U.S. patent application number 10/204108 was filed with the patent office on 2003-10-02 for polymer compositions and moulded bodies made therefrom.
Invention is credited to Endl, Thomas, Martl, Michael Gert, Zikeli, Stefan.
Application Number | 20030186611 10/204108 |
Document ID | / |
Family ID | 7631672 |
Filed Date | 2003-10-02 |
United States Patent
Application |
20030186611 |
Kind Code |
A1 |
Zikeli, Stefan ; et
al. |
October 2, 2003 |
Polymer compositions and moulded bodies made therefrom
Abstract
The invention relates to a polymer composition comprising a
biologically degradable polymer and a material from sea plants
and/or shells of sea animals or at least two components selected
from the group consisting of saccharides and the derivatives
thereof, proteins, amino acids, vitamins and metal ions. The
invention additionally relates to a molded article comprising said
polymer composition. Said molded article may be used packaging
material or fibrous material, in the form of fibrous material as
mixing component for the production of yarns, and in the form of
fibrous material for the production of nonwoven fabrics or woven
fabrics.
Inventors: |
Zikeli, Stefan; (Regau,
AT) ; Endl, Thomas; (Voecklabruck, AT) ;
Martl, Michael Gert; (Frankfurt am Main, DE) |
Correspondence
Address: |
MICHAEL BEST & FRIEDRICH, LLP
100 E WISCONSIN AVENUE
MILWAUKEE
WI
53202
US
|
Family ID: |
7631672 |
Appl. No.: |
10/204108 |
Filed: |
November 26, 2002 |
PCT Filed: |
January 8, 2001 |
PCT NO: |
PCT/EP01/00132 |
Current U.S.
Class: |
442/361 ;
428/364; 428/365; 428/373; 442/199 |
Current CPC
Class: |
D01F 2/00 20130101; D10B
2201/02 20130101; D10B 2201/28 20130101; C08L 5/04 20130101; Y10T
428/2929 20150115; Y10T 442/637 20150401; C08L 1/00 20130101; C08L
89/00 20130101; D02G 3/448 20130101; D10B 2201/24 20130101; D01F
2/10 20130101; D01F 1/10 20130101; B29B 7/007 20130101; Y10T
428/139 20150115; C08L 2201/06 20130101; D10B 2503/06 20130101;
D10B 2501/06 20130101; C08K 3/26 20130101; Y10T 428/2913 20150115;
D10B 2201/01 20130101; B29B 7/92 20130101; C08L 1/02 20130101; C08L
5/08 20130101; Y10T 442/3146 20150401; B29B 7/42 20130101; D10B
2331/04 20130101; D10B 2321/10 20130101; D03D 15/283 20210101; Y10T
442/30 20150401; Y10T 442/696 20150401; B29B 7/885 20130101; C08K
3/34 20130101; D10B 2321/022 20130101; Y10T 442/699 20150401; B29B
7/48 20130101; D10B 2505/08 20130101; D01F 2/06 20130101; Y10T
428/2915 20150115; D10B 2331/02 20130101; C08K 3/26 20130101; C08L
1/00 20130101; C08K 3/34 20130101; C08L 1/00 20130101; C08L 1/00
20130101; C08L 2666/02 20130101; C08L 1/02 20130101; C08L 2666/02
20130101; C08L 89/00 20130101; C08L 2666/02 20130101 |
Class at
Publication: |
442/361 ;
428/364; 428/365; 428/373; 442/199 |
International
Class: |
D03D 015/00; D04H
001/00; D04H 003/00 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 21, 2000 |
DE |
100 07 794.3 |
Claims
1. Polymer composition comprising a biologically degradable polymer
and a material from sea plants and/or shells of sea animals:
2. Polymer composition according to claim 1, wherein the material
from sea plants is selected from the group consisting of algae,
kelp, seaweed and mixtures thereof.
3. Polymer composition according to claim 2, wherein the material
from sea plants is selected from the group consisting of brown
algae, green algae, red algae, blue algae and mixtures thereof.
4. Polymer composition according to one of the preceding claims,
wherein the material from the shells of sea animals is selected
from the group consisting of sea sediments and grounded shells of
crabs, lobsters, crustaceans and mussels and mixtures thereof.
5. Polymer composition according to one of the preceding claims,
wherein the material from sea plants and/or shells of sea animals
is provided in an amount of 0.1 to 30 weight-% based on the weight
of the biologically degradable polymer.
6. Polymer composition according to one of the preceding claims,
wherein the biologically degradable polymer is cellulose and the
material from sea plants are algae.
7. Polymer composition comprising a biologically degradable polymer
and at least two components selected from the group consisting of
saccharides and the derivatives thereof, proteins, amino acids,
vitamins and metal ions.
8. Polymer composition according to claim 7, wherein at least three
components are present.
9. Polymer composition according to claim 7, wherein at least four
components are present.
10. Polymer composition according to one of claims 7 to 9, wherein
the at least two components are provided in an amount of 0.1 to 30
weight-% based on the weight of the biologically degradable
polymer.
11. Polymer composition according to one of claims 7 to 10, wherein
the at least two components are selected from the group consisting
of saccharides and the derivatives thereof and amino acids.
12. Polymer composition according to one of the preceding claims,
wherein the biologically degradable polymer is selected from the
group consisting of cellulose, modified cellulose, latex, vegetable
and animal protein, and mixtures thereof.
13. Molded article comprising a polymer composition according to
one of the preceding claims.
14. Molded article according to claim 13, wherein the molded
article is selected from the group consisting of tanks, films,
membranes, woven fabrics and fibers.
15. Molded article according to claim 14, wherein the fibers are
staple fibers, monofilaments or endless filaments.
16. Use of the molded article according to one of claims 13 to 15
as packaging material or fibrous material.
17. Use of the molded article according to one of claims 13 to 15
in the form of a fibrous material as mixing component for the
production of yarns.
18. Use of the molded article according to one of claims 13 to 15
in the form of a fibrous material for the production of nonwoven
fabrics or woven fabrics.
19. Use of the molded article according to one of claims 13 to 15
in the form of a fibrous material for the production of nonwoven
fabrics or woven fabrics, wherein a component selected from the
group consisting of cotton wool, lyocell, rayon, carbacell,
polyester, polyamide, cellulose acetate, acrylate, polypropylene or
mixtures thereof is additionally present in the nonwoven fabric or
woven fabric.
20. Use of the molded article according to claim 19, wherein 0.1 to
30 weight-% of the additional component are contained.
21. Woven fabric comprising a molded article according to one of
claims 13 to 15.
22. Nonwoven fabric comprising a molded article according to one of
claims 13 to 15.
23. Article of clothing comprising a molded article according to
one of claims 13 or 15.
24. Method of producing a molded article according to one of claims
13 to 15, comprising the following steps: (A) continuously or
discontinuously mixing the biologically degradable polymer and the
material from sea plants and/or shells of sea animals or the at
least two components selected from the group consisting of
saccharides and the derivatives thereof, proteins, amino acids,
vitamins and metal ions, (B) producing a moldable mass, (C)
processing the mass obtained in (B) to form a molded article, and
(D) subsequently treating the produced molded article.
25. Method according to claim 24, wherein a molded article
according to one of claims 13 to 15 is produced.
Description
[0001] The invention relates to a polymer composition comprising a
biologically degradable polymer, as well as to the use thereof of
the production of a molded article, the molded article produced
from said polymer composition, a method for the production thereof
and the use thereof, and to an article of clothing comprising the
molded article in form of fibers.
[0002] Polymer compositions with different additives for the
production of molded articles are known.
[0003] U.S. Pat. No. 5,766,746 describes a nonwoven fabric made of
cellulose fibers, which comprise a flame-resistant phosphoric
component.
[0004] U.S. Pat. No. 5,565,007 describes modified rayon fibers,
with a modifying agent for improving the dyeing properties of the
fibers.
[0005] U.S. Pat. No. 4,055,702 discloses melt-spun, cold-drawn
fibers from a synthetic organic polymer with additives. Said
additives may be receptors, flame-resistant rendering agents,
antistatic agents, stabilizers, mildew inhibitors or
antioxidants.
