GB1600161A - Graft-polymerised polymer fibres containing hydroxyl groups method of producing them and their utilisation - Google Patents

Graft-polymerised polymer fibres containing hydroxyl groups method of producing them and their utilisation Download PDF

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Publication number
GB1600161A
GB1600161A GB10983/78A GB1098378A GB1600161A GB 1600161 A GB1600161 A GB 1600161A GB 10983/78 A GB10983/78 A GB 10983/78A GB 1098378 A GB1098378 A GB 1098378A GB 1600161 A GB1600161 A GB 1600161A
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fibres
graft
parts
polymer
water
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GB10983/78A
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Lenzing AG
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Chemiefaser Lenzing AG
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M14/00Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/02Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin
    • D06M14/04Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives thereof

Description

(54) IMPROVEMENTS IN OR RELATING TO GRAFT-POLYMERISED POLYMER FIBRES CONTAINING HYDROXYL GROUPS, METHOD OF PRODUCING THEM, AND THEIR UTILISATION (71) We, CHEMIEFASER LENZING AK- TIENGESELLSCHAFT, a Company organised under the laws of Austria, residing at 4860 Lenzing, Austria, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The invention relates to graft-polymerised polymer fibres containing hydroxyl groups, in particular to cellulose fibres having graftpolymer chains which include acrylic acid and/or methacrylic acid units, and to their use.
Unless otherwise specified, all percentages, ratios and parts mentioned in this specification are by weight.
When manufacturing wet-layered nonwoven fabrics, in particular those with low basis weights, two fibre properties (i.e. the denier and length of a fibre) have a very strong influence on the production speed which can be used in the plants and on the quality of the non-woven fabrics produced. It has been known that there is a basic connection between on the one hand the denier and the length of a fibre, and on the other hand the density of stock which can be present in a stock inlet of a wet-layering-machine for non-woven fabrics. The finer the fibre denier and the longer the fibres, the lower is the stock density which can be obtained (and thus the production speed which can be used) in wet-layering-machines for non-woven fabrics.
Furthermore it is known that the tear propagation strength of non-woven fabrics increases as the length of the fibres used increases. Fine fibres offer a better opacity, due to the greater amount of fibres per unit area of the non-woven fabric. Thus it is desirable to use fine long fibres for the production of non-woven fabrics.
German Offenlegungsschrift No.
2,249,792 describes a method of modifying cellulose fibres by graft-polymerisation to produce modified fibres having a substantially increased dispersibility in an aqueous medium. The hydroxyl-group-containing fibres modified according to this method and having a fine denier and long length disperse even with relatively high stock density without getting entangled, and without the formation of knots and twisting of the fibres which would lead to the formation of inhomogeneities in non-woven fabrics formed therefrom. Aqueous dispersions of such modified fine and long fibres can be pumped easily, so that wet-layered non-woven fabrics can be produced from them using dispersions of fibres of high stock density and thus enabling the use of increased production speeds.These fibres have the disadvantage that they are difficult to disperse in hard water, so that if hard water is to be used it must first be softened. This generally requires a considerable amount of chemicals, e.g. in order to precipitate those compounds responsible for the hardness of the water in the form of oxalates or polyphosphates.
An object of the present invention is to provide graft-polymer fibres of the abovetype which do not suffer from poor dispersibility in hard water.
Accordingly, the present invention provides polymer fibres which have a main polymer chain containing hydroxyl groups, and graft polymer chains which include units derived from acrylic acid and/or methacrylic acid, the graft-polymer chain also including units derived from a hydroxyalkylmethacrylate.
Advantageously, the graft-polymer chain amounts to 5 to 60 %, preferably 10 to 40 %, of the weight of the polymer.
Preferably the weight ratio of the acrylic or methacrylic acid units in the graft-polymer chain to the hydroxyalkylmethacrylate limits in the graft polymer chain is from 3:1 to 1:3, preferably from 1.2:1 to 1:1.2.
Of the suitable hydroxyalkylmethacrylate components, hydroxyethylmethacrylate is preferred.
