CS251019B1 - Thermoreactive water-dilutable compositions and methods for their preparation - Google Patents

Abstract

Water-dilutable compositions based on copolymers of olefinically unsaturated monomers, optionally with functional groups, suitable especially for applications in the textile industry and in the field of coatings. They can be prepared as semi-continuous emulsion copolymers in the presence of surfactants, a water-soluble initiation system, and preferably in an inert atmosphere, carried out by adding to water with an additional content of surfactants and a known redox initiation system, preferably ? using the reducing component, an emulsion prepared from apopolymorphic acrylic monomers, water, surfactants and optionally ammonium hydroxide and/or aodor is added at a temperature of 65 to 90 °C with stirring over 1.5 to 6 hours and at the same time a solution of the initiation system in water is added over 1.5 to 7 hours, whereby after the end of the dosing of the emulsion, the reaction mixture is maintained at the stated temperature for another 1 to 4 hours, then cooled and finally and optionally further treated by adding additives, especially from the group comprising aqueous dispersions of thermoplastic copolymers, surfactants, defoamers, viscosity regulators, coalescent substances, pH regulators, acidic catalysts for lithification, fungicides, electrolytes, pigments, fillers and hydrophobic additives.

Description

The subject of the invention are water-dilutable thermoreactive compositions containing self-crosslinking aqueous copolymer dispersions based on aqueous olefinically unsaturated monomers, which are prepared by a special process. The compositions are suitable for various textile applications and as binders for water-dilutable coatings.

For various applications in the textile industry and in the coating industry, thermosetting compositions of aqueous dispersions of copolymers containing N-alkoxymethyl (meth)acrylamide groups are often used (e.g. British Pat. No. 1,025,562 and 1,002,451, German Pat. No. 1,194,146, Czechoslovak AO No. 165,265,

223 208) or methylol groups (e.g. Belgian Pat. No. 620 864» 621 836, 627 700, German Pat. No. 1 221 018, 1 228 064, 208 887). These copolymers are self-crosslinking, with the sulfurization temperature required for the reaction of N-alkoxymethyl (meth)acrylamide groups ranging from 130 to 160 °C. Copolymers containing methylol groups sulfurize at lower temperatures and these systems, however, have limited storage stability.

Other copolymers use hydroxyl groups (e.g. US Pat. No. 2,819,237, 3,218,280, 3,392,133, 3,428,749, British Pat. No. 956,799, 1,079,757, 1,083,011), but these require the addition of crosslinking agents, usually from the group of aramid resins, for their crosslinking. Due to the high temperatures required for sulfurization of thermosetting binders, this process is quite energy-intensive.

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The above-mentioned disadvantages are eliminated by the present invention, the subject of which are thermoreactive water-dilutable compositions based on copolymers of olefinically unsaturated monomers, optionally with functional groups, and a method for their preparation. The essence of the invention lies in the fact that the compositions can be prepared from 8 to 120 parts by weight of acrylic and/or methacrylic acid, 8 to 120 parts by weight of N-alkoxymethylacrylamide and/or N-alkoxymethylmethacrylamide, wherein the alkoxy group is a methoxy, propoxy, butoxy or isobutoxy group, 8 to 120 parts by weight of 2-hydroxyalkylacrylate and/or 2-hydroxyalkylmethacrylate, where the alkyl is ethyl or propyl, 440 to 776 parts by weight of other monomers from the group comprising esters of acrylic and/or methacrylic acid with a number of carbon atoms of 1 to 8 in the alkyl chain and optionally up to 320 parts by weight of styrene. and up to 16,000 parts by weight of additives, especially from the group including aqueous dispersions of thermoplastic copolymers, water, surfactants, defoamers, viscosity regulators, coalescent agents, pH regulators, acid sulfurization catalysts, fungicides, electrolytes, pigments and fillers. The essence of their preparation method is that up to 100 to 400 parts by weight. parts of water optionally containing up to 20 parts by weight of surfactants and up to 10 parts by weight of a known redox initiation system, preferably only the reducing component, is gradually added over 1.5 to 6 hours at a temperature of 65 to 90 °C with stirring, an emulsion prepared from 800 parts by weight of the above-mentioned monomers, 350 to 1200 parts by weight of water, 8 to 48 parts by weight of surfactants and optionally up to 10 parts by weight of ammonium and/or sodium hydroxide, and at the same time a solution of 1 to 20 parts by weight of the initiation system in 5 to 400 parts by weight of water is added over 1.5 to 7 hours, whereby after the addition of the monomer emulsion the reaction mixture is maintained at the stated temperature for another 1 to 4 hours, then cooled and finally optionally further treated by adding up to 200 parts by weight of the above-mentioned additives.