[0006] "Lenzinger Berichte", 76/97, page 126 moreover discloses a
lyocell fiber spun from a cellulose solution in
N-methylmorpholine-N-oxide (hereinafter called "NMMNO"), into which
may be incorporated 0.5 to 5 weight-%, relative to the cellulose
weight, of cross-linking agents for improving the wet abrasion
value. It is additionally described to incorporate lyocell fibers,
carboxymethylchitin, carboxymethylchitosan or polyethylene imine
for improving the fungicidal properties, polyethylene imine for the
adsorption of metal ions and dyes, hyaluronic acid for improving
the bactericidal properties, xanthene, guar, carubin, bassorin or
starch for improving hydrophilicity, water adsorption and water
vapor permeability, or starch for the accelerated enzymatic
hydrolysis.
[0007] WO 98/58015 describes a composition contaning fine particles
of solid matter for the addition to a formable solution of
cellulose in an aqueous tertiary amine oxide. The composition is
made of solid particles, tertiary amine oxide, water and at least
another substance. Said other substance may be a stabilizer or a
dispersing agent. The solid particles may be pigments.
[0008] Furthermore, it is known that high concentrations of iron
and transitional metals influence the stability of a spinning mass
of cellulose, NMMNO and water. High iron concentrations decrease
the disintegration temperature of the solution to such an extent
that explosion-like disintegration reactions of the solution may
occur. The disintegration and stabilization of cellulose solved in
NMMNO is described in "Das Papier", F. A. Buitenhuijs 40. year,
volume 12, 1986, which also mentions the influence of iron--Fe(III)
on said cellulose solutions. With an addition of 500 ppm of Fe(III)
more than 40% of the NMMNO were transformed into the disintegration
product N-methylmorpholine ("NMM"), whereby the addition of
Cu.sup.+2 also reduces the stability of the solution. With the
addition of copper to an NMMO cellulose solution free of copper the
disintegration temperature (T onset .degree. C.) was reduced from
175.degree. C. to 114.degree. C. in the presence of 900 mg
copper/kg of the mass. Moreover described is the positive effect of
stabilizers such as propyl gallate and ellagic acid.
[0009] The addition of additives to fibers moreover causes
difficulties in preserving the properties of the fibers such as
mechanical stabilities, fiber elongations, loop strength, abrasion
resistance, dye receptivity.
[0010] JP 1228916 describes a film made of two layers of woven
material or nonwoven fabric, between which fine flakes of algae
material such as Rhodophyceae are filled by means of adhesives or
by hot welding. Thus, a film is obtained which, when used, improves
the health.
[0011] Said film has, however, the disadvantage that the finely
grounded (comminuted) algae material is present in hollow spaces
between said two layers, so that the algae material escapes when
the film is torn and is separated from the environment by the
layers.
[0012] U.S. Pat. Nos. 4,421,583 and 4,562,110 describe a method,
wherein fiber material is produced from alginate. For this purpose,
alginate is obtained from the sea plants by means of an extraction
method, and the so obtained soluble alginate is directly spun to
form fibers.
[0013] DE 19544097 describes a method of producing molded articles
from polysaccharide mixtures by dissolving cellulose and a second
polysaccharide in an organic polysaccharide solvent mixable with
water, which may likewise contain a second solvent, by molding the
solution under pressure through a nozzle to form molded articles
and by solidifying the molded articles by means of coagulation in a
coagulating bath. Apart from cellulose, hexoses with glycosidic 1,4
and 1,6 linkage, uronic acids and starch, especially pullulan,
carubin, buaran, hyaluronic acid, pectin, algin, carrageenan or
xanthene are mentioned therein as second polysaccharides. Moreover,
it is described that, apart from a second polysaccharide, also a
third polysaccharide, preferably chitin, chitosan or, respectively,
a corresponding derivative may be used. The molded articles
obtained according to this method are used as means for binding
water and/or heavy metals, as fiber having bactericidal and/or
fungicidal properties or as yarn with an increased degradation
velocity in the stomach of ruminants.
[0014] The use of nucleation agents in the production of molded
articles from thermoplastic high polymers, especially
.alpha.-olefinic polymers is described in U.S. Pat. No. 3,367,926.
As nucleation agents amino acids, the salts thereof and proteins
are, inter alia, mentioned.
[0015] For reducing the fibrillation tendency in cellulosic molded
articles it is known to apply defibrillation agents on the freshly
spun or dried fiber in a subsequent treatment step. All previously
known defibrillation agents are cross-linking agents.
[0016] According to EP-A-0 538 977 cellulose fibers are treated in
an alkaline medium with a chemical reagent comprising 2 to 6
functional groups capable of reacting with cellulose, in order to
reduce the fibrillation tendency.
[0017] Another method for the reduction of the fibrillation
tendency of cellulosic molded articles by means of a textile
auxiliary agent is described in WO 99/19555. So far a solution for
reducing the fibrillation of the cellulose fibers during the
spinning process has not as yet been found.
[0018] It is, therefore, the object of the present invention to
provide a polymer composition containing an additive, with a good
stability and proccesability, as well as a molded article produced
therefrom having a small fibrillation tendency, and a method for
the production thereof.
[0019] This object is solved by a polymer composition comprising a
biologically degradable polymer and a material from sea plants
and/or shells of sea animals, by a molded article produced
therefrom as well as by a method for the production thereof
according to claims 1 to 6 and 12 to 25.
[0020] The object is additionally solved by a polymer composition
comprising a biologically degradable polymer and at least two
components selected from the group consisting of saccharides and
the derivatives thereof, proteins, amino acids, vitamins and metal
ions, by a molded article produced therefrom and by a method for
the production thereof according to claims 7 to 25.
[0021] The biologically degradable polymer is preferably selected
from the group consisting of cellulose, modified cellulose, latex,
vegetable or animal protein, especially cellulose, and mixtures
thereof. Polyamides, polyurethanes and mixtures thereof may
likewise be used, as far as they are biologically degradable. The
polymer composition according to the invention and the molded
article produced therefrom preferably contain no polymers which are
not biologically non-degradable, or mixtures thereof.
[0022] The polymer compositions according to the invention may also
contain polymers which are not biologically degradable. Certain
polymer solvents such as DMAc, DMSO or DMF etc. can also solve
synthetic polymers such as aromatic polyamides (aramides),
polyacrylonitrile (PACN) or polyvinyl alcohols (PVA), which, again,
may be combined to form polymer compositions in combination with
known cellulose solvents such as LiCl/DMAc, DMSO/PF, tertiary amine
oxides/water.
[0023] Examples for modified cellulose include carboxethyl
cellulose, methyl cellulose, nitrate cellulose, copper cellulose,
viscose xanthogenate, cellulose carbamate and cellulose acetate.
Examples for fibers from polycondensation and polymerization
products are polyamides substituted with methyl, hydroxy or benzyl
groups. Examples for polyurethanes are those formed on the basis of
polyesterpolyolen.
[0024] The sea plant material is preferably selected from the group
consisting of algae, kelp and seaweed, especially algae. Examples
for algae include brown algae, green algae, red algae, blue algae
or mixtures thereof. Examples for brown algae are Ascophyllum spp.,
Ascophyllum nodosum, Alaria esculenta, Fucus serratus, Fucus
spiralis, Fucus vesiculosus, Laminaria saccharine, Laminaria
hyperborea, Laminaria digitata, Laminaria echroleuca and mixtures
thereof. Examples for red algae include Asparagopsis armata,
Chondrus cripus, Maerl beaches, Mastocarpus stellatus, Palmaria
palmata and mixtures thereof. Examples for green algae are
Enteromorpha compressa, Ulva rigida and mixtures thereof, Examples
for blue algae are Dermocarpa, Nostoc, Hapalosiphon, Hormogoneae,
Porchlorone. A classification of algae can be inferred from the
Botanic Textbook for Colleges [Lehrbuch der Botanik fur
Hochschulen] E. Strasburger; F. Noll; H. Schenk; A. F. W. Schimper;
33. edition, Gustav Fischer Verlag, Stuttgart-Jena-New York;
1991.
