Printable swelling paste and application thereof
Abstract
The invention relates to a printable swelling paste containing the following mixture constituents: 1) polymers having carboxyl and amide group units and 2) an aldehyde or aldehyde-separating compound, as a cross-linking agent. The mixture can optionally contain other additives such as thickeners. The polymer component having carboxyl and amide groups is obtained by radical copolymerisation of monomers containing amide groups and of monomers containing carboxyl groups. Other comonomers can also be integrated by polymerization. The invention also relates to the use of the swelling paste for producing absorbent fibers, tissues and sheet material such as film by applying the swelling paste onto the supporting material and by subsequently treating thermally.
Term
Term ended
Expired 17 April 2018, 8.4 years ago.
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20 claims: 3 independent, 17 dependent
- 1Zastrzeżenia patentowe 1. Drukowalna pasta pęczniejąca zawierająca A) składnik 1 złożony z wodnego, częściowo lub całkowicie zobojętnionego roztworu polimeru, który stanowi produkt rodnikowej kopolimeryzacji mieszanin zawierających a) monomery zawierające grupy amidowe i b) monomery zawierające grupy karboksylowe i/lub grupy karboksylanowe, a także c) ewentualnie inne monomery polimeryzowalne rodnikowo, B) ze składnika 2 będącego substancją sieciującą i C) z ewentualnych innych dodatków, znamienna tym, że substancją sieciującą 2 jest aldehyd lub związek odszczepiający aldehyd, przy czym zawartość składnika sieciującego 2 wynosi 1 do 15% wagowych, w przeliczeniu na użyty polimer składnika 1.
- 2Drukowalna pasta pęczniejąca według zastrz. 1, znamienna tym, że polimer składnika 1 składa się z a) 1 do 80% molowych, korzystnie 1 do 60% molowych i najkorzystniej 1 do 20% molowych rodnikowo polimeryzowalnych monomerów zawierających grupy amidowe i z b) 20 do 99% molowych, korzystnie 40 do 99% molowych i najkorzystniej 80 do 99% molowych częściowo zobojętnionych, polimeryzowanych rodnikowo monomerów zawierających grupy karboksylowe, a także z c) 0 do 49% molowych, w przeliczeniu na monomery a) i b), dalszych, kopolimeryzowalnych z a) i b), wpolimeryzowanych monomerów.
- 3Drukowalna pasta pęczniejąca według zastrz. 1 albo 2, znamienna tym, że jako zawierające grupy amidowe monomery a) polimeru składnika 1 stosuje się akryloamid i/łub metakryloamid.
- 4Drukowalna pasta pęczniejąca według zastrz. 1 albo 2, znamienna tym, że jako zawierające grupy karboksylowe monomery polimeru składnika 1 stosuje się kwas akrylowy, kwas metakrylowy, kwas maleinowy, kwas fumarowy, kwas itakonowy lub mieszaniny tych kwasów.
- 5Drukowalna pasta pęczniejąca według zastrz. 1 albo 2, znamienna tym, że monomery b) wpolimeryzowane w polimer składnika 1 są zobojętnione w co najmniej 25% molowych, korzystnie w co najmniej 50% molowych.
- 6Drukowalna pasta pęczniejąca według zastrz. 1, znamienna tym. że składnik sieciujący 2 jako związki odszczepiające aldehyd lub aldehydy zawiera formaldehyd, paraldehyd, glioksal, kwas glioksalowy lub heksametylenotetraminę lub ich mieszaniny.
- 7Drukowalna pasta pęczniejąca według zastrz. 1, znamienna tym, że po usieciowaniu wykazuje ona retencję co najmniej 25 g/g, korzystnie co najmniej 60 g/g.
- 8Drukowalna pasta pęczniejąca według zastrz. 1, znamienna tym, że po usieciowaniu wykazuje ona na 10 g/m 2 naniesienia suchej substancji wysokość pęcznienia co najmniej 0,8 mm, korzystnie co najmniej 1,0 mm, a najkorzystniej co najmniej 1,5 mm.
- 9Zastosowanie drukowalnej pasty pęczniejącej określonej w zastrz. 1 do wytwarzania absorbujących włókien, wiązek włókien, włóknin, nici, tkanin i innych płaskich wyrobów przez nanoszenie pasty pęczniejącej na materiał nośnika i następną obróbkę termiczną.