These described thermosetting compositions are suitable for various textile applications, in particular for bonding various types of

251,019 textile materials based on synthetic and natural fibers and their mixtures. They are also used in the formulation of water-based coatings.

The above-mentioned thermoreactive water-dilutable compositions contain self-crosslinking aqueous copolymers and dispersions formed from at least four monomers. As a rule, however, the copolymer is formulated on the basis of five different comonomers, three of which form a thermoreactive system capable of sulfurization even at normal temperatures. By varying the mutual ratio and content of reactive comonomers, it is possible to achieve different degrees of crosslinking of the binder even at lower temperatures and without the need to add an external sulfurizing agent. Copolymers formulated in this way therefore allow applications at lower temperatures, which are only necessary for sufficiently rapid evaporation of the aqueous phase. In general, it is possible to prepare different types of copolymers, characterized by different hardness. This basic characteristic property of copolymers is determined by the ratio of basic monomers, such as styrene, methyl methacrylate (so-called hard comonomers) and, for example, acrylic or maleic acid esters (so-called soft comonomers).

The following table shows examples of the compositions of cross-linking thermosetting copolymers prepared according to the present invention:

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Copolymer composition % wt· I II III IV In VI VII VIII styrene 4 — 10 8 — — 30 ethyl acrylate - 30 60 10 - - - 50 butyl acrylate 78 40 - 60 72 8Ó 70 - raethyl methacrylate - - 30 - - - 10 - acrylic acid 6 - 1 5 15 - - methacrylic acid - 14 - - 2 - 6 3 2-hy droxye thy lme thakry lath 6 - - 9 2 - - 2-hydroxyethyl acrylate - - - 8 - - 12 12 2-hydroxypropyl methacrylate - - 15 - - - - - 2-hydroxypropyl acrylate - 14 - - - - N-is but oxymethylme thacry1amide 6 9 3 — Ií-but oxyme thy lme thacrylamide - - 14 - - - 2 - N-isobutoxymethylacrylamide - 2 - - - - - 5 N-but oxymethy lacrylamide *· — 7 ·· w — —

The method of preparation and application of the terraoreactive compositions obtainable according to the invention are shown in the following examples.

Example 1

The composition containing the dispersion of copolymers No. I is prepared by charging 200 parts by weight of water, 1 part by weight of ammonium salt of nonylphenol polyethylene glycol ether sulfate and 1 part by weight of sodium metabisulfite to the polymerization reactor. This batch is heated to 80 °C and an emulsion prepared from 600 parts by weight of water, 15 parts by weight of ammonium salt of nonylphenol polyethylene glycol ether sulfate, 6 parts by weight of ammonium peroxodisulfate and 800 parts by weight of copolymers No. 1 is gradually added over 3 hours. After the addition of the emulsion is completed, the reaction mixture is heated for another hour at a temperature of 80 °C, after which it is cooled and 0.8 parts by weight of defoamer is added. This composition is applied for the reverse treatment of synthetic furs in the following way:

Knitted synthetic fur is sprayed on the reverse side with an aqueous dispersion of an easily sulfurized acrylic copolymer I· in such a concentration that the dry weight gain moves p

in the range of 28 to 32 g/m · The spraying of the mentioned finishing material (the commercial product is diluted with cold water in a volume ratio of 2:1, 3:2, 1:1) is carried out with a spray nozzle onto the back of the fur, which is stretched (needle-stitched) on the guide arms of the drying and fixing frame, just before entering the drying field of the frame, followed by drying and heat treatment at a temperature of 140 °C, when partial fixation and shrinkage of the hair portions occur · At the same time, crosslinking of the acrylic copolymer takes place* Spraying, drying and fixing are carried out continuously*

The treatment has a multifunctional character: good dimensional stability, a significant reduction in hair shedding (improvement of hair cohesion), elastic flexibility of the knitwear and softness of the product are achieved.

Example 2

Synthetic fur with a knitted or woven base (cellulose, synthetics or a mixture) is sprayed onto the reverse side with a combination of an aqueous acrylate dispersion of copolymers I and a copolymer dispersion containing 46% by weight of butyl acrylate/styrene/methacrylamide/N-isobutoxymethyl methacrylate/acrylic acid copolymers in a weight ratio of 59/27/10/3/1 in volume ratios ranging from 1:10 to 10:1. The combination of both types of acrylate dispersions allows for wide variability in the required fullness and stiffness for individual types of synthetic fur. The technological concentration of the spray material is achieved by diluting with cold water so that the dry p

The weight gain ranged from 20 to 30 g/m. The following dilutions are usually used: 2:1, 3:2, 5:3, 1:1. The finishing compound is sprayed with a spray nozzle onto the back of the fur, which is stretched (needle-stitched) on the needles of the drying and fixing frame chain, just before entering the drying chamber.