[0025] The sea plant material can be obtained in different ways. At
first, it is harvested, whereby there are three different
harvesting methods:
[0026] 1. the sea plant material washed ashore is collected,
[0027] 2. the sea plants are cut from stones, or
[0028] 3. the sea plants are collected in the sea by divers.
[0029] The sea plant material obtained according to the third
method has the best quality and is rich in vitamins, minerals,
minor elements and polysaccharides. For the purpose of the present
invention the sea plant material harvested according to this method
is preferably used.
[0030] The harvested material can be processed in different ways.
The sea plant material can be dried at temperatures of up to
450.degree. C. and grounded by using ultrasound, wet ball mills,
pin-type mills or counterrotating mills, whereby a powder is
obtained, which may, if required, still be subjected to cycloning
for the classifying thereof. A so obtained powder may be used
according to the invention. Said sea plant material powder may, in
addition, be subjected to an extraction method, for instance, with
vapor, water or an alcohol such as ethanol, whereby a liquid
extract is obtained. Said extract may likewise be used according to
the invention.
[0031] The harvested sea plant material can moreover be subjected
to a cryocomminution, whereby it is comminuted into particles of
approximately 100 .mu.m at -50.degree. C. If desired, the so
obtained material may additionally be comminuted, whereby particles
having a size of approximately 6 to approximately 10 .mu.m are
obtained.
[0032] The material from the outer shell of sea animals is
preferably selected out of sea sediments, grounded shells of crabs
or mussels, lobsters, crustaceans, shrimps, corals.
[0033] A typical composition of a mixture of natural origin is
shown in table 1.
1TABLE 1 Components (%) Vitamins 0.2% Proteins 5.7% Fats 2.6%
Humidity 10.7% Ash 15.4% Carbohydrates 65.6%
[0034] Minerals of a mixture of natural origin according to table 1
are shown in table 2.1.
2TABLE 2.1 Concentration Concentration Concentration ELEMENT
[mg/kg] ELEMENT [mg/kg] ELEMENT [mg/kg] Sodium 41,800 Iron 895
Aluminum 1,930 Magnesium 2,130 Nickel 35 Sulfur 15,640 Calcium
19,000 Copper 6 Molybdenum 16 Manganese 1,235 Chlorine 36,800
Cobalt 12 Phosphor 2,110 Iodine 624 Tin <1 Mercury 2 Lead <1
Boron 194 Fluorine 326 Zinc 35 Strontium 749
[0035] Minerals of a mixture (humidity 94%, ignition residue 90%)
of natural origin are shown in table 2.2.
3TABLE 2.2 Concentration Concentration Concentration ELEMENT
[mg/kg] ELEMENT [mg/kg] ELEMENT [mg/kg] Sodium 5,100 Iron 2,040
Aluminum <5 Magnesium 24,000 Nickel 14 Sulfur 4,500 Calcium
350,000 Copper 10 Molybdenum 39 Manganese 125 Chlorine 1,880 Cobalt
6 Phosphor 800 Iodine 181 Tin <5 Mercury <0.3 Lead 460 Boron
17 Fluorine 200 Zinc 37
[0036] The material from sea animal shells can, in the case of sea
sediments, be used directly. If materials from the shells of crabs
or mussels, lobsters, crustaceans, shrimps are used, the same is
grounded.
[0037] Mixtures from sea plant materials and shells of sea animals
as well as the extracted products thereof may likewise be used. The
quantitative composition of sea plant materials and the shells of
sea animals is preferably 50 weight-% to 50 weight-%. Sea plant
materials are preferably used according to the invention.
[0038] The material from sea plants and/or shells of sea animals
may be present in the polymer composition and the molded article
produced therefrom in an amount of 0.1 to 30 weight-%, preferably
0.1 to 15 weight-%, more preferably 1 to 8 weight-%, especially 1
to 4 weight-%, based on the weight of the biologically degradable
polymer. Especially if the molded article is present in the form of
a fiber, the amount of material from sea plants and/or shells of
sea animals is preferably 0.1 to 15 weight-%, especially 1 to 5
weight-%.
[0039] An example for a material from sea plants used according to
the invention is a powder from Ascophyllum nodosum having a
particle size of 95% <40 .mu.m, which contains 5.7 weight-%
protein, 2.6 weight-% fat, 7.0 weight-% fibrous components, 10.7
weight-% humidity, 15.4 weight-% ash and 58.6 weight-%
carbohydrates. It moreover contains vitamins and minor elements
such as ascorbic acid, tocopherols, carotene, barium, niacin,
vitamin K, riboflavin, nickel, vanadium, thiamin, folic acid,
folinic acid, biotin and vitamin B.sub.12. In addition, it contains
amino acids such as alanine, arginine, asparagic acid, glutamic
acid, glycin, leucine, lysine, serine, threonine, tyrosine, valine
and methionine.
[0040] According to another embodiment the polymer composition
comprises a biologically degradable polymer and at least two
components selected from the group consisting of saccharides and
the derivatives thereof, proteins, amino acids, vitamins and metal
ions. The components may be of synthetic nature or of a natural
origin. Said components may be used in a dried form or with a
humidity, which preferably ranges between 5 and 15%.
[0041] In a preferred embodiment the polymer composition comprises
a biologically degradable polymer and at least three components,
especially preferably at least four components, selected from the
group consisting of saccharides and the derivatives thereof,
proteins, amino acids, vitamins and metal ions.
[0042] The polymer composition comprises especially preferably a
biologically degradable polymer and at least two components
selected from the group consisting of saccharides and the
derivatives thereof and amino acids.
[0043] The at least two components selected from the group
consisting of saccharides and the derivatives thereof, proteins,
amino acids, vitamins and metal ions may be present in the polymer
composition and the molded article produced therefrom in an amount
of 0.1 to 30 weight-%, preferably 0.1 to 15 weight-%, especially in
an amount of 4 to 10 weight-%, based on the weight of the
biologically degradable polymer.
[0044] The saccharides may be used in amounts of 0.05 to 9
weight-%, preferably in amounts of 2 to 6 weight-%, the vitamins in
amounts of 0.00007 to 0.04 weight-%, preferably in amounts of 0.003
to 0.03 weight-%, the proteins and/or amino acids in amounts of
0.005 to 4 weight-%, preferably in amounts of 0.2 to 0.7 weight-%,
and the metal ions and the counterions thereof in amounts of 0.01
to 9 weight-%, preferably in amounts of 0.5 to 1.6 weight-%, based
on the weight of the biologically degradable polymer.
[0045] The biologically degradable polymer is preferably selected
from the same group as in the preceding embodiment.
[0046] The saccharides or the derivatives thereof used may be
selected from the group consisting of monosaccharides,
oligosaccharides and polysaccharides. Mixtures containing alginic
acid, laminarin, mannitol and methylpentosanes are preferably
used.
[0047] The used proteins contain preferably alanine, arginine,
asparagic acid, glutamic acid, glycin, leucine, lysine, serine,
threonine, tyrosine, valine and methionine.
[0048] The amino acids are preferably the same ones contained in
the proteins as used.
[0049] Furthermore, the used vitamins may be selected from the
group consisting of ascorbic acid, tocopherol, carotene, niacin
(vitamin B3), phytonadione (vitamin K), riboflavin, thiamin, folic
acid, folinic acid, biotin, retinol (vitamin A), pyridoxine
(vitamin B6) and cyanocobalamin (vitamin B.sub.12).
[0050] The metal ions may be selected from the group consisting of
aluminum, antimony, barium, boron, calcium, chromium, iron,
germanium, gold, potassium, cobalt, copper, lanthanum, lithium,
magnesium, manganese, molybdenum, sodium, rubidium, selenium,
silicon, thallium, titan, vanadium, tungsten, zinc and tin.