The graft-polymerisation can be carried out in any known manner in which the reaction can be initiated by electron bombardment, Ce4+ ions, Fe2+ ions. Cellulose fibres are most preferred for use as the main polymer chain but polyvinyl-alcohol fibres are also suitable.
The production of fibres according to the invention may be performed by reacting a main polymer containing hydroxyl groups (in particular cellulose fibres) under grafting conditions with a mixture of acrylic acid and/or methacrylic acid and hydroxyalkylmethacrylate components.
In this way, one can produce fibres which disperse in hard water and which have a denier of 1.3 dtex or more. The fibres can be cut into lengths of 6mm to 50mm, and they disperse very well in hard water. We have found that the bivalent ions Ca2+ and Mg2+, which are responsible for the hardness of water, have no influence at all on the dispersibility of the fibres according to the invention, up to the highest degrees of hardness. The dispersibility of the fibres is basically connected with the water imbibition value of the fibres. In can, however, be reversed by ions of a higher valency, such as A13+, thus reducing also the water imbibition value of the fibres.It is thus possible to lower the water imbibition value of non-woven fabrics made of fibres of the present invention by treatment of the fibres with solutions of ions of high valencies, i.e. to give them more wet-strength. Accordingly, a principal field of application of the fibres according to the invention is the production of non-woven fabrics according to the wet-layering method, wherein the non-woven fabric, after being formed, is treated before drying with solutions of compounds of trivalent metals or of metals of higher valency. By this treatment the water-retaining ability of the fabric is is reduced, thus facilitating drying.
The present invention will now be illustrated in more detail by the following Examples.
Example 1: 10 parts of viscose staple fibres having a denier of 1.7 dtex and a length of 30 mm were suspended for 15 minutes in an emulsion produced from 4.6 parts of carbon bisulphide, 2.5 parts of sodium hydroxide, 0.1 part of "Triton" X--155 (Rohm & Haas) and 243 parts of water in accordance with, for example, the procedure described in U.S.
Patent No. 3359224 thereby introducing sodium xanthate groups into the viscose fibres. The fibres were then thoroughly washed and treated with 300 parts of a 0.005 % aqueous solution of ferroammonium sulphate. After further washing graft-polymerisation was carried out with 20 parts of an aqueous solution containing 16% of a 1:1 mixture of methacrylic acid and hydroxyethylmethacrylate in the presence of 0.03 parts of hydrogen peroxide as catalyst. For stabilisation of the water/methacrylic acid/hydroxyethylmethacrylate mixture, 1% of an emulsifying agent sold as K30 by Bayer AG was added. During the graft-polymerisation, which lasted for 1.5 hours, the temperature was kept at 60"C. Then the fibres were recovered by filtration, washed and dried.
Their weight increase was 28%, which means that 88% of the monomer mixture used was converted into a graft-polymer chain. The grafted fibres were converted with heavily diluted sodium lye into their corresponding sodium salt form and washed with water and dried. The grafted fibres prepared in this way and having a consistency of 0.3% dispersed in hard water having a dH (German hardness degree) of 28 , without twisting. A nonwoven fabric produced of this dispersion on a laboratory sheet-former exhibited uniformly distributed fibres without cloudy agglomerations. The same effect was achieved when the fibres were dispersed directly, without isolation of the salt form, in hard water having a dH of 28 and whose pHvalue was adjusted at 8.5.The water-retaining ability determined on the fibres of the wet non-woven fabric according to German Industrial Standard 53,814 was 253%. After spraying of a 1% aluminium-ammonium sulphate solution onto the non-woven fibre fabric, the water-retaining ability of the fibres was found to be 117%.
Example 2: The method of Example 1 was repeated but the mixture of water/hydroxyethylmethacrylate was preheated to 80 C, mixed with hydrogen peroxide and brought into contact with the fibres containing xanthate groups (1.7 dtex, 20 mm). After 15 minutes the graftpolymerisation process was stopped by the addition of cold water with which the fibres were washed. The weight increase of the fibres after drying was 27%, which means that 84.4% of the monomer mixture used was converted into a graft-polymer chain. After treatment with a sodium bicarbonate solution the fibres having a length of 20 mm and a consistency of 0.3% dispersed very well in water having a hardness dH of 28 and could be processed into a non-woven fabric without difficulties.
