DE2430502A1 - COTTON-FIBER JOINT WITH INCREASED ABSORPTION - Google Patents

Description

DIPL. ΙΝΞ. KLAUS BEHN

DIPL.-PHYS. ROBERT MÜNZHUBER _ _

PATENTANWÄLTE / H V U 0 U ώ

8 MUNICH 22 Wl DENMAYERSTRASSE 6 TEL. (089) 22 25 30 - 29 51 92

■ 25. June 1974 A 14574 pp / ib

Company COTTON, INCORPORATED, 1370 Avenue of the Americas, New York, New York 10019, USA

Cotton fiber connection with increased absorbency

The invention relates to a new cotton-fiber compound with increased absorbency and a process for producing the same *

There has been a long-standing demand for cotton fiber composites or products thereof, such as bath towels, diapers or the like, on the one hand because of their absorption properties, but on the other hand also because of the good and resilient quality properties. the The ability to absorb dye and other textiles is affected by treatments such as permanent pressing, ha also contributed to the popularity of cotton products. Research in the field of cotton fibers or their products with higher absorbency and greater resistance ' and increased receptivity for dyeing and other treatments affecting textiles continue.

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Merck, Finck & Co .. Munich, No. 25464 I Bankhaus H, Aufhäuser. Munich, No. 2613OO Postal check: Munich 20904-8OO Telegram address: patent senior

ORIGINAL IN

The present invention was made within the framework of this research.

Cotton fibers, which are carefully removed from the capsules and which must not be allowed to dry out, are known to show high internal mobility and are very porous. For example, they can be stretched further than fibers that have dried and rewetted before breaking, and reversal areas can be observed that spread in the direction of stretching. Using X-rays, several have concluded that cotton in an undried botanical growth state is amorphous, or at least has very little crystallinity if not stretched prior to drying, although others have stated otherwise who have studied the effect of penetration and accessibility or that of hydrolysis. Examples include: Berkley, EF and Kerr, T., "Structure and Plasticity of Undried Cotton Fibers," Ind. Eng. Chem., 38, 304 (19-6); Berriman, LP, "The Role of Growth Rings in Cotton Properties," text. Res. J., 36, 272 (1966); Usmanov, HU, "Physical Chemistry of Native Cellulose", J. Polymer Sol., 23, 83I (1957); Heyn, ANH, "Crystalline State of Cellulose in Fresh and Dried Native Cotton Fibers from Unopened Bolls as Studied by X-ray Diffraction", J. Polymer Sci., A-3 » I25I (1965); Colvin, JR, "Structure and Biosynthesis of Cellulose", CRC Critical Revs, in Macromol. ScI., 1_,

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47 (1972); Nelson, HL and Mares, T., "Accessibility and Material Order Distribution of the Cellulose in the Developing Cotton Fibers," text. Res. J. , 35, 592 (1965); Ono, Y., "Studies on the Cotton Fiber as the Material for Cotton Spinning", Part I. Japan Cotton Textile Institute (1958), Osaka, Japan.-In the above-mentioned article, for example, Heyn reports the results of his X-ray diffraction studies on cotton fiber samples that have either been dried directly or of which it is said "... the water was separated in various 'indirect' ways, which have been determined to better preserve the original structure and consist of the following steps: (a) Solvent Exchange, (b) freeze drying, (c) drying above the critical temperature of the liquids and (d) drying after the cellulose of the wet fibers has been crosslinked ". Greater dye accessibility was described for the samples with solvent exchange (benzene and pentane). However, no practical aspects have been suggested that would serve to further develop the conventional techniques.

It is therefore the main object of the invention to find new cotton-fiber compounds or to create products thereof with increased absorbency. Another aim of the invention is to develop new To create cotton fiber compounds or products thereof with improved resistance (deformability). The end-

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In addition, the new products should have an improved absorption capacity have influencing treatments for various textiles. Another object of the invention is to provide methods for the manufacture of these new cotton-fiber compounds and their products.

Further objects of the inventions will become clear to the person skilled in the art from the following:

According to the invention, a cotton-fiber connection with increased absorbency is produced from cotton fibers exists, which in its never-dried, botanical growth state fixes and stabilizes and becomes a fiber or Textile compound or a textile product are formed.