[0051] The counterions of the metal ions may, for example, be
fluoride, chloride, bromide, iodide, nitrate, phosphate, carbonate
and sulfate. The amount of metal ions or, respectively, the
pertinent counterions is adjusted such that, when the at least two
components or, respectively, the polymer composition are ashed, an
ash content in the range of 5-95%, preferably a range of 10-60% is
formed.
[0052] For the purposes according to the invention particles of the
material from sea plants and/or shells of sea animals or the at
least two components selected from the group consisting of
saccharides and the derivatives thereof, proteins, amino acids,
vitamins and metal ions in the particle-size range of 200 to 400
.mu.m, preferably of 150 to 300 .mu.m may be used. Smaller sized
particles may also be used, such as at 1 to 100 .mu.m, preferably
0.1 to 10 .mu.m, more preferably 0.1 to 7 .mu.m, especially 1 to 5
.mu.m (measuring method: laser diffraction apparatus: Sympatec
Rhodos). Also grain size mixtures of a uniform material or,
respectively, different algae material may be used.
[0053] In order to obtain the material from sea plants and/or
shells of sea animals or the at least two components in this
fineness, the material from sea plants and/or shells of sea animals
or the at least two components may be grounded, for instance, with
commercially available pin-type mills, whereupon the fine fraction
is then separated by means of corresponding classifiers. Such a
classifying process for toner for the development of electrostatic
pictures is described in DE 19803107, whereby a fine fraction is
classified out of the product at approximately 5 .mu.m.
[0054] Given this process, however, only the fine fraction can be
obtained, and the main fraction is thereby not used in the polymer
composition according to the invention.
[0055] Another possibility to obtain the material from sea plants
and/or shells of sea animals or the at least two components in the
required particle size resides in disintegrating the material from
sea plants and/or shells of sea animals or the at least two
components by means of jet mills with static or rotating internal
or external classifiers. Jet mills typically comprise a flat
cylindrical mill chamber, around which a plurality of jet nozzles
distributed about the periphery are arranged. The grinding is
substantially based on a mutual exchange of kinetic energy. The
disintegration achieved by particle impact is followed by a
classifying zone towards the center of the mill chamber, whereby
the fine fraction is discharged by means of static or rotating
internal or external classifiers. The coarse fraction remains in
the milling space by means of centrifugal forces and is further
grounded. A portion of the components being hard to mill may be
discharged from the milling space through suitable apertures.
Corresponding jet mills are described, for example, in the U.S.
Pat. No. 1,935,344, in EP 888818, EP 603602, DE 3620440.
[0056] A typical particle size distribution is shown in FIG. 1.
[0057] The molded articles according to the invention can be
produced from the polymer composition according to the invention
with conventional methods, whereby the biologically degradable
polymer and the material from sea plants and/or shells of sea
animals or the at least two components, selected from the group
consisting of saccharides and the derivatives thereof, proteins,
amino acids, vitamins and metal ions are at first mixed to produce
the polymer composition and the molded article can then be
produced.
[0058] The continuous or discontinuous mixing of the biologically
degradable polymer and the material from sea plants and/or shells
of sea animals or the at least two components, selected from the
group consisting of saccharides and the derivatives thereof,
proteins, amino acids, vitamins and metal ions can take place with
apparatus and on the basis of methods described in WO 96/33221,
U.S. Pat. No. 5,626,810 and WO 96/33934.
[0059] The molded article according to the invention especially
preferably provided in the form of fibers, most preferably in the
form of cellulose fibers. The molded article according to the
invention may also be provided in the form of an endless filament,
or membrane, or in the form of a hose or a flat film.
[0060] Methods of producing the cellulose fibers according to the
invention such as the lyocell or NMMO methods, the rayon or viscose
methods or the carbamate method are known.
[0061] The lyocell method may be performed according to the
following description. For producing a moldable mass and the
cellulose fibers according to the invention a solution from
cellulose, NMMNO and water is produced by first forming a
suspension from cellulose, NMMNO and water, whereby said suspension
is continuously transported by rotating elements over a heat
exchange surface in a layer having a thickness of 1 to 20 mm and
under a reduced pressure. During this process water is evaporated
until a homogenous cellulose solution is formed. The so obtained
cellulose solutions may contain an amount of cellulose of 2 to 30
weight-%, an amount of NMMNO of 68 to 82 weight-% and an amount of
water of 2 to 17 weight-%. If desired, additives like anorganic
salts, anorganic oxides, finely distributed organic substances or
stabilizers may be added to said solution.
[0062] The material from sea plants and/or shells of sea animals or
the at least two components, selected from the group consisting of
saccharides and the derivatives thereof, proteins, amino acids,
vitamins and metal ions are then continuously or discontinuously
added to the so obtained cellulose solution in the form of powder,
a powder suspension or in a liquid form, as extract or
suspension.
[0063] In dependence on the method the material from sea plants
and/or shells of sea animals or the at least two components,
selected from the group consisting of saccharides and the
derivatives thereof, proteins, amino acids, vitamins and metal ions
may also be added after or during the continuous disintegration of
the dry cellulose, e.g. in the form of algae material in the
original size, as powder or highly concentrated powder suspension.
The powder suspension can be produced in water or any optional
solvent in the desired concentration required for the method.
[0064] Furthermore, it is possible to subject the material from sea
plants and/or shells of sea animals or the at least two components,
selected from the group consisting of saccharides and the
derivatives thereof, proteins, amino acids, vitamins and metal ions
to a pulping process with simultaneous disintegration, or to feed
to a refiner. The pulping can be carried out either in water, in
caustic solutions or in the solvent required for dissolving the
cellulose at a later stage. Here, too, the material from sea plants
and/or shells of sea animals or the at least two components,
selected from the group consisting of saccharides and the
derivatives thereof, proteins, amino acids, vitamins and metal ions
may be added in a solid, powdery, suspension-like or in liquid
form.
[0065] In the presence of a derivatization agent and/or a solvent
known for the dissolving process the polymer composition enriched
with the material from sea plants and/or shells of sea animals or
the at least two components, selected from the group consisting of
saccharides and the derivatives thereof, proteins, amino acids,
vitamins and metal ions can be transferred into a moldable
extrusion mass.
[0066] Another possibility of adding the material from sea plants
and/or shells of sea animals or the at least two components,
selected from the group consisting of saccharides and the
derivatives thereof, proteins, amino acids, vitamins and metal ions
resides in the addition during a continuously controlled dissolving
process as is described in EP 356419, U.S. Pat. No. 5,049,690 and
U.S. Pat. No. 5,330,567.
[0067] Alternatively, the addition may be carried out
discontinuously by obtaining a master batch of the cellulose
solution. Preferably the material from sea plants and/or shells of
sea animals or the at least two components, selected from the group
consisting of saccharides and the derivatives thereof, proteins,
amino acids, vitamins and metal ions is added continuously.
[0068] The material from sea plants and/or shells of sea animals or
the at least two components, selected from the group consisting of
saccharides and the derivatives thereof, proteins, amino acids,
vitamins and metal ions may be added in any other stage of the
production process for the molded article. It can, for instance, be
fed into a pipeline system, where it is correspondingly mixed by
static mixing elements or, respectively, stirring elements such as
known inline refiners or homogenizers, e.g. apparatus from Ultra
Turrax, positioned therein. If the process is carried out in the
continuous batch operation, e.g. by means of a stirred vessel
cascade, the algae material can be introduced in a solid, powdery,
suspension-like or liquid form at the point which is optimal for
the process. The fine distribution can be achieved with known
stirring elements adjusted to the method.
[0069] In dependence on the applied particle size the formed
incorporated extrusion or spinning mass can be filtrated prior or
after the incorporation. In response to the fineness of the applied
product the filtration may also be omitted in spinning methods
using large nozzle diameters.
[0070] If the spinning masses are very sensitive, the material can,
in a suited form, directly be fed upstream of the spinning nozzle
or the extrusion die via an injection location.
[0071] If the algae material or the at least two components,
selected from the group consisting of saccharides and the
derivatives thereof, proteins, amino acids, vitamins and metal ions
are liquid, it is additionally possible to feed them to the
continuously spun thread during the spinning process.