- 10Zastosowanie drukowalnej pasty pęczniejącej według zastrz. 9, znamienne tym, że polimer składnika 1 składa się z a) 1 do 80% molowych, korzystnie 1 do 60% molowych i najkorzystniej 1 do 20% molowych rodnikowe polimeryzowalnych monomerów zawierających grupy amidowe i z b) 20 do 99% molowych, korzystnie 40 do 99% molowych i najkorzystniej 80 do 99% molowych częściowo zobojętnionych, polimeryzowanych rodnikowo monomerów zawierających grupy karboksylowe, a także z c) 0 do 49% molowych, w przeliczeniu na monomery a) i b), dalszych, kopolimeryzowalnych z a) i b), wpolimeryzowanych monomerów. 189 442
- 11Zastosowanie drukowalnej pasty pęczniejącej według zastrz. 9 albo 10, znamienne tym, że jako zawierające grupy amidowe monomery a) polimeru składnika 1 stosuje się akryloamid i/lub metakryloamid.
- 12Zastosowanie drukowalnej pasty pęczniejącej według zastrz. 9 albo 10, znamienne tym, że jako zawierające grupy karboksylowe monomery polimeru składnika 1 stosuje się kwas akrylowy, kwas metakrylowy, kwas maleinowy, kwas fumarowy, kwas itakonowy lub mieszaniny tych kwasów.
- 13Zastosowanie drukowalnej pasty pęczniejącej według zastrz. 9 albo 10, znamienne tym, że monomery b) wpolimeryzowane w polimer składnika 1 są zobojętnione w co najmniej 25% molowych, korzystnie w co najmniej 50% molowych.
- 14Zastosowanie drukowalnej pasty pęczniejącej według zastrz. 9, znamienne tym, że składnik sieciujący 2 jako związki odszczepiające aldehyd lub aldehydy zawiera formaldehyd, paraldehyd, glioksal, kwas glioksalowy lub heksametylenotetraminę lub ich mieszaniny.
- 15Zastosowanie drukowalnej pasty pęczniejącej określonej w zastrz. 1 do wytwarzania kabli energetycznych i komunikacyjnych, oraz włóknin i tkanin dla rolnictwa, dla przemysłu odzieżowego, dla przemysłu wyrobów higienicznych i dla branży pogrzebowej.
- 16Zastosowanie drukowalnej pasty pęczniejącej według zastrz. 15, znamienne tym, że polimer składnika 1 składa się z a) 1 do 80% molowych, korzystnie 1 do 60% molowych i najkorzystniej 1 do 20% molowych rodnikowo polimeryzowalnych monomerów zawierających grupy amidowe i z b) 20 do 99% molowych, korzystnie 40 do 99% molowych i najkorzystniej 80 do 99% molowych częściowo zobojętnionych, polimeryzowanych rodnikowo monomerów zawierających grupy karboksylowe, a także z c) 0 do 49% molowych, w przeliczeniu na monomery a) i b), dalszych, kopolimeryżowalnych z a) i b), wpolimeryzowanych monomerów.
- 17Zastosowanie drukowalnej pasty pęczniejącej według zastrz. 15 albo 16, znamienne tym, że jako zawierające grupy amidowe monomery a) polimeru składnika 1 stosuje się akryloamid i/lub metakryloamid.
- 18Zastosowanie drukowalnej pasty pęczniejącej według zastrz. 15 albo 16, znamienne tym, że jako zawierające grupy karboksylowe monomery polimeru składnika 1 stosuje się kwas akrylowy, kwas metakrylowy, kwas maleinowy, kwas fumarowy, kwas itakonowy lub mieszaniny tych kwasów.
- 19Zastosowanie drukowalnej pasty pęczniejącej według zastrz. 15 albo 16, znamienne tym, ze monomery b) wpolimeryzowane w polimer składnika 1 są zobojętnione w co najmniej 25% molowych, korzystnie w co najmniej 50% molowych.
- 20Zastosowanie drukowalnej pasty pęczniejącej według zastrz. 15 albo 16, znamienne tym, że składnik sieciujący 2 jako związki odszczepiające aldehyd lub aldehydy zawiera formaldehyd, paraldehyd, glioksal, kwas glioksalowy lub heksametylenotetraminę lub ich mieszaniny.