A key feature of the invention is the discovery that bonds of fixed, never-dried cotton fibers an increased absorbency as well as improved penetration and diffusion characteristics compared to similar ones Have fiber bonds formed from dried cotton. The fiber connections according to the invention can also have an improved resistance (deformability or elongation) and an improved Have the ability to absorb treatments with fabrics that affect textiles, such as a wrinkle-proof making agent.

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Further features and advantages will become clear from the description below.

On the drawing is an embodiment of the invention for example, show:

Fig. 1 Water absorption isotherms for fixed, never made from dried cotton fibers Fabric and yarn and for fabric and yarn made from dried cotton fibers;

Fig. 2 Diffusion constants for water from fixed, never made from dried cotton fibers Fabrics and fabrics made from dried cotton fibers;

3 shows the permeation constants for water at off fixed, never dried cotton fibers and in the case of made from dried cotton fibers Tissue; and

Fig. 4 Color rates (direct blue) for fixed, never dried Cotton fibers and for dried cotton.

As mentioned above, the new cotton fiber compounds achieved or produced according to the invention by a process which involves fixing the cotton fibers in their never-dried, botanical growth state and in which then die.fixierten cotton fibers in a fiber connection can be formed.

The cotton fibers used are in their never-dried, botanical growth state

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consist of such cotton fibers, which are taken from a cotton boll have been removed, which should not have dried out to a certain extent, and which after the decrease should also not have dried out to a certain extent. In other words, the cotton fibers in their never-dried, botanical growth state, essentially all of their moisture content original condition retained.

Cotton fibers that have never been dried have been shown to be highly crystalline and, when drying or stretching, an irreversible hydrogen bond occurs in the fibers. In the case of water absorption behavior, the cotton that has never been dried contains 100 % more water than if it was dried and re-moistened once. In addition, a cotton fiber that has never been dried has a stretch that is at least 50% greater than that of a cotton fiber that has been dried and re-moistened once.

Cotton fibers in their never-dried, botanical growth state can be obtained by harvesting or otherwise of the ripe cotton bolls before they "burst". Before fixing, the unopened capsules should be completely be kept wet, for example immersed in water.

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The cotton fibers in their never-dried, botanical wax turns state can be used under any conditions are fixed, which avoid the irreversible formation of hydrogen bonds between the crystalline cellulose basic elements, which form the fiber, with hydrogen bonding normally occurring during the initial fiber drying occurs.

Preferably the never dried cotton fibers fixed by treating the fibers with at least one locking collar. The term "Sperragens" (blocking agent) is used here used to determine any chemical component which, when added to the fiber that has never been dried, becomes irreversible Would avoid formation of hydrogen bonds, as outlined above. These blocking payments can also can be divided into two classes: (1) permanent blocking payments and (2) temporary blocking payments. The following will be Examples of these materials are given under their respective headings, these examples not being limiting meant to be:

Permanent blocking agents.

This class of blocking agents includes any means which are permanent because of reaction with the cellulose or physical inclusion in the cellulose phase.

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Formaldehydes, acrylamides and dyes are preferred elements of this class.

Other polymerized materials can be used for this process. Such substances can either be direct grafted onto the cellulose or polymerized "in situ" to create an irreversible hydrogen bond during the first Avoid drying the cotton fibers. Vinyl or vinylidene derivatives can be polymerized in situ or directly on the fibers are grafted on using various conventional triggering techniques, such as peroxides, Redox systems and irradiation. Non-limiting examples of such substances are: Acrylics (for example Acrylonitrile, acrylamides, methyl acrylate and ethylacry-Ie), Methacrylic acids (methyl methacrylic acid ester, ethyl methacrylic acid ester), Dienes (butadienes, isoprene and chloroprene), and pyridines (2-vinylpyridines and 4-vinylpyridines). Condensation polymers can also be used in a manner similar to the vinyl or vinylidine derivatives. as Non-limiting examples of these substances can be given in the first place Line: The precursors to polyester production (e.g. polyethylene, terephthalic acid ester), polyester amides (e.g. nylon 6,6), polyurethanes, silicones, polyethers, aminoplasts and furan resins. The admixture of these materials is known per se for fiber systems in textile production.