[0072] The so obtained cellulose solution is spun according to
conventional methods such as the dry-jet-wet method, the
wet-spinning method, the melt-blown method, the pot spinning
method, the funnel spinning method or the dry spinning method. When
the spinning takes place according to the dry-jet-wet spinning
method, the yarn sheet can also be cooled in the air gap between
the nozzle and the coagulating bath by quenching. An air gap of
10-50 mm has proved to be suitable. The parameters for the cooling
air are preferably air temperatures of 5-35.degree. C. with a
relative humidity of up to 100%. Patent documents U.S. Pat. No.
5,589,125 and 5,939,000 as well as EP 0574870 B1 and WO 98/07911
describe spinning methods for the production of cellulose fibers
according to the NMMO method.
[0073] If required, the formed molded articles are subjected to the
conventional subsequent chemical fiber treatment methods for
filaments or staple fibers.
[0074] Obtained is a cellulose fiber according to the invention
with a material from sea plants and/or shells of sea animals or
with at least two components, selected from the group consisting of
saccharides and the derivatives thereof, proteins, amino acids,
vitamins and metal ions, preferably at least three components,
especially preferably at least four components.
[0075] Apart from the spinning method also extrusion methods for
the production of flat films, round films, skins (sausage skins)
and membranes can be used.
[0076] The viscose method can be carried through as follows. Pulp
with approximately 90 to 92 weight-% of .alpha.-cellulose is
treated with aqueous NaOH. Afterwards the cellulose is transformed
into cellulose xanthogenate by means of conversion with carbon
disulfide, and a viscose solution is obtained by adding aqueous
NaOH under constant stirring. Said viscose solution contains
approximately 6 weight-% cellulose, 6 weight-% NaOH and 32 weight-%
carbon disulfide, based on the cellulose content. After the
suspension was stirred, the material from sea plants and/or shells
of sea animals or the at least two components, selected from the
group consisting of saccharides and the derivatives thereof,
proteins, amino acids, vitamins and metal ions are added either as
powder or liquid extract. If desired, common additives such as
surfactants, dispersing agents or stabilizers can be added.
[0077] The material from sea plants and/or shells of sea animals or
the at least two components, selected from the group consisting of
saccharides and the derivatives thereof, proteins, amino acids,
vitamins and metal ions can, again, be added at any stage of the
process.
[0078] The so obtained solution is then spun to form fibers, as is,
for instance, described in U.S. Pat. No. 4,144,097.
[0079] The carbamate method can be carried out as follows. For this
purpose, cellulose carbamate is produced from pulp with
approximately 90 to 95 weight-% of .alpha.-cellulose, as is
described, for example, in U.S. Pat. No. 5,906,926 or in DE
19635707. Alkali cellulose is thereby produced from the applied
pulp by treating it with aqueous NaOH. After the defibration the
alkali cellulose is subjected to maturing and the caustic soda
solution is then washed out. The so activated cellulose is mixed
with urea and water and is introduced into a solvent in a reactor.
The so obtained mixture is heated. The obtained carbamate is
separated and a carbamate spinning solution is produced therefrom,
which is described in DE 19757958. The material from sea plants
and/or shells of sea animals or the at least two components,
selected from the group consisting of saccharides and the
derivatives thereof, proteins, amino acids, vitamins and metal ions
are added to said spinning solution.
[0080] The so obtained spinning solution is spun to form fibers
according to known methods, and cellulose fibers according to the
invention are obtained.
[0081] It has surprisingly been found that, despite the addition of
an additive, the cellulose fibers according to the invention show
the same excellent properties as cellulose fibers without
additives, namely in view of their fineness, breaking force,
breaking force variation, elongation, wet elongation, breaking
tenacity, wet tenacity, fineness-related loop strength, wet
abrasion upon breakage, wet abrasion variation and wet modulus, and
have, at the same time, the positive properties conferred by the
material from sea plants and/or shells of sea animals or the at
least two components, selected from the group consisting of
saccharides and the derivatives thereof, proteins, amino acids,
vitamins and metal ions. This is especially surprising, as the
addition of additives to spinning masses from cellulose, NMMNO and
water has the drawback that the same discolor at the temperature of
application, are not resistant to storage and incorporate
impurities into the final cellulose products.
[0082] Furthermore, it could surprisingly be proved that the ionic
components incorporated with the material remain in the fiber
compound even when subjected to a forming method with an aqueous
bath liquid, and do not escape into the spinning bath during the
short spinning period.
[0083] After the spinning process the pH-value of the produced
staple fiber was determined according to the DIN method 54 275. In
comparison to a fiber not incorporated with sea plants and/or
shells of sea animals the pH-value of the incorporated fiber
increased, which indicates the extraction of ionic fiber
components. By said property, in connection with the body humidity,
the bioactivity of the skin can positively and healthfully be
influenced when articles of clothing are worn.
[0084] Moreover, it has shown that by the addition of the material
from sea plants and/or shells of sea animals or the at least two
components, selected from the group consisting of saccharides and
the derivatives thereof, proteins, amino acids, vitamins and metal
ions, the fibrillation of the fibers, produced according to the
lyocell method, is reduced. Thus, the fiber according to the
invention, e.g. a cellulose fiber incorporated with algae, can be
applied in a more favorable manner during the subsequent textile
treatment of the fiber.
[0085] Despite the incorporation of a material from sea plants
and/or shells of sea animals or the at least two components,
selected from the group consisting of saccharides and the
derivatives thereof, proteins, amino acids, vitamins and metal
ions, which is rich in iron and metal concentrations if a sea plant
is concerned, advantageously no disintegration of a spinning
solution from cellulose, NMMNO and water is observed. It has, on
the contrary, shown that the disintegration temperature of such a
spinning solution even increased when material from sea plants
and/or shells of sea animals was added. This means that despite the
presence of metal ions, no negative influence on the stability of
the spinning mass could be observed.
[0086] By the incorporation of the material from sea plants and the
incorporation of metals connected therewith, therefore, also
chemical reactions on the fiber material may be carried out, such
as ion exchange processes by the incorporated metal ions (e.g.
increase of the hydrogen ion concentration in the fibrous material)
or the deacetylation of chitin.
[0087] Another advantage conferred upon the molded articles
according to the invention by the addition of material from sea
plants and/or shells of sea animals or at least two components,
selected from the group consisting of saccharides and the
derivatives thereof, proteins, amino acids, vitamins and metal ions
is the homogenous incorporation of the active substances into the
fiber matrix with different produceable fiber diameters. Moreover,
the processing as monofilament or endless filament yarn is
feasible. This results in a particularly favorable application of
technical articles.
[0088] Especially if the molded article according to the invention
is produced from a polymer composition containing exclusively
biologically degradable material, the complete biological
degradability thereof is an advantage.
[0089] The molded articles according to the invention may be used
as packaging material, fiber material, nonwoven fabrics, textile
compounds, fibrous webs, fiber fleeces, needlefelts, upholstery
cotton wool, woven fabrics, knitted fabrics, as home textiles such
as bed linen, as filling material, flocking fabric, hospital
textiles such as sheets, diapers or mattresses, as fabrics for
heating blankets, shoe inserts and dressings. Additional
possibilities of using the same are described the Dictionary for
textile interior design [Lexikon der textilen Raumausstattung],
Buch und Medien Verlag Buurmann KG, ISBN 3-98047-440-2.
[0090] If a woven fabric is produced from the molded article
according to the invention in the form of fibers, it may either
consist of said fibers exclusively or contain an additional
component. Said additional component can be selected out of the
group consisting of cotton wool, lyocell, rayon, carbacell,
polyester, polyamide, cellulose acetate, acrylate, polypropylene or
mixtures thereof. The fibers containing a material from sea plants
and/or shells of sea animals are present in the woven fabric
preferably in an amount of up to approximately 70 weight-%. The
material from sea plants and/or shells of sea animals or the at
least two components, selected from the group consisting of
saccharides and the derivatives thereof, proteins, amino acids,
vitamins and metal ions are present in the woven fabric preferably
in an amount of 1 to 10 weight-%.
