between the rolls of the calender or the nip rolls is such that the thickness of the foam layer by about 1/10 to 9/10 and preferably by 1/5 to 1/6 of the original thickness. After the laminate has been pressed in this way, the foam mass is hardened, for example by heating to temperatures for a period of 1 to 5 minutes from 135 to 177 "C (255 to 3500F). This hardening stage does not have to be immediately after be carried out after crushing.

It should be noted that the foam can also be used on other substrates can be applied with or without crushing. Examples of such substrates are leather, paper, wood such as plywood, metals such as steel, iron, aluminum, copper, Brass or zinc, these metals can be bare or with an epoxy or may be primed with an epoxy / aminoplast primer layer.

You can't just put a single layer of foam on a single one Apply substrate layer, regardless of whether it is a textile fabric, Paper, wood or the like is, rather the foam layer can also be used as Layer of adhesive used between two layers of other materials is applied. The foam layer can also be on each side of a different substrate be applied. In either case, the foam layers can be crushed, however, they can also remain undamaged if necessary. The pounding should in any event, if so desired, before final curing of the foam layer be carried out by heat.

After the copolymer of the invention with the aminoplast, the Foam stabilizers and suitable pigments are formulated been is, it can be easily converted into the foamed state due to the fact that the polymer mass is such that excessive thickening of the formulation does not occur under acidic or alkaline conditions, which are therefore adhered to to ensure the most effective mode of action of the foam stabilizer. Furthermore, the copolymer is such that in the formulation used for the preparation of Crushed foams are suggested to give the foam its softness and flexibility Maintains at least down to a temperature of -230C (10 ° F) at low temperatures and is not sticky after hardening. Furthermore, the foam is against washing in normal detergents used for cleaning textiles in general and decorative fabrics in particular, it is also resistant to a Clean chemically. By providing a foam that is less than dry-cleaning and washing is permanent, the foam is very suitable for lamination of Textiles that are often dry-cleaned and washed.

A general recipe for making a foam that is suitable for the lamination of textiles is suitable is the following: component parts by weight preferred parts by weight of polymer 100 100 aminoplast 1 - 10 3 - 5 pigment (filler) 0 - 60 1 - 55 Foam stabilizer 3 - 10 2 - 6 The pH value of the mass can may be discontinued. This can be done either by adding an acid, such as hydrochloric acid or sulfuric acid, to generate a certain pH value happen on the acidic side, furthermore one can also add ammonia to the medium to make something alkaline, for example to bring it to a pH of 8 to 10 bring. The formulation can contain between 35 and 60% total solids.

In practicing the following examples embodying the invention explain, the partial data relate, unless otherwise stated is, on weight, while temperatures are to be understood in "C."

Examples 1 to 7 (1) An emulsion consisting of: deionized Water 2575 parts sodium lauryl sulfate 87 acrylic acid 80 acrylamide 315 acrylonitrile 900 n-Butyl Acrylate 7695 gradually becomes one over a period of 2 hours Solution of 0.05 parts of iron (II) sulfate / heptahydrate in 4497 parts of deionized Water added, the temperature of the reaction mixture being kept at 60.degree. At the same time, a solution of 14 parts of sodium persulfate in 600 parts of water and 13 parts of sodium bisulfite in 600 parts of water separately to initiate the Polymerization added. After the additions described above have been completed, 5 parts of tert-butyl hydroperoxide and 5 parts of sodium formaldehyde sulfoxylate added in 350 parts of water to terminate the polymerization.

The product is cooled to remove small amounts of coagulum, if available, filtered and packaged.

(2) The emulsion copolymer dispersion produced in (1) is mixed in the following formulation: Product Solids Dispersion 200 100 titanium dioxide (Titanox RA-45) 25 25 clay (Acme WW) 30 30 melamine / formaldehyde resin 4.6 3.7 (Aerotex MW) ammonium stearate 14 4.6 water 70 ammonia (28%) 4 solids - 47.0 t. 347.6 163.3 Foams are made in the way that air is introduced into the formulation using a kitchen mixer (Model C) with a density of approximately 0.016 g / cm3 being set. The foam will then poured on a cotton blanket to a thickness of 1524 A, during one Dried for a period of 1.75 minutes at a temperature of 1380C, on a Pound the padder and finally at 1500C for 5 minutes hardened.

The crushed foam is up against more than 5 washing and 10 dry cleaning cycles resistant and has a cold bending temperature of -260C.

(3) The procedure described under (1) is repeated with the Except that 135 parts of itaconic acid, 315 parts of acrylamide, 5850 parts of ethyl acrylate, 405 parts of acrylonitrile and 2305 parts of n-butyl acrylate are used as monomers.