Independent claims20
105 paragraphs, as filed
The present invention relates to a printable swelling paste containing a mixture of polymers constituting the product of radical copolymerization of monomers containing carboxyl group units and amide group units with aldehyde crosslinkers. The invention also relates to the use of this paste. The swelling paste can be stored for a long time without thickening or gelation. It is used to coat various carrier materials and is crosslinked on them under the influence of temperature, with the result that structures are formed that have the ability to absorb large amounts of water and aqueous liquids.
Super-absorbing polymers have been known for a long time and are commercially available in the form of powders, for example called Favor or Cabloc. However, processing such powders
189 442 is technically troublesome, and their abrasion causes the formation of dusty, inhaled particles, and therefore they cause reservations due to occupational hygiene.
Alternative polymerization is known on previously prepared surfaces or on threads, however, due to the need to use a protective gas technique and compliance with relevant safety regulations, this method is limited to chemical industry plants and cannot be transferred to other industries, such as industry polygraphy and textile.
EP 188 091 describes an absorbent, porous flat textile product produced by fularding a mixture of an aqueous solution of a non-crosslinked prepolymer with a crosslinking substance on a nonwoven and subsequent thermal crosslinking. The disadvantage of said method is the possibility of introducing a cross-linking substance of the type polyhaloalkanols, haloepoxyalkanes and poly (glycidyl ethers), due to their high reactivity, only immediately before processing, because otherwise there are undesirable thickening of the mixture, and in addition the said crosslinkers are very harmful.
EP 357 474 describes the spraying of low-viscosity aqueous solutions of non-crosslinked poly (acrylic acids) onto a flat cellulose fabric and subsequent thermal crosslinking to water swellable gels under the action of simultaneously applied crosslinkers. Ions of multivalent metal, as well as epoxides, aziridines, poly (glycidyl ethers), which due to their carcinogenic properties cannot currently be used, have been described as cross-linking substances, and their use in the hygiene and food packaging industry is particularly problematic. In addition, when the coating solutions are stored at room temperature, they are prematurely crosslinked, which prevents further processing of a very sticky or gelled mass.
DE-OS 2 327 249 describes a washing method that uses water-insoluble cationic solid exchangers based on polymers of (meth) acrylic acid, (meth) acrylamide and formaldehyde or formaldehyde-amine condensates. Polymerization of monomers takes place in the presence of formaldehyde and leads directly to cross-linked, water-insoluble polymers. It does not pass through a separate, water-soluble state in which processing in the form of dissolved polymer would be possible.
US-Re No. 32 659, page 7, mentions glyoxal as a possible crosslinker in the production of superabsorbent materials, however, as in DE-OS 2 327 249, it is polymerization that leads to crosslinked polymers in one step insoluble in water, in which no intermediate steps leading to soluble polymers can be separated.
The patent application De No. 195 21 431 A1 describes a method in which reactive cross-linking substances such as polyfunctional epoxides, aziridines, poly (glycidyl ethers) and epihalohydrin are introduced shortly before printing into an aqueous solution of pre-crosslinked poly (acrylic acid). Although a printable paste has also been described, the reactive crosslinkers used have the major disadvantage that the mixture of the two components, due to the thickening already present at room temperature, cannot be stored for a long time and must be prepared again and again.
The object of the present invention was therefore to develop a printable paste, which is applied in one operation to a pre-prepared flat product and which, after subsequent heat treatment, can swell in the presence of water or aqueous solutions, and increase the initial volume many times. The finished paste should be able to be stored at room temperature for at least 1 week without changing the viscosity of the paste or deteriorating swelling capacity after processing. In addition, the paste must not contain flammable and hazardous substances. Crosslinking should be possible already at 140 ° C and at a temperature of 160 ° C should last no more than 5 minutes due to thermal load on the carrier material or for economic reasons. After this time, crosslinking should be completed and the coated substrate should have sufficient swelling capacity and swelling rate. In addition, the resulting gel should have sufficient strength.
189 442
The problem according to the invention is surprisingly solved by means of a mixture of two components, component 1 being an aqueous copolymer solution of monomers containing carboxyl groups and amide groups and component 2 being an aldehyde crosslinker, where other additives may optionally be present in the mixture.