[0091] If the molded article is provided in the form of a fibrous
material or a woven fabric, articles of clothing such as jumpers,
jackets, dresses, suits, t-shirts, underwear or the like can be
produced therefrom.
[0092] The articles of clothing produced from said fibers or woven
fabrics according to the invention are extremely comfortable to
wear and in general improve the state of health of the individual
wearing said article of clothing. The health-improving effect of
sea plant materials is, for instance, described in JP 1228916.
[0093] Due to the high portion of negative ions in the material
from sea plants and/or shells of sea animals or the at least two
components, selected from the group consisting of saccharides and
the derivatives thereof, proteins, amino acids, vitamins and metal
ions the pH-value of the skin is positively influenced in as far as
it arranges for alkaline and thus healthy conditions on the skin.
In addition, the skin temperature is increased more when wearing
the articles of clothing according to the invention, in contrast to
wearing an article of clothing made of fibers without the material
from sea plants and/or shells of sea animals or the at least two
components, selected from the group consisting of saccharides and
the derivatives thereof, proteins, amino acids, vitamins and metal
ions, whereby a positive effect is exerted on the blood circulation
of the skin.
[0094] Due to the incorporated elements the fiber according to the
invention passes the active substances on to the body, namely via
the liquid present during the wearing in response to the body
humidity. Due to the cellulosic material articles of clothing
having good breathing properties can thus be produced. Moreover,
the active substances can purposively be supplied to the skin, as
is common in cosmetics or Thalami therapy. Due to the incorporation
the active substances remain in the fiber or the woven fabric for a
long time, even after frequent washing.
[0095] The minor elements and the vitamins supplied via the woven
fabric made of the fibers according to the invention can support
the body due to the remineralizing, stimulating and heating
effect.
[0096] If the fiber according to the invention is provided in the
form of staple fibers or disintegrated filaments, surfaces of
carriers such as woven fabrics or films can be flocked therewith.
For this purpose the surface of the carrier to be flocked is
treated with an adhesive and the staple fibers or disintegrated
filaments are applied thereon.
[0097] The invention will hereinafter by explained by means of
examples.
COMPARATIVE EXAMPLE 1
Without Admixture
[0098] 3,086 g NMMNO (59.8%), 308 g MoDo, DP 500, dry contents
94%,1.8 propylgallate (0.63% related to the cellulose contents)
were mixed, and the so obtained mixture was heated to 94.degree. C.
Obtained was a discontinuously produced spinning solution having a
cellulose content of 11.8% and a viscosity of 4,765 Pa.multidot.s.
The so obtained spinning solution was spun to form fibers, whereby
the following spinning conditions were observed:
4 Temperature of the store tank 90.degree. C. Temperature spinning
block, nozzle 80.degree. C. Spinning bath 4.degree. C. Spinning
bath concentration (start) 0% (distilled water) Spinning bath
concentration (end) 5% NMMNO Spinning pump 20.0 cm.sup.3/min.
Nozzle filter 19200 M/cm.sup.2 Spinning nozzle 495 Hole 70 .mu.m;
Au/Pt Final drawing-off 25 m/min.
[0099] The fibers were cut to a staple length of 40 mm, were washed
free of a solvent and finished with a 10 g/l lubrication (50%
Leomin OR-50% Leomin WG (nitrogen-containing fatty acid polyglycol
ester Clariant GmbH)) at 45.degree. C. or, respectively, the fat
add-on for the better continued processing of the fibers was
applied, and dried at 105.degree. C. Subsequent to the drying a
fiber humidity of 11% was adjusted. An additional bleaching process
prior to the drying was not performed in this case.
[0100] The spinning behavior of the spinning solution obtained
according the present example was good.
5TABLE 3 Fiber data comparative example 1 Comparative Example 1
Fineness - Titer [dtex] 1.48 Breaking tenacity dry [cN/tex] 42.20
Breaking tenacity wet [cN/tex] 36.30 Breaking tenacity loop
[cN/tex] 15.20 Breaking elongation - dry [%] 15.50 Breaking
elongation - wet [%] 15.20 Wet modulus [cN/tex] 202.00
COMPARATIVE EXAMPLE 2
Without Admixture: Treatment of the Filaments in the Air Gap
[0101] The spinning solution was produced analogously to
comparative example 1. The spinning solution was spun to fibers,
whereby, in deviation from comparative example 1, the temperature
of the spinning block was adjusted to 95.degree. C. and the
temperature of the nozzle to 105.degree. C. In the air gap between
the nozzle and the coagulating bath the yarn sheet was quenched
with humid air (temperature: 20.degree. C., humidity: 70%).
[0102] Otherwise, the test performance was carried out like in
comparative example 1.
6TABLE 4 Fiber data comparative example 2 Comparative Example 2
Fineness - Titer [dtex] 1.25 Breaking tenacity dry [cN/tex] 45.10
Breaking tenacity wet [cN/tex] 37.10 Breaking tenacity loop
[cN/tex] 22.10 Breaking elongation - dry [%] 15.40 Breaking
elongation - wet [%] 18.50 Wet modulus [cN/tex] 234.00
EXAMPLE 1
[0103] 3,156 g NMMNO (61.4%), 315 g MoDo, DP 500, dry contents 94%,
1.9 g propylgallate (0.63% related to the cellulose content) as
well as 11.6 g of a powder--shown in table 1--(in total 3.9%
related to the cellulose content) were mixed and heated to
94.degree. C. Obtained was a spinning solution having a solids
content of 12.4% and a viscosity of 6,424 Pa.multidot.s. The so
produced spinning solution was spun to fibers like in comparative
example 1,
7TABLE 5 Fiber data example 1 Example 1 Fineness - Titer [dtex]
1.40 Breaking tenacity dry [cN/tex] 38.60 Breaking tenacity wet
[cN/tex] 30.70 Breaking tenacity loop [cN/tex] 11.40 Breaking
elongation - dry [%] 12.40 Breaking elongation - wet [%] 13.00 Wet
modulus [cN/tex] 199.00
EXAMPLE 2
[0104] Analogously to example 1, 2.951 g NMMNO (60.84%), 305 g
MoDo, DP 500, dry contents 94%, 1.8 g propylgallate (0.63% related
to the cellulose content) as well as 17.5 g of the mixture used in
table 1--(in total 6.1% related to the cellulose content) were
mixed and heated to 94.degree. C. Obtained was a spinning solution
having a solids content of 12.9% and a viscosity of 7.801
Pa.multidot.s. The so produced spinning solution was spun to fibers
like in comparative example 1.
8TABLE 6 Fiber data example 2 Example 2 Fineness - Titer [dtex]
1.48 Breaking tenacity dry [cN/tex] 36.60 Breaking tenacity wet
[cN/tex] 32.40 Breaking tenacity loop [cN/tex] 13.30 Breaking
elongation - dry [%] 12.10 Breaking elongation - wet [%] 13.50 Wet
modulus [cN/tex] 188.00
EXAMPLE 3
[0105] Analogously to example 1, 2,750 g NMMNO (60.3%), 305 g MoDo,
DP 500, dry contents 94%, 1.7 g propylgallate (0.63% related to the
cellulose content) as well as 11.2 g of a powder--shown in table
2.2-- (in total 4.1% related to the cellulose content) were mixed
and heated to 94.degree. C. Obtained was a spinning solution having
a solids content of 13% and a viscosity of 6.352 Pa.multidot.s. The
so produced spinning solution was spun to fibers like in
comparative example 1.