(4) The procedure described under (3) is repeated with the Exception that 675 parts of acrylonitrile and 2035 parts of n-butyl acrylate are used.

(5) The dispersion produced according to (4) is specified as under (2) mixed and foamed. The foamed mass is applied to a polyester decorative fabric applied and then by passing through the nip of a pair of rollers pound. The crushed foam obtained has a cold bending temperature of -90C and is resistant to more than 5 washing and 10 dry cleaning cycles.

(6) The procedure described under (1) is repeated with the Except that 180 parts of acrylic acid, 315 parts of acrylamide, 900 parts of acrylonitrile and 7605 parts of n-butyl acrylate are used as monomers.

(7) The procedure described under (1) is repeated with with the exception that 45 parts of acrylic acid, 315 parts of acrylamide, 1800 parts of acrylonitrile and 6840 parts of n-butyl acrylate are used as monomers.

(8) An emulsion of: deionized water 2775 parts sodium dodecylbenzenesulfonate 67 methacrylic acid 270 acrylamide 180 acrylonitrile 375 butyl acrylate 2250 ethyl acrylate 5925 gradually becomes a solution of 36 over a period of 2 hours Parts of ammonium persulfate, dissolved in 600 parts of water, are added, while the temperature at 80 to 82 "C. After the addition, the dispersion is kept at 850C during heated for a period of 1/2 hour and then cooled to 450C. Then will 5 parts of tert-butyl hydroperoxide in 350 parts of water and 5 parts of sodium formaldehyde sulfoxylate added in 350 parts of water. The product is cooled to 250C for removal small amounts of coagulum, if any, filtered and packaged.

(9) The procedure described under (8) is repeated, with the exception that the methacrylic acid is replaced by 45 parts of itaconic acid, while the amount of butyl acrylate is changed to 2475 parts.

(10) The procedure described under (8) is carried out using adhered to the following emulsion: deionized water 2750 Parts sodium lauryl sulfate 127 itaconic acid 170 methacrylic acid 200 acrylamide 135 acrylonitrile 450 n-butyl acrylate 2700 ethyl acrylate 3485 (11) The procedure described under (1) is complied with, with the exception that the sodium lauryl sulfate by 550 parts Octylphenoxypolyäthoxyäthanol is replaced.

(12) The procedure described under (1) is used using the following emulsion carried out: deionized water 3000 parts of octylphenoxypolyethoxyethanol (40 ethoxy units) 620 methacrylic acid 135 acrylamide 180 acrylonitrile 630 butyl acrylate 5400 isopropyl acrylate 3655 (13) The procedure described under (8) is used complied with, with the exception that the 180 parts acrylamide by a mixture of 90 parts of methacrylamide and 90 parts of acrylamide are replaced.

(14) The procedure described under (8) is used using adhered to the following emulsion: deionized water 2750 parts of sodium lauryl sulfate 87 itaconic acid 135 acrylamide 270 acrylonitrile 630 butyl acrylate 5400 Ethyl acrylate 1285 parts of methyl acrylate 1285 r (15) The procedure described under (1) is complied with, with the exception that n-butyl acrylate is replaced by isobutyl acrylate will.

(16) The procedure described under (3) is repeated with the exception that the 2305 parts of n-butyl acrylate by 2305 parts of 2-ethylhexyl acrylate be replaced.

(17) The method of Example 1 is carried out using 135 parts Itaconic acid, 130 parts of acrylamide, 185 parts of N-methylolacrylamide, 5850 parts of ethyl acrylate, 405 parts of acrylonitrile and 2305 parts of n-butyl acrylate instead of those given in Example 1 Monomers are used.

Example 18 This example shows a sweep shot polymerization method.

A monomer emulsion is made from the following components: deionized water 550 parts itaconic acid 30.1 parts acrylamide 67.1 parts methylol acrylamide 41.6 parts SDBS1 SDBS (Siponate DS-10) 17.7 parts ethyl acrylate 1910.0 parts 2616.5 Parts 1 Sodium Dodecylbenzenesulfonate A reaction vessel is then filled with the following Ingredients filled: deionized water 1470.0 parts sodium sulfate 15.4 parts SDBS 1.77 parts After the batch has been processed for a period of Has been flushed with nitrogen for 30 minutes, 1375 parts of the monomer emulsion become added. A catalyst mixture is then added to the reaction vessel in the following order added.

0.044 part FeSO47H2 0 in 1 part deionized water, 3.0 parts Ammonium persulfate in 33 parts deionized water, 0.75 parts sodium bisulfite in 33 parts of deionized water, 0.44 parts of sodium hydrosulfite in 10 parts of deionized Water.

