EP1257598A1

EP1257598A1 - Cellulose shaped body and method for the production thereof

Info

Publication number: EP1257598A1
Application number: EP01915282A
Authority: EP
Inventors: Stefan Zikeli; Thomas Endl; Michael Gert Martl
Original assignee: ZiAG Plant Engineering GmbH
Current assignee: LL Plant Engineering AG
Priority date: 2000-02-21
Filing date: 2001-02-20
Publication date: 2002-11-20
Also published as: AU4242601A; WO2001062845A1

Abstract

The invention relates to a shaped body comprising cellulose having a crystallinity index of < 45 %. The invention also relates to a shaped body comprising cellulose with a proportion of cellulose IV of at least 50 %. The shaped body can contain, as an additive, a material based on marine plants and/or shells of marine animals. This shaped body can be used as packaging material or as fiber material, in the form of fiber material as a mixing constituent for producing yarns as well as in the form of fiber material for producing nonwovens or wovens.

Description

Cellulose molded body and process for its production

The invention relates to a cellulose molded body and a method for its production

It is known that cellulose occurs in five crystalline modifications, namely 1.11, III, IV and X. Of these, however, only the modifications I to IV are fibrous and are therefore of interest for textile processing. The cellulose I god is used in a large number Found natural celluloses, as in celluloses from plants, bacteria, or algae cellulose II, is the most frequently used modification industrially, since it is contained in all regenerated celluloses. Furthermore, it is known that the crystalline modifications can be converted into one another

Cellulose IV, which can also be obtained by heating cellulose III, is a crystalline modification of cellulose, which is also found in many plants and in seaweed

US Pat. No. 4,950,597 describes a method for screening and isolating spontaneously occurring or induced cellulose II-producing microorganisms. Acetobacter or algae are mentioned as examples of corresponding microorganisms

No. 5,322,524 describes cellulose fibers with improved resistance to abrasion and improved permeability to chemicals, the crystal lattice of which consists of highly stable cellulose III and cellulose IV, in particular cellulose III

US Pat. No. 4,871,370 also discloses a process for the production of cellulose fibers by which fibers with improved resistance to abrasion and improved permeability to chemicals are obtained. The cellulose fibers are treated with ammonia vapor at a defined pressure and temperature, with highly stable, crystalline cellulose III is obtained The crystalline cellulose III can further be converted into cellulose IV It is also known that cellulose fibers of the amine oxide type (lyocell fibers) which are precipitated in water have a higher degree of plasticity and longer and thinner crystals than cellulose fibers of the viscose type

A high degree of cellulose is disadvantageous, however, because the fibers show an increased property as an undesirable property

The object of the present invention is therefore to provide a shaped body which contains cellulose and has a low tendency to fill, and a process for its production

The problem is solved by a shaped body comprising cellulose with a degree of stability of <45%. Furthermore, the task is solved by a shaped body comprising cellulose with a proportion of cellulose IV of at least 50%. Another solution to the task is a shaped body comprising Cellulose with a degree of conductivity of <45% and a proportion of cellulose IV of at least 50%

In a preferred embodiment, the cellulose has a degree of crystallinity of <36%, in particular <34%. Furthermore, the proportion of cellulose IV is preferably at least 70%. The rest of the cellulose is preferably in the form of cellulose II

As an additive, the shaped body can contain a material from marine plants and / or shells from marine animals, such as Ascophyllum nodosum, Lammana digitata or üthothamnium calcaraeum, particularly preferably Ascophyllum nodosum. Ascophyllum nodosum differs from üeumothamnium calculus in terms of the composition of the additives due to a higher proportion of organic material The additive is preferably contained in an amount of at least 3% by weight, preferably 5 to 25% by weight, in particular in an amount of 8 to 12% by weight, based on the cellulose content

The molded body according to the invention can be selected from the group consisting of containers, foils, membranes, fabrics and fibers. The fibers can be staple fibers, monofilaments or continuous filaments If the shaped body according to the invention is a fiber, the fiber can be a lyocell, viscose or carbamate fiber, particularly preferably a lyocell fiber

The shaped body is preferably used as packaging material or fiber material. Furthermore, the shaped body according to the invention in the form of fiber material can be used as a mixture component for the production of yarns or for the production of nonwovens or woven fabrics

Furthermore, the molded body is used in a preferred embodiment in the form of fiber material for the production of nonwovens or fabrics, wherein in the nonwoven fabric or fabric an additional component is selected from the group consisting of cotton Lyocell, rayon, Carbacell polyester, polyamide, cellulose security , Acrylic polypropylene or mixtures thereof is present

The solution to the problem is also a method for producing a shaped body, comprising the following steps