Example 3: Three parts of viscose staple fibres (1.7 dtex, 15 mm) were, as described in U.S.
Patent No. 3,083,118, immersed into 477 parts of a 0.2% chromium (III) chloride solution for 5 minutes at a pH-value of 3.7, then separated and washed with water. These three parts of viscose staple fibres were introduced into a mixture of 210 parts of water, 12 parts of acrylic acid and 12 parts of hydroxyethylmethacrylate at 72"C, then heated to 90"C. This temperature was maintained for one hour. After separating, washing and drying the weight increase of the fibres was 28%. The resultant fibres having a consistency of 0.1% dispersed very well in hard water (28 dH).
Example 4: In this example the method of E. Schwab et al. (TAPPI, 45, page 390) was used. 5 parts of viscose fibres (1.7 dtex, 12 mm) were distributed in 400 parts of water with introduction of nitrogen and stirring, in a suitable reaction vessel (comprising a gas-introduction pipe, a stirrer and a dropping funnel). Still under nitrogen, 12 ml of a solution which contained 0.1 mole of cer (IV)-ammonium nitrate and 1 mole of nitric acid per litre was added. Under vigorous stirring, 10 parts of a mixture containing methacrylic acid and hydroxyethylmethacrylate, in a weight ratio of 1:1 and which had been stabilised with 0.3 parts of the emulsifying agent K 30 (Bayer AG) were added. After a reaction time of 1.5 hours at room temperature, the fibres were separated by filtration and thoroughly washed, at first with water and then with acetone.After further washing with water, the fibres were allowed to rest in a diluted sodium bicarbonate solution and then separated and washed. A weighed part of the fibres treated in this way dispersed very well in hard water of the hardness 25 dH. A knot-free sheet could be formed from the aqueous dispersion of fibres on a laboratory sheet-former. The weight increase of the fibres was determined on the dried remaining fibres. It was 30%.
Example 5: 10 parts of polyvinyl alcohol fibres having a denier of 1.7 dtex and a length of 20 mm were pretreated under the conditions described in Example 1, and graft-polymerised at 70"C with 20 parts of a 16% mixture containing equal parts of hydroxyethylmethacrylate and methacrylic acid in water and also containing 0.03 parts of hydrogen peroxide. The graft-polymerisation was performed in such a way that the fibres increased in weight by 25%. The finished product thus contained 20% graft-polymer chains. After conversion of the carboxyl groups of the graft-polymer chains into the corresponding sodium salt using diluted soda solution (20/0), the graft-modified polyvinylalcohol fibres dispersed very well in hard water having a hardness dH of 22".
The word "Triton" used in this specification is a registered Trade Mark.
WHAT WE CLAIM IS: 1. Polymer fibres which have a main polymer chain containing hydroxyl groups, and graft polymer chains which include units derived from acrylic acid and/or methacrylic acid, the graft-polymer chain also including units derived from a hydroxyalkylmethacrylate.
2. Fibres according to Claim 1, wherein the weight of the graft-polymer chain amounts to 5 to 60% of the weight of the polymer.
3. Fibres according to Claim 2, wherein the weight of the graft-polymer chain amounts to 10 to 40% of the weight of the polymer.
4. Fibres according to Claim 1, 2 or 3, wherein the weight ratio of the acrylic and methacrylic acid units in the graft-polymer chain to the hydroxyalkylmethacrylate units in the graft polymer chain is from 3:1 to 1:3.
5. Fibres according to Claim 4, wherein the said weight ratio is from 1.2:1 to 1:1.2.
6. Fibres according to any one of the preceding claims, wherein the said hydroxyalkylmethacrylate is hydroxyethylmethacrylate.
7. Fibres according to any one of the preceding claims, wherein the main polymer chain is a cellulose polymer.
8. Fibres according to Claim 1, substantially as hereinbefore described in any one of the Examples.
9. A method of producing fibres according to any one of the preceding claims, which method comprises grafting a mixture of acrylic acid and/or methacrylic acid and hydroxyalkylmethacrylate components onto a main polymer chain containing hydroxyl groups.
10. A method of producing fibres according to Claim 9, substantially as hereinbefore described in any one of the Examples.
I I. Polymer fibres according to any one of Claims 1 to 8 whenever produced by a method as claimed in Claim 9 or 10.
12. A non-woven fabric produced from polymer fibres as claimed in any one of Claims I to 8 or 11.
13. A non-woven fabric according to Claim 12, wherein the formed fabric before drying has been treated with a solution of a compound of a trivalent metal or of a metal of higher valency.
14. A non-woven fabric according to
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (14)