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Another type of blockage, fixation, or stabilization; the never dried cotton condition could a direct reaction with the hydroxyl groups on the cellulose molecules cause. Both esterification and etherification reactions can be used. The esterification reactions include carboxylation with acyl halides or anhydrides, phosphorylation (e.g. phosphoric acid and cyanamides), an ester formation of halogen acid, and organic halides. Examples of etherification include reactions with methylolamides and their derivatives, Epoxy, cyanuric chloride and vinyl suIfogroups. Such Ingredients have been used in textile manufacture and the reaction conditions are well known to those skilled in the art common.

The dyeing can in particular from the process present Invention be dependent. That is, if the cotton fiber is dyed in the never-dried state, the dyeing process can also become the process of a fiber fixation, that is, the dyeing does not just give the fiber a different one Color, rather the coloring itself, avoids the normally irreversible Hydrogen formation that occurs during drying of the virgin fiber. The different color classes are known to the color chemist. Examples are: anthraquinone derivatives, naphthalenes derivatives and others Multi-ring systems that contain functional groups that

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neither react with the hydroxyl groups in the cellulose nor form a tight secondary bond.

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Other permanent barrier agents can contain insoluble, inorganic salts and oxides, which are doubled Implementation have been deposited. Organic materials that are insoluble in water, in a suitable solvent but are soluble can be deposited by solvent exchange techniques such as paraffin wax.

Short-term blocking payments .

Numerous materials, such as water-soluble salts or soaps, can be used to temporarily block the Hydroxyl groups can be used. Although intermittent blocking is not a preferred feature of the invention, so it is conceivable that certain textile applications (disposable diapers for example) will not have long-term stability the more common permanent blocking agents. In such cases, it might be desirable to have short-term blocking payments to use, such as water-soluble soaps, salts and detergents, as well as ureas and starches, to name just a few.

The examples of the permanent and short-term blocking or fixing agents that are given in this embodiment are to be assessed purely as examples and other considerations

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components may appear applicable to one skilled in the art.

The never dried cotton fibers are thereby fixed that they are treated with at least one of the blocking agents described above. During the deposit and Fixing should be the never dried fibers in their undried ones State to be maintained. The barrier agents can for example be applied in aqueous solution, in the the undried fibers are immersed.

It is also preferable, but not necessary, that there be any excess of barring agents or others Chemicals generated during deposition are washed out of the fiber before it is dried.

An attachment and / or a reaction of the blocking or fixing agents within the undried cotton is controlled by the diffusion pathway, with blocking agents smaller gram molecular weight are more favorable from the standpoint of practical treatment times. With regard to barrier agents with molecular weights of from 10 to 100,000 gram molecular weight can then be used. Preferable is the range from a molecular weight of 30 to 2000 moles

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The optimal pH for the various types of reactions can be determined by one skilled in the art in view of the present description. Any pH from 2 to 12 would not be unfavorable for fiber properties, but a pH in the range from 1 to 8 is preferred. Similar considerations apply to fixation response times and temperatures. The temperatures in the range from about 0 ° to 100 ° C. are suitable, but are preferably
between 20 ° and 90 ° C.

The amount of barrier or fixation agent can be between about 0.1 and 100 $ by weight of the dry fiber material, but preferably in a range of 0.1 to 10 $. It should be noted that the maximum amount of admixture that is possible for many of the blocking agents can only be a few percent. In such cases, an amount of about 0.1 wt -.% To be sufficient.

Once a fixation has been carried out, the cotton fibers become washed to remove any excess chemicals, dried and then refined. It can one or more gins can be performed to obtain the desired fiber lengths.

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The fixed cotton fibers can then in any Paser connection are formed, but especially in those Paser connections in which the absorbency represents an important point of view from the point of view of the user. Such cotton fibers can be produced as yarns and then brought into woven vein non-woven or knitted fabrics. The cotton fibers can can also be made in fabric or wadding form for use as disposable diapers or the like. Provided the fixed, never dried cotton fiber compounds according to the invention can absorb 100/6 more water than Normally dried cotton + fiber connections, so these can can be used for typical applications, such as Drying towels, tracksuits, towels, diapers, Sanitary towels and blotting paper, to name a few. Further applications are known to those skilled in the art common.