251 019 frame fields After drying, partial fixation and shrinkage of the pile takes place in the next field at a temperature of 140 °C. At the same time, crosslinking of the acrylic copolymers also takes place.

The treatment not only achieves dimensional stability and improved hair cohesion, but also prevents the fur from stiffening to the desired stiffness.

Example 3

A composition containing a dispersion of copolymer No. 11 or 111 is prepared by charging 400 parts by weight of water and 20 parts by weight of ethylene glycol to a polymerization reactor. parts of sodium alkylmethylsuccinate The batch is heated to 68 to 70 °C, 6 parts by weight of ammonium peroxydisulfate and 3 parts by weight of sodium metabisulfite are added, after which an emulsion containing 1,200 parts by weight of water, 40 parts by weight of sodium alkylsulfosuccinate and 800 parts by weight of copolymer II or III is added over 5 hours At the same time, a solution of 12 parts by weight of ammonium peroxydisulfate in 300 parts by weight of water and a solution of 6 parts by weight of sodium metabisulfite in 150 parts by weight of water are added and the temperature is maintained in the range of 70 to 75 °C After the addition of the emulsion is complete, the reaction mixture is heated to 85 °C and after 3 hours of heating it is cooled These compositions are particularly suitable for modifying the properties of fabrics The method of their application is as follows:

Printed or plain-dyed cellulose or mixed fabric (e.g. ba/Vss/PADh) in various manipulations is impregnated on the reverse side of the fabric with an aqueous dispersion of acrylate copolymer II with a concentration of 20 to 250 g/l using a PI-3 film impregnator (MA plate method) so that the wet weight gain ranges from 35 to 50% of the fabric weight. After preparation, the fabric is dried in a drying needle frame at a temperature of 110 to 130 °C and, if necessary, calendered on a roller or silk calender.

The treatment is suitable for both dress fabrics and decorative and interior textiles.

Example 4

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Φ 2

Cellulose bulk material weighing 140 to 170 g/m is impregnated on a classic £ ulan with a preparation bath containing 40 to 60 g/l of acrylic dispersion III and 10 to 30 g/l of silicone elastomer ( , (AR-dihydroxypolysiloxane)). After the bath is wrung out (the wet weight is 60 to 75% of the fabric weight), the bulk material is dried in a drying jet frame at a temperature of 120 to 140 °C. The treatment is completed by calendering on a roller calender at a temperature of 60 to 80 °C or on a special calender at a temperature of 120 to 140 °C.

The treatment, together with mechanical processing, reduces the interstitial spaces in the fabric and thus reduces the penetration of feathers and dust through the bulk material.

Example 5

The composition containing copolymer dispersion No. IV, or V, or VI, or VII is prepared by introducing 350 parts by weight of water into the polymerization reactor, which is heated to 85 °C. An emulsion containing 450 parts by weight of water, 8 parts by weight of sodium salt of alkyl polyethylene glycol ether sulfate, 40 parts by weight of ethoxylated nonylphenol and 20 units of ethylene oxide in the molecule and 800 parts by weight of copolymer IV, V, VI or VII is added to it with stirring over a period of 2 hours. 8 parts of ammonium peroxodisulfate dissolved in 24 parts by weight of water are added at the same time. The temperature is maintained at 85 °C for another hour after the end of the dosing of the emulsion and initiator. After this time, the product is cooled. The use of these compositions in textile applications is as follows:

Progressive flat fabric, which is made from a web of waste textile fibers and reinforced with mullein with a total weight of the raw fabric of 60 to 100 g/m, is treated by spraying acrylate dispersion IV, so that the finished product contains 10 to 25 g/m of dry polymerized acrylate. After drying, the nonwoven fabric is usually processed on a smooth roller calender or processed on an embossing calender, which gives the product a plastic relief on its surface.

Easily crosslinking aqueous acrylic dispersion IV functions as a high-quality binder for textile fibers and influences a number of physical, mechanical and chemical properties of the finished product.