9TABLE 7 Fiber data example 3 Example 3 Fineness - Titer [dtex]
1.41 Breaking tenacity dry [cN/tex] 33.40 Breaking tenacity wet
[cN/tex] 29.20 Breaking tenacity loop [cN/tex] 9.00 Breaking
elongation - dry [%] 12.60 Breaking elongation - wet [%] 8.60 Wet
modulus [cN/tex] 182.00
EXAMPLE 4
[0106] Analogously to example 3, 3,345 g NMMNO (59.5%), 318 g MoDo,
DP 500, dry contents 94%, 1.9 g propylgallate (0.63% related to the
cellulose content) as well as 23.6 g of a mixture similar to the
one used in table 3 (in total 7.9% related to the cellulose
content) were mixed and heated to 94.degree. C. The mixture used in
this example differs from the one used in example 3 above all by a
higher potassium content and a lower calcium content (.about.12.6%
to .about.35%). Obtained was a spinning solution having a solids
content of 12.4% and a viscosity of 7.218 Pa.multidot.s. The so
produced spinning solution was spun to fibers like in comparative
example 1.
10TABLE 8 Fiber data example 4 Example 4 Fineness - Titer [dtex]
1.42 Breaking tenacity dry [cN/tex] 41.40 Breaking tenacity wet
[cN/tex] 32.90 Breaking tenacity loop [cN/tex] 8.30 Breaking
elongation - dry [%] 11.90 Breaking elongation - wet [%] 12.00 Wet
modulus [cN/tex] 212.00
EXAMPLE 5
[0107] 3,204 g NMMNO (59.5%), 318 g MoDo, DP 500, dry contents
94.4%, 1.9 g propylgallate (0.63% related to the cellulose content)
and 25.4 g brown algae (8.5% related to the cellulose content) of
the type Laminaria were mixed, and the so obtained mixture was
heated to 94.degree. C. Obtained was a discontinuously produced
spinning solution having a cellulose content of 13.24% and a
viscosity of 6.565 Pa.multidot.s. The so obtained spinning solution
was spun to fibers, whereby the following spinning conditions were
observed:
11 Temperature of the store tank 90.degree. C. Temperature spinning
block, nozzle 80.degree. C. Spinning bath 4.degree. C. Spinning
bath concentration (start) 0% (distilled water) Spinning bath
concentration (end) 7% NMMNO Spinning pump 20.0 cm.sup.3/min.
Nozzle filter 19200 M/cm.sup.2 Spinning nozzle 495 Hole 70 .mu.m;
Au/Pt Final drawing-off 30 m/min.
[0108] The fibers were cut to a staple length of 40 mm, were washed
free of a solvent and finished with a 10 g/l lubrication (50%
Leomin OR-50% Leomin WG (nitrogen-containing fatty acid polyglycol
ester Clariant GmbH)) at 45.degree. C. or, respectively, the fat
add-on for the better continued processing of the fibers was
applied, and dried at 105.degree. C. Subsequent to the drying a
fiber humidity of 10% was adjusted. An additional bleaching process
prior to the drying was not performed in this case.
[0109] The spinning behavior of the spinning solution obtained
according the present example was good.
[0110] The following table 9 shows the physical properties of the
so obtained cellulose fibers.
12 TABLE 9 Fineness [dtex] 1.42 Breaking force [cN] 5.85 Breaking
force variation [%] 15.8 Elongation [%] 11.9 Wet elongation [%]
12.0 Breaking tenacity [cN/tex] 41.4 Breaking tenacity wet [cN/tex]
32.9 Loop breaking tenacity [cN/tex] 8.3 Wet abrasion upon breakage
[turns] 10 Wet abrasion variation [%] 19.7 Wet modulus [cN/tex]
212
[0111] The elementary analyses of the applied material from sea
plants, brown algae Laminaria digitata and the fiber sample with
incorporated brown algae is shown in the following table 10.
13TABLE 10 Fiber sample with incorporated Brown algae brown algae
material Analyses [mg/kg] material Laminaria digitata Sodium 28,300
460 Magnesium 51,300 3,400 Calcium 126,000 8,100 Chromium 850 50
Manganese 670 55 Iron 32,600 2,000 Nickel 210 20 Copper 30 8
Molybdenum <5 <5 Cobalt 19 <5
[0112] FIG. 2 moreover shows that a spinning solution with 8.5%
Laminaria digitata is stable over thermal disintegration up to
approximately 200.degree. C.
EXAMPLE 6
[0113] 3,687 g NMMNO (62%), 381 g MoDo, DP 500, dry contents 94.4%,
2.27 g propylgallate (0.63% related to the cellulose content) and
3.6 g brown algae flour Laminaria digitata (1% related to the
cellulose content) were mixed and heated to 94.degree. C. Obtained
was a spinning solution having a cellulose content of 12.78% and a
viscosity of 8.424 Pa.multidot.s. The so produced spinning solution
was spun to fibers like in comparative example 1.
[0114] The physical properties of the so obtained cellulose fibers
are shown in the following table 11.
14 Fineness [dtex] 1.40 Breaking force [cN] 6.10 Breaking force
variation [%] 21.8 Elongation [%] 13.0 Wet elongation [%] 12.7
Breaking tenacity [cN/tex] 42.4 Breaking tenacity wet [cN/tex] 37.7
Loop breaking tenacity [cN/tex] 8.81 Wet abrasion upon breakage
[turns] 14 Wet abrasion variation [%] 34.7 Wet modulus [cN/tex]
254
[0115] The so obtained fibers were spun to a yarn. The spinning was
carried out under the conditions 63% relative air humidity and
20.degree. C. by means of carding, stretching and spinning with a
rotor spinning machine, to form 75 g of yarn with approximately 20
tex. FIG. 3 shows that the spinning solution with 1% Laminaria
digitata, related to the cellulose content, is stable up to a
temperature of approximately 200.degree. C.
EXAMPLE 7
[0116] A cellulose xanthogenate was produced from a mixture of 33
weight-% cellulose, 17 weight-% caustic soda solution and 50
weight-% water by adding 32% carbon disulfide related to cellulose.
Thereafter the xanthogenate was transferred by stirring for 2
hours, with the addition of diluted caustic soda solution, into a
spinning solution with 6 weight-% cellulose, 6 weight-% NaOH and
substantially water and reaction products resulting from the
xanthate production. To the so obtained viscose solution 0.9
weight-% of brown algae material were added to the spinning
solution. The viscose solution was allowed to stand for
approximately 6 hours under a vacuum for degassing and thereupon
filtrated. The so obtained viscose solution had a maturity level of
10.degree. Hottenroth and was spun to fibers.
[0117] The spinning conditions were:
15 Nozzle [n/.mu.m] 1,053/60 Hole throughput [g/hole/min.] 0.07
Temperature of coagulating bath [.degree. C.] 30 Sulfuric acid in
the coagulating bath [%] 10.8 Sodium sulfate in the coagulating
bath [%] 20.0 Zinc sulfate in the coagulating bath [%] 1.5
Drawing-off speed [m/min.] 36
[0118] The physical properties of the so obtained rayon fibers are
shown in the following table 12.
16 TABLE 12 Fineness - Titer [dtex] 1.7 Breaking tenacity dry
[cN/tex] 21.7 Breaking tenacity wet [cN/tex] 12.4 Fineness-related
loop strength [cN/tex] 6.0 Breaking elongation - dry [%] 14.2
Breaking elongation - wet [%] 15.8 Wet modulus [cN/tex] 2.9
EXAMPLE 8
[0119] Rayon fibers were produced in accordance with example 7,
except for the fact that 0.1 weight-% of brown algae material
instead of 0.9 weight-% were added to the spinning solution.
[0120] The physical properties of the so obtained viscose or rayon
fibers are shown in table 13.
17 TABLE 13 Fineness - Titer [dtex] 1.7 Breaking tenacity dry
[cN/tex] 23.7 Breaking tenacity wet [cN/tex] 14.1 Loop strength
[cN/tex] 6.5 Breaking elongation - dry [%] 16.9 Breaking elongation
- wet [%] 18.5 Wet modulus [cN/tex] 3.0
COMPARATIVE EXAMPLE 3
[0121] As comparison, a viscose fiber was produced in accordance
with example 7, except for the fact that no brown algae material
was added.
[0122] The physical properties of said viscose fiber are shown in
table 14.