The subject of the invention is therefore a printable swelling paste comprising A) component 1 consisting of an aqueous, partly or completely neutralized polymer solution which is the product of radical polymerization of mixtures containing
a) monomers containing amide groups and
b) monomers containing carboxyl groups and / or carboxylate groups, as well as
c) optionally other radical polymerizable monomers, and from B) component 2 which is a crosslinker, and also from C) optional other additives which is characterized in that the crosslinker 2 is an aldehyde or an aldehyde splittering compound, the content of crosslinker 2 being 1 up to 15% by weight, based on the polymer of component 1 used.
The polymer of component 1 preferably consists of
a) 1 to 80 mole%, more preferably 1 to 60 mole% and most preferably 1 to 20 mole% of radically polymerizable monomers containing amide groups and
b) 20 to 99 mole%, more preferably 40 to 99 mole% and most preferably 80 to 99 mole% partially neutralized, radically polymerizable carboxyl group-containing monomers.
The amide-containing monomers of a) are, for example, (meth) acrylic acid amides such as acrylamide, methacrylamide and vinylcarboxylic acid amides such as N-vinylformamide and N-vinylacetamide. Acrylamide is preferably used.
As monomers containing carboxyl groups according to b), methacrylic acid, maleic acid, fumaric acid, itaconic acid as well as their salts and mixtures are also involved in addition to acrylic acid. As counterions, for example, sodium, potassium, an ammonium group, alkylammonium groups, alkanolammonium groups or mixtures thereof are involved. Preferably, acrylic acid with sodium counterion is used as the carboxyl group-containing monomer.
The degree of neutralization of the carboxyl groups of the polymers of the present invention co-determines the swelling and retention properties of crosslinked swelling pastes and is preferably at least 25 mol%, more preferably at least 50 mol%. According to the invention, the neutralization of carboxyl groups can take place before or after polymerization, often with some of the neutralizing agent being introduced prior to polymerization and the remainder after polymerization. In any case, however, care must be taken to avoid undesirable saponification of the monomers containing amide groups as a result of the introduction of alkaline substances. It may also be desirable to form amino groups in the polymer already formed by the acid saponification of units formed, for example, from vinyl carboxylic acid amides, which amino groups can in turn react cross-linking with component 2 of the crosslinker.
In addition to monomers a) and b), polymer component 1 may be polymerized
c) 0 to 49 mole% of other, anionic or nonionic monomers, such as, for example, (meth) allylsulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, alcohol mono (meth) acrylic acid esters vinyl, alkyloxyethanes and alkylphenoloxylates to modify polymer properties, for example, to improve adhesion to a carrier material, to increase salt resistance, or to adjust flexibility.
Polymers are generally used in the form of aqueous solutions at a concentration of 15 to 60% by weight, preferably at a concentration of 20 to 40% by weight, to make the swelling pastes of the invention. In special cases, for example during the production of the film, it may be necessary to add alcoholic additives to the aqueous phase to improve film formation.
The production of copolymers takes place according to the state of the art and takes place either in the adiabatic or isothermal polymerization of the monomer solution, where neutralization can take place in whole or in part already in the monomer solution or only in the finished polymer. Usually, polymerization is initiated using the system as initiator
189 442 redox or by means of a thermally initiating catalyst or a mixture of both. Typical redox systems that are particularly used during aqueous solution polymerization include: hydrogen peroxide-ascorbic acid, sodium persulfate, sodium bisulfite; hydroxylamine hydrochloride-hydrogen peroxide; ascorbic acid-t-BHP. redox systems containing metal salts and other known systems. If the polymerization is carried out in organic solvents, organic peroxides are often used, optionally together with redox partners. To regulate molecular weight, it may be desirable to use chain transfer compounds, so-called regulators, such as, for example, mercaptoethanol, thioglycolic acid and others.
In some cases, it has proved advantageous to pre-crosslink the copolymers of the present invention during their preparation with small amounts of radically crosslinking monomers, with no water insoluble parts being formed. Aqueous solutions of these lightly crosslinked polymers may give the swelling paste of the present invention, inter alia, favorable rheological properties, or may improve film-forming properties and swelling of the cross-linked final product.
Component 2 acts as a cross-linking substance and connects the individual polymer chains in the Mannich reaction through the acrylamide functional groups embedded in them to form a water insoluble but still water-swellable network. Crosslinking agents are all water-soluble or easily water-dispersible compounds with at least one aldehyde function or compounds which release aldehyde groups in the presence of water and when heated. Examples include: formaldehyde, hexamethylenetriamine, acetaldehyde, paraldehyde, glyoxal, glyoxal hydrate trimer and glyoxylic acid.