A direct consequence of this increased absorbency in the case of the fixed, never-dried fibers is to be found therein see that the cotton fibers or fiber compounds not only absorb more color than the normally dried cotton fibers to be able to, but that they can also do this with a

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absorb greater absorption speed. As a result, darker and more brilliant tints are achieved with the same color while also achieving greater uniformity of coloration.

The fixed, never dried cotton fibers or fiber compounds are particularly receptive to treatments with agents influencing textiles, such as anti-crease agents (e.g. methylol melamine, Dimethyloldihydroxydäthylen-Urea), dirt solvents, paints, burn inhibitors, mercerization substances, Water repellants and fabric softeners. The use of many of these fabric affecting agents can be synergistic or bring improved results if they are used on the fixed, never dried cotton fibers or fiber compounds compared to the usually dried cotton fibers or fiber compounds.

The invention is further illustrated by the following examples. All proportions and percentages in the examples are given for weights unless otherwise stated.

example 1

An unopened (green) boll, which has been removed in the wet state (immersed in distilled

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2A30502

Water at 4 ° C) was opened under water and a cotton fiber sample of approximately 300 mg was removed. the Cotton fiber sample was then obtained in its never-dried botanical growth state using the following Fixing solution fixed:

10.2 ml of an aqueous solution of 37 $ formaldehyde, which has been stabilized with $ 12 methanol

17 »2 ml of an aqueous solution of 38 $ sulfuric acid 72.6 ml of water

The never-dried cotton fiber sample was allowed to stand in the above-described fixing solution at 25 ° C. for one hour react. After fixation, the sample was washed three times in distilled water and air dried.

An analysis of the manner treated as described above Fiber sample showed that the cotton was $ 0.35 bound Formaldehyde. In addition, the sample showed long tapering break tips instead of the normal ones when rewetted short breakpoints found in unprocessed, re-moistened cotton. In addition, the length at the break was $ 20 for the fixed sample compared to about $ 10 for nor-

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paint, re-moistened cotton, which is also an indicator for high, internal mobility of the fixed, never dried cotton fiber. In addition, higher absorption properties compared to the unfixed, dried Tree fibers found.

Example '2

A sample of 100 mg was taken from an unopened cotton boll as in Example 1. This sample was placed in an aqueous solution with 500 mg of acrylamide and about 10 ml of a 5 ^ strength aqueous solution of CuClp and bubbled with pure nitrogen for 30 minutes. The sample ampoule was then sealed and at 25 ° C from a cobalt 60 gamma source at a dose of 0.145 megarads irradiated at a dose rate of 0.05 megarads / hour. After Irradiation, the fixed, never dried sample was thoroughly leached with water and dried.

An analysis of the sample treated in the manner described above showed that the cotton had 14 # dripped acrylamide contained. In a manner similar to Example 1, these fibers showed a length of $ 22 when rewetted at the break. versus the $ 10 for the normally re-moistened, dried one Fiber. The fiber fixed with acrylamide had long

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running fracture tips, which are a sign of high internal mobility are to be assessed. In addition, the fixed, never dried cotton fibers have high absorption properties found after fixation by acrylamide.

Example 3

Cotton fibers that had never been dried were removed from the unopened capsules under water, as described in Example 1 has been. The cotton fibers were placed in an aqueous solution of acidified formaldehyde for 3 hours at 25 ° C and then rinsed with water to remove any remaining chemicals. The fixed, never dried ones Cotton fibers were then air dried.

The same procedure was used for the preparation of the control fiber, excluding the fixation step Formaldehyde repeated.

The control and the fixed cotton fibers were combined in fabric form. Before fabric manufacture, both samples were ginned to separate the fibers from their seeds. Then, a cotton yarn (18 ^! > Of both the control and the fixed cotton fibers for weaving was spun in a fabric form. The respective samples were turned into

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into a yarn form, and then a fabric with a width of 40 cm was made. Before weaving, each sample was made sized using a carboxymethyl cellulose, which has been removed by washing after weaving.