18 TABLE 14 Fineness - Titer [dtex] 1.7 Breaking tenacity dry
[cN/tex] 24.8 Breaking tenacity wet [cN/tex] 14.2 Loop strength
[cN/tex] 6.4 Breaking elongation - dry [%] 17.2 Breaking elongation
- wet [%] 21.1 Wet modulus [cN/tex] 2.9
EXAMPLE 9
[0123] For the production of cellulose carbamate an alkali
cellulose was first produced from a chemical pulp with 92-95%
alpha-content (Ketchikan). The caustic soda solution was washed out
of the matured alkali cellulose (35 weight-% cell; 15 weight-%
NaOH; 50 weight-% water) with water. After squeezing out the so
activated cellulose (70 weight-% water) 10 kg of the squeezed out
activated cellulose were mixed with urea (1.5 kg) in a kneader. The
urea is thereby separated in the water contained in the cellulose
and is evenly distributed in the cellulose. Said cellulose pulp was
transferred into a reactor equipped with stirrer and reflux cooler,
into which o-xylol (30 kg) had been fed. The contents in the
reactor was then heated for approximately 2 hours at 145.degree. C.
and filtered off.
[0124] The so obtained residue was passed back into the reactor,
into which approximately 25 kg water had been fed. The xylol still
adhering to the carbamate was stripped off at 88.degree. C. After
the filtration the carbamate was washed out with hot water
(50.degree. C.) and with cold water. Thereafter the carabamate was
squeezed out.
[0125] 3.45 kg Stark-solution were produced from 1.02 kg of said
carbamate with 1.1 kg caustic soda solution (30 weight-%), 1.30 kg
water and with the corresponding amount of brown algae (0.03 kg).
All reactants were pre-cooled. The reaction itself took place at a
temperature of 0.degree. C. (Composition of the Stark-lye: 11.0
weight-% cell, 9.5 weight-% NaOH).
[0126] A spinning mass (5 kg) was produced from the cooled
Stark-solution by adding 1.55 kg cooled caustic soda solution (3.03
weight-%) at a temperature of 0.degree. C. The cooled spinning mass
was filtrated through a filter with degrees of fineness of 10-40
.mu.m and was spun.
[0127] The following spinning conditions were observed:
19 Nozzle [n/.mu.m] 36/60 Hole throughput [g/hole/min.] 0.11
Temperature of coagulating bath [.degree. C.] 35 Sulfuric acid in
the coagulating bath [%] 90 Sodium sulfate in the coagulating bath
[%] 140 Drawing-off speed [m/min.] 30
[0128] The physical properties of the so obtained Carbacell.RTM.
fibers are shown in table 15.
20 TABLE 15 Fineness - Titer [dtex] 3.1 Breaking tenacity dry
[cN/tex] 14.8 Breaking tenacity wet [cN/tex] 5.7 Loop strength
[cN/tex] 7.5 Breaking elongation - dry [%] 4.0 Breaking elongation
- wet [%] 4.7 Wet modulus [cN/tex] 100
EXAMPLE 10
[0129] Carbacell.RTM. fibers were produced in accordance with
example 9, except for the fact that 0.1 weight-% of brown algae
flour instead of 0.6 weight-% were added to the spinning mass.
[0130] The physical properties of the so obtained Carbacell.RTM.
fibers are shown in the following table 16.
21 Fineness - Titer [dtex] 3.3 Breaking tenacity dry [cN/tex] 17.8
Breaking tenacity wet [cN/tex] 5.8 Loop strength [cN/tex] 7.5
Breaking elongation - dry [%] 4.6 Breaking elongation - wet [%] 5.4
Wet modulus [cN/tex] 129
COMPARATIVE EXAMPLE 4
[0131] Carbacell.RTM. fibers were produced in accordance with
example 9, except for the fact that no brown algae flour was
added.
[0132] The physical properties of the so obtained fibers are shown
in the following table 17.
22 TABLE 17 Fineness - Titer [dtex] 3.1 Breaking tenacity dry
[cN/tex] 18.0 Breaking tenacity wet [cN/tex] 5.8 Loop strength
[cN/tex] 7.9 Breaking elongation - dry [%] 4.7 Breaking elongation
- wet [%] 5.5 Wet modulus [cN/tex] 135
EXAMPLES 11 TO 15
[0133] Lyocell cellulose fibers were continuously produced in
accordance with example 5, whereby the respective amounts, the
conditions of the continuously performed process and the physical
properties of the obtained fibers are shown in the following table
18.
23TABLE 18 Example Example Example Example Example Unit 11 12 13 14
15 Pulp Type Alicell Modo Alicell Alicell Alicell VLV Drown VLF VLV
VLV Dissolving DP Pulp 9 540 530 540 540 540 Feed hole kg/h 161.8
161.8 173.0 167.2 161.7 Cellulose % 13.0% 13.0% 12.0% 12.5% 13.0%
Water % 10.7% 10.7% 11.3% 11.0% 10.7% NMMO % 76.3% 76.3% 76.7%
76.5% 76.3% Solution flow kg/h 138.5 138.5 150.0 144.0 138.5 Vapor
kg/h 23.3 23.3 23.0 23.2 23.3 condensate System pressure mbar 55 55
55 55 55 abs. Spinning temp. .degree. C. 117 110 72 80 117 Fiber
draft 10.9 10.9 4.3 10.5 11.81 Titer dtex 1.3 1.3 1.3 1.3 1.18 Air
gap height mm 20 20 7 12 20 Air quantity Nm.sup.3/h 130 130 130 180
135 Air temperature .degree. C. 17.5 18.5 17.2 17.9 19 Hole
throughput g/hole 0.030 0.060 0.028 0.134 0.028 min Hole diameter
.mu. 100 100 65 100 100 Brown algae g/h 181.9 182.3 1528.0 1531.8
2704.0 powder Amount Coagulating bath .degree. C. 20 20 6 6 20
temperature Spinning bath % 20 20 20 20 20 concentration NMMO Final
drawing-off m/mm 35 70 30 150 35 Titer dtex 1.40 1.42 1.38 1.40
1.21 Strength dry cn/tex 42.1 41.4 41.8 42.4 41 Elongation dry %
12.8 11.9 13.0 13.2 13.8 Wet strength cn/tex 32.9 34.8 37.7 37.7
33.4 Wet elongation % 12.0 12.3 12.7 12.0 12.8 Loop strength cn/tex
15.4 13 8.3 8.9 13.8 Wet modulus cn/tex 238 254 212 212 242
EXAMPLE 16
[0134] Based on the fibers produced in accordance with comparative
example 1 and 2 and in accordance with examples 1 to 4 cryo-breaks
in liquid nitrogen were produced, whereof photographs were taken by
means of a field emission electron-scanning microscope (Joel 6330
F) after the fibers had been sputtered with platinum.
[0135] The fiber produced according to comparative example 1 or 2
according to the standard process shows a splinted break. The
fibrillary structure can clearly be recognized on the broken
surface. The strong orientation of the fibrilla can be seen on the
standing out longitudinal ridges and on the strongly fissured
structure along the longitudinal axis.
[0136] The photographs of the fibers from examples 1 to 4 show
something completely different. The partly blunt and clean broken
surfaces can clearly be recognized. Moreover, it can be recognized
that the distinct high longitudinal orientation in the fiber
according to comparative example 1 is much less distinct in
examples 1 to 4.
[0137] On the basis of the electron-scanning microscope photographs
striking differences in the structure of the fiber were
detected.
[0138] Above all, the strongly repressed longitudinal orientation
shows that the use according to the invention of material from sea
plants and/or shells of sea animals or of at least two components
selected from the group consisting of saccharides and the
derivatives thereof, proteins, amino acids, vitamins and metal ions
results in a smaller fibrillation of the fibers during the
production of cellulose fibers.
[0139] It had been especially interesting and unexpected that
mixtures with different substances contained therein show said
effect, as all previously known defibrillation agents are
cross-linking agents. The smaller fibrillation is presumably due to
a change of the crystallization properties of the cellulose during
the extrusion.
* * * * *