The polymerization then begins, the temperature being due to it Reached exothermic character 85 to 95 "C. After the temperature maximum has been reached 5 parts of an aqueous ammonia are added. The batch will then cooled to 46-480 ° C., whereupon the remaining monomer emulsion (1241.5 parts) was added will. At 35 to 40 "C a catalyst mixture will be in the following order added: 3.00 parts ammonium persulfate in 90 parts deionized water, 0.75 Parts of sodium bisulfite in 30 parts of deionized water, 0.88 parts of sodium hydrosulfite in 22 parts of deionized water.

The polymerization is then continued and achieved through their exothermic character 80 to 850C. It will stay at this value for a period of time held for 10 minutes. The reaction mixture is then cooled to 750C. then 1.43 parts of tert-butyl hydroperoxide and 0.11 part of SDBS are deionized in 4 parts Water and 1 part of sodium formaldehyde sulfoxylate in 20 parts of deionized water added while cooling continues.

After the temperature reaches 400C or below, the reaction product becomes filtered to remove small amounts of coagulum, if any coagulum is present and packed.

Claims (13)

Claims 1. Mass, characterized in that it consists of a aqueous dispersion of an emulsion copolymer consists of a monomer mixture, which is essentially composed of the following components: a) 0.5 to 3 % By weight of itaconic acid, acrylic acid or methacrylic acid or a mixture thereof, b) 1 to 5 wt .- acrylamide, methacrylamide, n-methylolacrylamide or a mixture thereof, c) 0 to 86 wt .-% butyl acrylate, d) O - 95 wt .-% ethyl acrylate, propyl acrylate, Methyl acrylate or a mixture thereof and e) 0 to 10% by weight of acrylonitrile, wherein the sum of components (c) and (d) is 85 to 95% by weight and the ratio from butyl acrylate to acrylonitrile, if any, varies between 4.5: 1 and 8.6: 1. 2. Composition, characterized in that it is an emulsion copolymer according to claim 1, wherein the monomer component a) from itaconic acid, the monomer component b) from acrylamide or an essentially equimolar mixture of acrylamide and N-methylolacrylamide and the monomer component d) consists of ethyl acrylate, and wherein the ratio of butyl acrylate to acrylonitrile varies between 5.7: 1 and 7.5: 1. 3. Composition according to claim 1, characterized in that the monomer mixture consists essentially of the following components: a) itaconic acid, b) an im essentially equimolar mixture of acrylamide and N-methylolacrylamide and c) ethyl acrylate. 4. Composition according to claim 3, characterized in that the monomer mixture consisting essentially of about 30 parts of itaconic acid, about 67 parts of acrylamide and about 42 parts of N-methylol acrylamide and about 1910 parts of ethyl acrylate consists. 5. Composition according to claim 1, characterized in that the monomer mixture essentially of 135 parts of itaconic acid, 315 parts of acrylamide, 5850 parts of ethyl acrylate, 405 parts of acrylonitrile and 2305 parts of n-butyl acrylate, the mass being 2 Contains up to 6 parts by weight of ammonium stearate as a foam stabilizer. 6. Composition according to claim 1, characterized in that the monomer mixture essentially of 135 parts of itaconic acid, 130 parts of acrylamide, 185 parts of N-methylolacrylamide, 5850 parts of ethyl acrylate, 405 parts of acrylonitrile and 2305 parts of n-butyl acrylate and contains 2 to 6 parts by weight of ammonium stearate as a foam stabilizer. 7. Composition according to claim 1, characterized in that it is 0 to 60 parts by weight of a pigment and 3 to 10 parts by weight of a foam stabilizer, based on the weight of the copolymer. 8. Composition according to claim 2, characterized in that it is 1 to 55 parts by weight of a pigment and 2 to 6 parts by weight of a foam stabilizer, based on the weight of the copolymer. 9. Composition according to claim 1, characterized in that it is 1 to 10%, based on the copolymer weight, of a water-soluble aminoplast condensate of formaldehyde with urea, melamine or N, N'-ethylene urea, based on the Weight of the copolymer. 10. Composition according to claim 9, characterized in that the aminoplast is a melamine / formaldehyde resin in an amount of 3 to 5% by weight. 11. The mass according to claim 2, characterized in that it is 1 to 10%, based on the copolymer weight, of a water-soluble aminoplast condensate of formaldehyde with urea, melamine or N, N'-ethylene urea, based on the Weight of the copolymer. 12. Composition according to claim 11, characterized in that the aminoplast is a melamine resin in an amount of 3 to 5% by weight. 13. Use of one produced from the compositions according to claims 1 to 12 cellular mass for coating textile fabrics, the cellular layer optionally in crushed form.