  1. **WARNING** start of CLMS field may overlap end of DESC **.
    water having a hardness dH of 28 and could be processed into a non-woven fabric without difficulties.
    Example 3: Three parts of viscose staple fibres (1.7 dtex, 15 mm) were, as described in U.S.
    Patent No. 3,083,118, immersed into 477 parts of a 0.2% chromium (III) chloride solution for 5 minutes at a pH-value of 3.7, then separated and washed with water. These three parts of viscose staple fibres were introduced into a mixture of 210 parts of water, 12 parts of acrylic acid and 12 parts of hydroxyethylmethacrylate at 72"C, then heated to 90"C. This temperature was maintained for one hour. After separating, washing and drying the weight increase of the fibres was 28%. The resultant fibres having a consistency of 0.1% dispersed very well in hard water (28 dH).
    Example 4: In this example the method of E. Schwab et al. (TAPPI, 45, page 390) was used. 5 parts of viscose fibres (1.7 dtex, 12 mm) were distributed in 400 parts of water with introduction of nitrogen and stirring, in a suitable reaction vessel (comprising a gas-introduction pipe, a stirrer and a dropping funnel). Still under nitrogen, 12 ml of a solution which contained 0.1 mole of cer (IV)-ammonium nitrate and 1 mole of nitric acid per litre was added. Under vigorous stirring, 10 parts of a mixture containing methacrylic acid and hydroxyethylmethacrylate, in a weight ratio of 1:1 and which had been stabilised with 0.3 parts of the emulsifying agent K 30 (Bayer AG) were added. After a reaction time of 1.5 hours at room temperature, the fibres were separated by filtration and thoroughly washed, at first with water and then with acetone.After further washing with water, the fibres were allowed to rest in a diluted sodium bicarbonate solution and then separated and washed. A weighed part of the fibres treated in this way dispersed very well in hard water of the hardness 25 dH. A knot-free sheet could be formed from the aqueous dispersion of fibres on a laboratory sheet-former. The weight increase of the fibres was determined on the dried remaining fibres. It was 30%.
    Example 5:
    10 parts of polyvinyl alcohol fibres having a denier of 1.7 dtex and a length of 20 mm were pretreated under the conditions described in Example 1, and graft-polymerised at 70"C with 20 parts of a 16% mixture containing equal parts of hydroxyethylmethacrylate and methacrylic acid in water and also containing 0.03 parts of hydrogen peroxide. The graft-polymerisation was performed in such a way that the fibres increased in weight by 25%. The finished product thus contained 20% graft-polymer chains. After conversion of the carboxyl groups of the graft-polymer chains into the corresponding sodium salt using diluted soda solution (20/0), the graft-modified polyvinylalcohol fibres dispersed very well in hard water having a hardness dH of 22".
    The word "Triton" used in this specification is a registered Trade Mark.
    WHAT WE CLAIM IS: 1. Polymer fibres which have a main polymer chain containing hydroxyl groups, and graft polymer chains which include units derived from acrylic acid and/or methacrylic acid, the graft-polymer chain also including units derived from a hydroxyalkylmethacrylate.
  2. 2. Fibres according to Claim 1, wherein the weight of the graft-polymer chain amounts to 5 to 60% of the weight of the polymer.
  3. 3. Fibres according to Claim 2, wherein the weight of the graft-polymer chain amounts to 10 to 40% of the weight of the polymer.
  4. 4. Fibres according to Claim 1, 2 or 3, wherein the weight ratio of the acrylic and methacrylic acid units in the graft-polymer chain to the hydroxyalkylmethacrylate units in the graft polymer chain is from 3:1 to 1:3.
  5. 5. Fibres according to Claim 4, wherein the said weight ratio is from 1.2:1 to 1:1.2.
  6. 6. Fibres according to any one of the preceding claims, wherein the said hydroxyalkylmethacrylate is hydroxyethylmethacrylate.
  7. 7. Fibres according to any one of the preceding claims, wherein the main polymer chain is a cellulose polymer.
  8. 8. Fibres according to Claim 1, substantially as hereinbefore described in any one of the Examples.
  9. 9. A method of producing fibres according to any one of the preceding claims, which method comprises grafting a mixture of acrylic acid and/or methacrylic acid and hydroxyalkylmethacrylate components onto a main polymer chain containing hydroxyl groups.
  10. 10. A method of producing fibres according to Claim 9, substantially as hereinbefore described in any one of the Examples.
  11. I I. Polymer fibres according to any one of Claims 1 to 8 whenever produced by a method as claimed in Claim 9 or 10.
  12. 12. A non-woven fabric produced from polymer fibres as claimed in any one of Claims I to 8 or 11.
  13. 13. A non-woven fabric according to Claim 12, wherein the formed fabric before drying has been treated with a solution of a compound of a trivalent metal or of a metal of higher valency.
  14. 14. A non-woven fabric according to
    Claim 12, substantially as hereinbefore described in Example 1, 2 or 4.
GB10983/78A 1977-04-14 1978-03-20 Graft-polymerised polymer fibres containing hydroxyl groups method of producing them and their utilisation Expired GB1600161A (en)