The swelling paste is made by mixing an aqueous polymer solution (component 1) with a cross-linking substance (component 2) and can be processed immediately afterwards. It has often proved advantageous to incorporate the crosslinker in the form of a solution. The weight ratio of polymer to crosslinker can vary widely. The content of crosslinker, based on the polymer content, can be from 1 to 15% by weight, preferably from 1 to 9% by weight. Depending on the content of monomers containing amide groups, it is necessary to use more or less crosslinker to obtain the desired swelling and retention properties. It should also take into account the crosslinking activity of the crosslinker when determining the amount used. Exact amounts of crosslinker can be determined by a skilled person without difficulty in optimizing the product.
One skilled in the art can use dilution with water or the addition of thickeners or surfactants to adjust the desired viscosity of the swelling pastes of the invention. Unlike the mixtures according to German Patent Application DE 195 21 431 A, the swelling paste can be stored for several weeks without deterioration of its properties, which greatly facilitates the production process. The use of highly toxic, carcinogenic or mutagenic cross-linking substances by persons not normally trained in the use of such substances is also dropped, so it is still necessary according to the state of the art for earlier patent applications EP No. 188 091, EP No. 357 474 and DE No. 195 21 431.
In the swellable paste, other non-polymerized additives with beneficial effects may be included. In particular, they are substances that reduce the dryness of the dry product, reduce stickiness, improve printing viscosity and increase conductivity. Thus, in order to improve the gel stability and set the desired printing viscosity, ordinary water-effective thickeners, such as, for example, cellulose derivatives, as well as more strongly crosslinked polyacrylates, produced under the name "Cabloc CTF" by Stockhausen are added. They do not swell as usual in a polyacrylate solution, but clearly improve viscosity during printing.
The swelling paste produced in this way can be applied by known methods to a flat textile product, a fabric, a nonwoven fabric or a thread. Preferably, it is printed or applied with a squeegee using a template on the fabric or on the nonwoven fabric to achieve a uniform pattern.
189 442
Next, crosslink the polymer to be applied, which can be achieved by heat treatment. The duration of the heat treatment depends on the temperature used and the concentration of the selected crosslinker, as well as the molar ratio of the polymer-related amide units. This temperature may be in the range of 100 ° C to 160 ° C, preferably 130 ° C to 160 ° C, most preferably 140 ° C to 150 ° C. In any case, the crosslinking temperature must be above the boiling point of the solvent (water) and below the shrinkage temperature of the carrier. For economic reasons, the crosslinking time available is usually less than 5 minutes, preferably less than 2 minutes.
Preferably, the swelling paste of the present invention after crosslinking has a retention of at least 25 g / g, more preferably at least 60 g / g and furthermore, after crosslinking, has a swelling height for applying a dry substance of 10 g / m<sup>2</sup> at least 0.8 mm, preferably at least 1.0 mm and most preferably at least 1.5 mm.
The production of carrierless films is carried out first by applying the swelling paste to a support material, preferably a metal or plastic support, and optionally using release agents. After removal of the solvent, which optionally takes place below the boiling point of the solvent, and after thermal cross-linking, the film is removed from the support material, often after annealing.
The subject of the invention is therefore also the use of the swelling paste previously discussed for the production of absorbent fibers, fiber bundles, nonwovens, threads, fabrics and other flat products, for example webs by applying the swelling paste on the support material and subsequent heat treatment, as well as for the production of power and communication cables and fibers and fabrics for agriculture and the clothing industry, for example in the cable industry, in the hygiene industry, in food packaging, as well as in the funeral industry.
The testing of various swelling pastes was always carried out on a comb table using a template by applying them with a squeegee on a polyester fabric, followed by drying in a Heraeus circulating air dryer. The application of the dry substance varied within certain limits usually occurring in laboratory conditions.