(A) continuous or discontinuous mixing of the cellulose with an additive,

(B) producing a deformable mass, (C) processing the mass obtained in (B) into a shaped body, and

(D) aftertreatment of the molded article produced

In the process in step (A), N-methyl-morphohn-N-oxide (NMMO) is preferably added

Furthermore, in a preferred embodiment, the molded body produced can be washed out and treated in step (D) for further treatment. Aftertreatments can be, for example, bleaching processes, processes for adjusting the fat build-up or other impregnation processes with chemicals Washed out with water or on the already dried in a chemical and mechanical manner It has surprisingly been found that fibers according to the invention produced by the Lyocell process have an astonishingly low degree of kink instinct, which is well below the kink instinct degree of the known Lyocell fibers

Furthermore, it has surprisingly been found that the molded body produced by the incorporation of algae material has a high porosity, which can be used positively for the corresponding aftertreatment processes to adjust the product properties of the molded body. It was also possible to demonstrate an improved absorbency of the fibers produced according to the invention

The invention is explained below with the aid of examples

Comparative example 1 (without admixture)

3,086 g of NMMNO (59.8% ιg), 308 g of MoDo, DP 500, dry matter content 94%, 1.8 g of propyl gallate (0.63% based on the cellulose content) were mixed and the mixture thus obtained was mixed up 94 ° C. A discontinuously produced spinning solution with a cellulose content of 11.8% and a viscosity of 4 765 Pa • s was obtained. The spinning solution thus obtained was spun into fibers, the following spinning conditions being maintained

Storage tank temperature 90 ° C

Temperature spinning block nozzle 80 ° C

Spin bath 4 ° C Spin bath concentration (beginning) 0% (distilled water)

Spin bath concentration (end) 5% NMMNO

Spinning pump 20.0 cm ³ / min

Nozzle filter 19200 M / cm ²

Spinning nozzle 495 hole 70 μm Au / Pt end draw 25 m / min

The fibers were cut into 40 mm stacks and washed solvent-free and with a 10 g / l softener (50% Leomin OR-50% Leomin WG (nitrogen-containing fat acid polyglycol ester Fa Clanant GmbH)) at 45 ° C or the fat layer applied for better fiber processing and dried at 105 ° C. After drying, a fiber moisture of 11% was set. An additional bleaching process before drying was not carried out in this case

The spinning behavior of the spinning solution obtained according to this example was good

Furthermore, the x-ray degree x _{c was} determined by means of X-ray wide-angle examinations (WAXS). Measurements were also carried out with X-ray small-angle diffraction (SAXS). Pores in the order of magnitude of approximately 2 nm to 100 nm were detected

Table 1 Fiber data and further test results from Comparative Example 1

Comparative Example 2 (without admixture; treatment of the filaments in the air gap)

A spinning solution was prepared analogously to Comparative Example 1. The spinning solution was spun into fibers, in contrast to Comparative Example 1 the temperature of the spinning block was set to 95 ° C. and the temperature of the nozzle to 105 ° C. The faded coulter was included in the air gap between the nozzle and the falling bath humid air (temperature 20 ° C, humidity 70%) blown π The experiment was otherwise carried out as in Comparative Example 1

Table 2 Fiber data and further test results from comparative example 2

example 1

3 156 g of NMMNO (61.4% ιg), 315 g of MoDo, DP 500, dry content 94% 1.9 g of propyl gallate (0.63% based on the cellulose content) and 11.6 g of a mixture Ascophyllum present as a powder nodosum - shown in Table 3 - (in total 3.9% based on the cellulose content) were mixed and heated to 94 ° C. A spin solution with a solids content of 12.4% and a viscosity of 6,424 Pa • s was obtained the spinning solution thus prepared was spun into fibers as in Comparative Example 1

Table 3: Composition of Ascophyllum nodosum

Table 4 Fiber data and further test results from Example 1

Example 2

Analogously to Example 1, 2 951 g NMMNO (60.84% ιg), 305 g MoDo, DP 500, dry content 94% 1 8 g propyl gallate (0.63% based on the cellulose content) and 17.5 g of the in Example 1 mixture used (in total 6.1% based on the cellulose content) mixed and heated to 94 ° C. A spinning solution with a solids content of 12.9% and a viscosity of 7 801 Pa • s was obtained. The spinning solution thus produced was spun into fibers as in Comparative Example 1

Table 5 Fiber data and further test results from Example 2 FB - tear strength loop I [cN / tex] 13 30