Some absorption isotherms are shown in Fig. 1 for the Control yarn and the control fiber, as well as for the fixed, never dried fiber or the same yarn are shown. The fixed materials clearly show that they absorb more water than the control fiber. The corresponding Diffusion and permeation constants for each of the fibers are shown in FIGS. Here you can see that the total permeation constant in the case of fabric made from fixed, never-dried fibers by about $ 100 is higher.

Additional properties for the dried control cotton fibers and the fixed, never-dried cotton fibers (with 0.25 # bound formaldehyde) that were used during manufacture of the fabric are shown in the table below.

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Test (20 ⁰ C; 65% RH) control tissue Fixed, never

dried tissues

Micronaire 3.52 3-35

2.5 $ Span I.188 I.l4o

% Uniformity 46.7 42.0

% Short Fiber 4.33 & 77

Pressley "θ" gauge psi 83590 73-120

Gram / tex. 3mm gauge 24.98 21.07

% Length 5.25 6.00

% Non-lint 13-50 12.9

As can be seen from the above, the transport (water) properties of the firm, never dried cotton fiber, of the yarns and fabrics that have improved absorption properties with respect to the control fibers, fabrics and - Yarns can be obtained from usually dried cotton fibers.

Example 4

The coloring is carried out using a blue direct color (Amanil Sky blue FF), namely · of the never used

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dried cotton fibers, the fixed, never dried cotton fibers and the once dried control fibers which have been explained in Example 3. The results are compiled in FIG. 4, from which the dyeing speeds for fixed, never-dried cotton fibers and for cotton fibers that have been dried once can be seen. As FIG. ¹ "shows the dye rates for the never-dried and fixed, never-dried samples are almost the same. The actual increase in dyeing speed over the Kontro11 cotton fibers is about $

Similar processes using a red reactive dye (Procion Red MX5B) indicate that high staining strengths occur with never dried cotton fibers with colors of this class. A dyeing t reactive colors is also used to fix the never dried cotton fibers in their botanical growth state.

The principle, the preferred embodiments and the Methods of the invention have been described in the foregoing. It should be noted, however, that the here too protective invention can also be carried out in modified forms without departing from the aim of the invention will.

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Claims (10)

PATENT CLAIMS 1. A method for producing a cotton-fiber connection with increased absorbency, characterized in that the cotton fibers are fixed in their never-dried, botanical growth state and the fixed cotton fibers in a fiber connection can be brought. 2. The method according to claim 1, characterized in that the never dried cotton fibers by a treatment with be fixed at least one locking collar. 3. The method according to claim 2, characterized in that the Sperragens is selected from the group of formaldehydes, acrylamides and colors. 4. The method according to claim 1, characterized in that To form the fiber connection, a yarn is created from the fixed cotton fibers and a fabric is produced from the yarn will. 409885/1492 - P ^ - 5. The method according to claim 1, characterized in that the Paser connection then with at least one textile influencing agent is treated, which is from the group of crease-proofing agents, dirt-dissolving agents, colors, incombustible substances, mercerising agents, impregnating agents and fabric softener is selected. 6. cotton fiber compound, produced according to claim 1, characterized in that it is used for increased absorbency Made from cotton fibers that have never been used in theirs dried, botanical wax and turned into a Are connected. 7 · Cotton-fiber connection according to claim 6, characterized in that that the fixed fibers have at least one barrier layer deposited in them. 8. Cotton-fiber connection according to claim 7 *, characterized in that that the Sperragens is selected from the group of formaldehyde, acrylamides and colors. 9. cotton fiber connection according to claim 6, characterized in that that the fiber connection is a fabric which is woven from yarns of the fixed cotton fibers. - 24 A09885 / U92 10. Baumwo11 fiber connection according to claim 6, characterized in that that the compound is then treated with at least one agent influencing textiles that consists of -the group of crease-proofing agents, dirt-dissolving agents, paints, non-flammable materials, foodstuffs, Waterproofing agents and fabric softeners is selected. 409885 / U92