Technical utility measurements:
Measurement of swelling height and swelling rate:
To measure the swelling height and swelling rate, a round section with an area of 25.4 cm2 of coated flat textile product is placed in a plastic cup with an inside diameter of 80.5 mm and a height of 30 mm. Two thin polyester nonwovens (0.5 mm thick) are placed on this nonwoven followed by a round punch with a diameter of 80 mm and a weight of 100 g. This punch has 60 through holes, each with a diameter of 2 mm. During the measurement, the height of the upper edge of the stamp is monitored. 75 ml of VE water (conductivity <0.1 mS) is introduced into the cup and the lifting of the upper edge of the punch after 1 minute and 10 minutes is recorded (double mark), with the upper edge of the punch being taken as the zero point before entering the water. In order to eliminate the effect of applying different amounts, the swelling height measured in one operation is calculated based on the polymer application of 10 g / m2.
Determination of retention.
To determine retention, a round piece of printed fabric 3 cm in diameter is welded to a commercial tea bag. The bag is then immersed in a dish with distilled water for 30 minutes, suspended for 10 minutes and centrifuged for 5 minutes at 1200 rpm in a commercial linen centrifuge. The weight of the centrifuged tea bag is determined. To calculate retention, the weight of the dry fabric bag is subtracted from the weight of the centrifuged tea bag and divided by the weight of the printed polymer.
Examples.
Example 1
1000 g of a copolymer solution of 90 mole% acrylic acid and 10 mole% acrylamide, with a degree of neutralization of 50%, a dry matter content of 25% by weight and an average molar mass of 200,000 g / mol was mixed with 37.5 g of 40% glyoxal. The paste obtained had a viscosity of 9700 mPas (marked with a Brookfield viscometer, spindle 8)
189 442 no 4, 10 revolutions per minute) and it was printed after 1 hour using a template on polyester fabric. All printed substrates were heated for 2 minutes in circulating air on a tension frame in a Heraeus dryer. The following results were obtained:
<td>Example No.</td><td>applied dry substance</td><td>Temperature</td><td>Swelling amount after 1 minute</td><td>Swelling height after 10 minutes</td><td>Swelling height per 10 g / m2<sup>2</sup></td><td>Retention, g / g</td>
<td>la</td><td> 17,0</td><td>145 ° C</td><td>1.1 mm</td><td>2.55 mm</td><td>1.5 mm</td><td>97.5 g / g</td>
<td>b</td><td> 14,3</td><td>150 ° C</td><td>2.1 mm</td><td>2.35 mm</td><td>1.6 mm</td><td>71.7 g / g</td>
<td>ic</td><td> 11,5</td><td>155 ° C</td><td>2.1 mm</td><td>2.3 mm</td><td>2.0 mm</td><td>60.5 g / g</td>
Example II
The prepared, ready but unused mixture of Example 1 was stored for 1 week at room temperature. It then had a viscosity of 10,200 mPas (20 ° C, Brookfield, spindle 4.10 rpm). The paste was also processed as described in Example 1:
<td>Example No.</td><td>applied dry substance</td><td>Temperature</td><td>Swelling amount after 1 minute</td><td>Swelling height after 10 minutes</td><td>Swelling height per 10 g / m2</td><td>Retention, g / g</td>
<td> 2</td><td>14.2 g</td><td>145 ° C</td><td>2.05 mm</td><td>2.60 mm</td><td>1.8 mm</td><td>84.9 g / g</td>
Example III
The paste from Example 1 was stored for a total of 4 weeks. After this time, the paste had a viscosity of 9600 mPas.
Processing as described in Example 1:
<td>Example No.</td><td>applied dry substance</td><td>Temperature</td><td>Swelling amount after 1 minute</td><td>Swelling height after 10 minutes</td><td>Swelling height per 10 g / m2</td><td>Retention, g / g</td>
<td>III</td><td>17.4 g</td><td>145 ° C</td><td>1.0 mm</td><td>2.65 mm</td><td>1.5 mm</td><td>87.0 g / g</td>
Example IV
100 g of the aqueous copolymer solution of Example 1 instead of glyoxal was mixed with 3.83 g of a 50% aqueous solution of glyoxylic acid and after storage for 1 day was processed as described in Example I.