Ultimate tensile strength - dry I [%] 12 10

Ultimate tensile strain - wet I [%] 13 50

Wet module [cN / tex] 188 00

WAXS results

Degree of crunch instinct x _c [%] 43

K dimensionite D101 [nm] 4 60

Crystallite dimension D10-1 [nm] 4.70

Crystallite dimension D002 [nm] 3 70

SAXS results

Porosity wv [%] 0.33

Average pore size Iv [nm] 7.81

Specific surface area Osp [m / cm ^b ] 1 68

birefringence

Fiber diameter D [μm] 12.30

Fiber diameter Delta D [μm] 5.50

Birefringence delta n [nm] 0.0315

Example 3

Analogously to Example 3, 3,345 g of NMMNO (59% 5%), 318 g of MoDo DP 500 dry content 94% were 1.9 g of propyl gallate (0.63% based on the cellulose content) and 23.6 g of a mixture of Lammana in powder form digitata, which is similar to the Lithothamnium calcaraeum mixture shown in Table 6 (in total 7.9% based on the cellulose content), mixed and heated to 94 ° C. The Lammana digitata mixture used in this example differs from the Lithothamnium calcaraeum mixture mainly by one higher potassium content and a lower calcium content (~ 12 6% to -35%) A spinning solution with a solids content of 12% and a viscosity of 7,218 Pa • s was obtained. The spinning solution thus produced became fibers as in Comparative Example 1 spun Table 6: Composition of Lithothamnium calcaraeum

Table 7: Fiber data and further test results from Example 3

Example 4

Analogously to Example 1, 3 315 g NMMNO (60.5% ιg), 325 g MoDo DP 500, dry content 94% 1.9 g propyl gallate (0.63% based on the cellulose content) and 24 4 g of the mixture used in Example 1 Ascophyllum nodosum (in total 8.0% based on the cellulose content) were mixed and heated to 94 ° C. Three different mixtures were prepared, the mixture Ascophyllum nodosum impregnated with mitialuminum impregnated with NMMO, washed free of NMMO and subjected to the tests in dried form A spinning solution with a solids content of 12.5% and a viscosity of 5 801 Pa • s was obtained in each case. The spinning solutions thus produced were spun into fibers as in Comparative Example 1

Table 8: Fiber data of the fibers produced according to Example 4 Table 9: Further test results of the asers produced according to example 4

Claims

Expectations:

1 molded body, comprising cellulose with a degree of kink initiation of <45%

2 moldings, comprising cellulose with a proportion of cellulose IV of at least 50%

3 shaped bodies comprising cellulose with a degree of kink initiation of <45% and with a proportion of cellulose IV of at least 50%

4 Shaped body according to claim 1 or 3, wherein the degree of folding is <36%

5 molded article according to claim 4, wherein the kink initiality degree is <34%

6 molded article according to one of claims 2 to 5, wherein the proportion of cellulose IV is at least 70%

7 molded article according to one of claims 2 to 6, wherein the rest of the cellulose is present as cellulose II

8 shaped body according to one of the preceding claims, wherein the shaped body contains as an additive a material from seaweed and / or shells of sea animals

9 molded article according to claim 8, wherein the Fomnkoper contains Ascophyllum nodosum as material from seaweed

10 Shaped body according to claim 8, wherein the shaped body contains Lammana digitata as material from marine plants

11 Shaped body according to one of claims 8 to 10, wherein the additive is contained in an amount of 5 to 25 wt% A molded article according to claim 11, wherein the additive is contained in an amount of 8 to 12% by weight

Shaped body according to one of the preceding claims, wherein the shaped body is selected from the group consisting of containers, films, membranes, fabrics and fibers

Shaped body according to claim 13, wherein the fibers are staple fibers, mono- or endios filaments

Shaped body according to claim 13 or 14, wherein the fibers are lyocell, viscose or carbamate fibers

Use of the shaped body according to one of the preceding claims as packaging material or fiber material

Use of the shaped body according to one of claims 1 to 15 in the form of fiber material as a mixture component for the production of yarns

Use of the shaped body according to one of claims 1 to 15 in the form of fiber material for the production of nonwovens or fabrics

Use of the shaped body according to one of claims 1 to 15 in the form of fiber material for the production of nonwovens or fabrics, wherein in the nonwoven fabric or fabric additionally a component selected from the group consisting of cotton, lyocell, rayon, carbacell polyester, polyamide, cellulose acetate, Acrylate polypropylene or mixtures thereof is present

A process for producing a molded article according to any one of claims 1 to 15, comprising the following steps

(A) continuous or discontinuous mixing of the cellulose with an additive,

(B) Making a deformable mass (C) processing the mass obtained in (B) into a shaped body, and

(D) aftertreatment of the molded article produced

The method of claim 20, wherein in step (A) N-methylmorpholine-N-oxide is added