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AT258977A AT354972B (en) 1977-04-14 1977-04-14 GRAFT-POLYMERIZED HYDROXYL GROUP-CONTAINING POLYMER FIBERS

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DE (1) DE2811541A1 (en)
FR (1) FR2387250A1 (en)
GB (1) GB1600161A (en)
IT (1) IT1102690B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2254332A (en) * 1991-03-18 1992-10-07 Etsuko Sugo Deodorizing material for animal breeding and process for producing the same.

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5487942A (en) * 1994-04-28 1996-01-30 Nippon Sanmo Sensyoku Co., Ltd. Carboxyl group-modified acrylonitrile fiber and process of producing same
EP0681053B1 (en) * 1994-04-29 2001-11-07 Nippon Sanmo Sensyoku Co.,Ltd. Carboxyl group-modified cellulose or acryl fiber and process of producing same
US6074964A (en) * 1995-12-19 2000-06-13 Toray Industries, Inc. Fabric and a production process therefor

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3434870A (en) * 1965-02-17 1969-03-25 Cotton Producers Inst Treating cellulosic textiles
GB1157300A (en) * 1966-05-11 1969-07-02 Minoru Imoto A process for preparing a Graft-Copolymerised Cellulose

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2254332A (en) * 1991-03-18 1992-10-07 Etsuko Sugo Deodorizing material for animal breeding and process for producing the same.
GB2254332B (en) * 1991-03-18 1995-06-21 Etsuko Sugo Deodorizing material for animal breeding and process for producing the same
US5641482A (en) * 1991-03-18 1997-06-24 Sugo; Tetsuko Deodorizing material for animal breeding and process for producing the same

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AT354972B (en) 1980-02-11
IT7848813A0 (en) 1978-04-10
FR2387250A1 (en) 1978-11-10
DE2811541A1 (en) 1978-10-19
ATA258977A (en) 1979-07-15
IT1102690B (en) 1985-10-07

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PS Patent sealed [section 19, patents act 1949]
PCNP Patent ceased through non-payment of renewal fee