<td>Example No.</td><td>Dry substance applied</td><td>Temperature</td><td>Swelling amount after 1 minute</td><td>Swelling height after 10 minutes</td><td>Swelling height per 10 g / m2</td><td>Retention, g / g</td>
<td>IVa</td><td>17.6 g / m2</td><td>135 ° C</td><td>0.7 mm</td><td>1.4 mm</td><td>0.8 mm</td><td>160 g / g</td>
<td>IVb</td><td>14.3 g / m2</td><td>140 ° C</td><td>1.0 mm</td><td>2.35 mm</td><td>1.6 mm</td><td>101 g / g</td>
<td>IVc</td><td>12.9 g / m2</td><td>145 ° C</td><td>1.7 mm</td><td>1.95 mm</td><td>1.5 mm</td><td>84.9 g / g</td>
<td>IVd</td><td>14.9 g / m2</td><td>150 ° C</td><td>1.2 mm</td><td>1.6 mm</td><td>1.1 mm</td><td>48.2 g / g</td>
<td>IVe</td><td>15.3 g / m2<sup>2</sup></td><td>155 ° C</td><td>0.9 mm</td><td>1.4 mm</td><td>0.9 mm</td><td>35 g / g</td>
Example V
100 g terpolymer solution with 94 mole% acrylic acid, 5 mole% acrylamide and 1 mole% methacrylic acid ester with methoxypoh (ethylene glycol) (1000), (product Bisomer S 10 W) with a degree of neutralization of 50%, dry matter content
189 442
25% by weight and a viscosity of 11,000 mPas were mixed with 3.75 g of 40% glyoxal and processed further as described in Example 1.
<td>Example No.</td><td>Dry substance applied</td><td>Temperature</td><td>Swelling amount after 1 minute</td><td>Swelling height after 10 minutes</td><td>Swelling height per 10 g / 2</td><td>Retention, g / g</td>
<td>V</td><td>7.8 g / m2<sup>2</sup></td><td>150 ° C</td><td>0.9 mm</td><td>1.5 mm</td><td>1.9 mm</td><td>180 g / g</td>
Example VI
100 g of the copolymer solution of Example 1 was mixed with 3 g of hexamethylenetetramine and processed as described in Example 1.
<td>Example No.</td><td>Dry substance applied</td><td>Temperature</td><td>Swelling amount after 1 minute</td><td>Swelling height after 10 minutes</td><td>Swelling height per 10 g / m2</td><td>Retention, g / g</td>
<td>VI</td><td>15.0 g / m2</td><td>150 ° C</td><td>1.65 mm</td><td>1.5 mm</td><td>1.0 mm</td><td>29 g / g</td>
<td>VIb</td><td>14.3 g / m2</td><td>160 ° C</td><td>1.6 mm</td><td>1.5 mm</td><td>1.0 mm</td><td>27 g / g</td>
Example VII
Example 6 was repeated with the difference that the degree of neutralization of the copolymer used with sodium hydroxide was increased to 60 mol% or 70 mol% before the introduction of hexamethylenetetramine.
<td>Example No.</td><td>Dry substance applied</td><td>Degree of neutralization</td><td>Height swelling 1 minute</td><td>Swelling height after 10 minutes</td><td>Swelling height per 10 g / m2</td><td>Retention, g / g</td>
<td>VIIa</td><td>15.0 g / m2</td><td>60 molar</td><td>1.9 mm</td><td>165 mm</td><td>1.1 mm</td><td>67.6 g / g</td>
<td>VIIb</td><td>16.6 g / m2</td><td>70 molar</td><td>1.0 mm</td><td>1.3 mm</td><td>0.8 mm</td><td>92.7 g / g</td>
Example VIII
The swelling paste according to example 4 was diluted with water in a 1: 1 ratio and then applied to aramid fibers. The aramid fibers obtained in this way were subjected to a short heat treatment with a hot air blower. The treated aramid fibers were then subjected to a swelling test, such as that described in EP Patent No. 482 703. page 5, from line 50. A polymer loading of 16% by weight was obtained. The product was immediately tight and kept tight until the end of the test after 6 days.
Comparative Example 1.
The polymer of Example 1 was mixed with 2% by weight bisglycidyl ethylene glycol ether. This product had an initial viscosity of 11,000 mPas. After storage for 4 hours at room temperature, the viscosity has already increased to 27,000 mPas. After storage for 48 hours, the product was completely cross-linked and could be removed from the dish in pieces with a sharp-edged tool, only with great effort.
Comparative Example 2.
A polymer comparable to the polymer of Example 1 with a viscosity of 200 mPas was used with the difference that it was a pure acrylic acid homopolymer with a degree of neutralization of 50%, which means that no amide functional groups were bound in the polymer chain. This polymer, which was in the form of a 30% aqueous solution, was mixed with 3.75% by weight glyoxal, printed as in Example 1 and dried.