Example 6

For the reverse treatment of synthetic fabric made of 100% PAI>»fibre for sports and special purposes, a coating paste was prepared consisting of 100 parts by weight of an aqueous acrylate dispersion of copolymers No. V or VI, 6 parts by weight of a thickener based on polymeric polyacrylic acid and 1.5 parts by weight of an aqueous ammonia solution. The coating paste was applied to the textile substrate with an air trowel with a layer of 20 to 40 g/m. The film is dried in a large-diameter steam-heated drum at a temperature of 100 to 120 °C. The coating is usually applied to the reverse side of the textile, while the face of the fabric has a water-repellent treatment using silicone hydrophobizing TPPs based on hydrogenmethylpolysiloxane or dimethylpolysiloxane with an appropriate catalytic system, which ensures the formation of a silicone film. The production technology is two-stage; coating of the reverse side and hydrophobicizing of the fabric by classic impregnation on a felt, drying, high-temperature processing and hot calendering

Example 7

The composition containing an aqueous dispersion of copolymers No. VII is foamed using a foaming agent based on sodium alkylbenzene sulfonate or sodium alkylpolyethylene glycol sulfonate with 2 to 4 moles of ethylene oxide so that the foaming of the product is 1:3. The foam coating is applied with a roller trowel to the back of the treated fabric with the following weight addition:

in P up to 120 g/m for curtain and decorative fabrics up to 100 g/m2 for deckchairs, tents, fabrics for cushions

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up to 40 g/m reverse reinforcement of plush, mattress fabrics, upholstery

Drying at 100 to 120 °C, calendering after cooling on a roller calender, or application of other special treatments (hydrophobic, antifungal, oleophobic, resinous and others)

Example 8

The composition containing the dispersion of copolymers No. VIII is prepared in a similar manner to the composition containing the dispersion of copolymers No. I. After cooling, 160 parts by weight of butyl glycol acetate as a coalescing agent*, 5 parts by weight of a fungicide based on organotin compounds, 5 parts by weight of sodium salt of polyacrylic acid for viscosity adjustment are added to the product slowly over 3 hours and the pH of the product is adjusted with ammonia to a value of 7.5 to 8.5. This composition is used as a penetrating coating for wood. It can also be applied as a coating or used to formulate dispersion paints.

The paint film is hard and shiny after three days of aging at room temperature; it can be further hardened at a temperature of around 60 °C.

-/íSubject of the invention

Claims (2)

Object of the invention 251 019 Thermoreactive water-dilutable compositions based on copolymers of olefinically unsaturated monomers, optionally with functional groups, suitable in particular for applications in the textile industry and in the paint industry, prepared from 8 to 120 parts by weight of acrylic and / or methacrylic acid, 8 to 120 parts by weight of N-alkoxymethyl acrylamide and / or N-alkoxymethylraethacrylamide, optionally alkoxy, methoxy, propoxy, butoxy or isobutoxy, 8 to 120 parts by weight of 2-hydroxyalkyl acrylate and / or 2-hydroxyalkyl methacrylate, wherein alkyl is ethyl or propyl, 440 to 776 parts by weight of other monomers from the group consisting of esters of acrylic and / or methacrylic acid having 1 to 8 carbon atoms in the alkyl chain and optionally up to 320 parts by weight of styrene and up to 16,000 parts by weight additives, in particular from the group comprising aqueous dispersions of thermoplastic copolymers, water surfactants, defoamers, viscosity regulators, coalescing agents, pH regulators, acidic sulfur catalysts, fungicides, electrolytes, pigments, fillers and hydrophobic additives. Process for the preparation of the thermoreactive water-dilutable compositions according to item 1, by semi-continuous emulsion copolymerization in the presence of surfactants, of a water-soluble initiator system, preferably in an inert atmosphere, characterized in that up to 100 to 400 parts by weight of water, optionally containing up to 20 parts by weight. parts of the surfactants and up to 10 parts by weight of the known redox initiation system, preferably only the reducing component, are added gradually at a temperature of 65 to 90 ° C with stirring over a period of 1.5 to 6 hours an emulsion prepared from 800 parts by weight of the above % of monomers, 350 to 1200 wt. parts of water, 8 to 48 parts by weight of surfactants, and optionally up to 10 parts by weight of ammonium and / or sodium hydroxide, and simultaneously a solution of 1 to 20 parts by weight of the initiator system in 5 to 400 parts is added over a period of 1.5 to 7 hours. % by weight of water, wherein 251 019 after the monomer emulsion dosing is complete, the reaction mixture is maintained at this temperature for 1 to 4 hours, then cooled and eventually treated by adding up to 200 parts by weight of the above additives.