189 442
<td>Comparative Example No.</td><td>applied dry substance</td><td>Temperature</td><td>Swelling amount after 1 minute</td><td>Swelling height after 10 minutes</td><td>Swelling height per 10 g / m2<sup>2</sup></td><td>Retention, g / g</td>
<td> 2</td><td>17.8 g</td><td>150 ° C</td><td>0.0 mm</td><td>0.15 mm</td><td>0.1 mm</td><td>0.0 g / g</td>
Example IX
An aqueous polymer solution with 30 mole% acrylic acid, 30 mole% sodium acrylate and 40 mole% acrylamide with a dry substance content of 28% and a viscosity of 7800 mPas was mixed with 0.75% by weight 40% glyoxal and processed as described in Example I. The printed fabric was heated in a Heraeus dryer for 2 minutes at 150 ° C.
<td>Example No.</td><td>applied dry substance</td><td>Temperature</td><td>Swelling amount after 1 minute</td><td>Swelling height after 10 minutes</td><td>Swelling height per 10 g / m2<sup>2</sup></td><td>Retention, g / g</td>
<td>IX</td><td>17 g</td><td>150 C.</td><td>0.49 mm</td><td>1.32 mm</td><td>0.78 mm</td><td>109 g / g</td>
Example X
An aqueous polymer solution of 20 mole% acrylic acid, 20 mole% sodium acrylate and 60 mole% acrylamide with a dry substance content of 27% and a viscosity of 14,400 mPas was mixed with 0.75% by weight and 0.5% by weight glyoxal and processed as described in example I. The drying took 2 minutes in circulating air in a Heraeus dryer at 150 ° C.
<td>Example No.</td><td>wt% glioksanolu</td><td>Dry substance applied</td><td>Swelling amount after 1 minute</td><td>Swelling height after 10 minutes</td><td>Swelling height per 10 g / m2</td><td>Retention, g / g</td>
<td>xa</td><td> 0,75</td><td> 15,5</td><td>0.99 mm</td><td>1.91 mm</td><td>1.23 mm</td><td> 37</td>
<td>xb</td><td> 0,5</td><td> 16,5</td><td>0.71 mm</td><td>1.21 mm</td><td>0.73 mm</td><td> 90</td>
UP Department of Publications. Circulation of 50 copies
Price PLN 2.00
16 members in 10 offices
Priority claims6
| Document | Office | Kind | Date |
|---|---|---|---|
| 19717395 | Germany | A | |
| 9802286 | European Patent Office (EPO) | W | |
| 9719717395 | – | – | – |
| 98EP9802286 | – | – | – |
| DE1997117395 | – | – | – |
| WO1998EP02286 | – | – | – |
Members16
| Document | Office | Kind | |
|---|---|---|---|
| CA2284054A1 | Canada | A1 | |
| DE19717395A1 | Germany | A1 | |
| WO9847932A1 | World Intellectual Property Organization (WIPO) | A1 | |
| AU7645098A | Australia | A | |
| DE19717395C2 | Germany | C2 | |
| EP0975681A1 | European Patent Office (EPO) | A1 | |
| TR199902477T2 | Türkiye | T2 | |
| BR9809414A | Brazil | A | |
| PL336412A1 | Poland | A1 | |
| AU722977B2 | Australia | B2 | |
| US6133369A | United States of America | A | |
| EP0975681B1 | European Patent Office (EPO) | B1 | |
| DE59809809D1 | Germany | D1 | |
| DK0975681T3 | Denmark | T3 | |
| PL189442B1This record | Poland | B1 | |
| CA2284054C | Canada | C |
Numbers
- Publication, DOCDB
- 189442
- Publication, EPODOC
- PL189442B
- Application
- 98336412
- Application, DOCDB
- 33641298
- Application, EPODOC
- PL19980336412
Titles2
- English
- PRINTABLE SWELLING PASTE AND APPLICATION THEREOF
- Polish
- Drukowalna pasta pęczniejąca oraz jej zastosowania
Classification
- CPC, 7
- D06N3/042
- C08F8/28
- C08F8/32
- C08F2800/10
- C08F2810/20
- C08K5/0025
- C09D11/10
- IPC, 5
- A61L15 00
- C08F8 28
- C08K5 00
- C09D11 10
- D06N3 04