DE1946075C3 - Process for modifying cellulosic fiber materials - Google Patents

Description

Until now, cellulosic fiber materials have been modified by using as modifying agents N-methylolated derivatives and / or alkylated N-methylol derivatives of amino compounds with active nitrogen used, such as urea, melamine, ethylene-urea or glyoxalmonourein to improve wrinkle resistance and smoothness when drying. Derivatives of this type are to be referred to as “N-methylol compounds” for short in the following.

Typical examples of such modifiers are urea-formaldehyde resins, melamine-formaldehyde resins, Dimethylol-ethylene-urea resins and meioylol-glyoxal-monourein resins, for example 1 ^ -DimethyloM.S-dihydroxy-I-imidazolidinone.

Tetraoxane and pentaoxane have the following structures

CH ₂ OCH ₂
ü O
CH ₂ OCH ₂
Tetraoxane

above-mentioned N-methylol compounds occur easily can.

The present invention thus relates to a process for modifying cellulose fiber materials by applying a solution or dispersion of a cyclic ether and subsequent heat treatment at at least 100 ⁰ C in the presence of an acid catalyst, which is characterized gekennzeichne in that as cyclic ether tetraoxane

Pentaoxane or mixtures thereof are used.

The present invention also relates to new compositions for treating cellulosic fibrous materials, which contain tetraoxane and / or pentaoxane and an acidic catalyst.

Tetraoxane and / or pentaoxane used in the present invention are cyclic Compounds which themselves show no reactivity towards cellulosic fiber materials. It is believed However, that rings these compounds through

the action of acidic substances at elevated temperature during the heat treatment given above be opened and that the resulting product reacts with the cellulose fiber material. A well known compound, the cyclic ArI

and is similar to tetraoxane or pentaoxane, isi trioxane, which has the following structure

CH ₂ OCH ₂ O
O CH ₂

CH ₂ OCH ₂ O
Pentaoxane

These materials have not yet been used to modify fibers. It became a Process found, according to which cellulosic fiber material is modified and thereby higher Wrinkle resistance and slip on drying (evaluation of appearance) is imparted than when used of the above-mentioned N-methylol compounds. It has also been found that the persistence of the new modification is very excellent compared to washing and that no damage by chlorine occurs, a deficiency caused by the use of the O-CH,

O -CH ₁

This compound is used as an additive to N-Methy lol compounds in the treatment of cellulose Fiber materials used to reduce the wet and dry crease angles and other properties of the be acted to increase fiber material (see. British patent 1081039).

Our own tests showed, however, when a cellulose fiber material with trioxane in the absence of a Impregnated N-methylol compound and heated in the presence of an acidic substance that the to would decrease, if any, in the wrinkle strength and smoothness of the treated material as it dries Fiber material is very low and of a prak

946

table point of view is completely inadequate, regardless of the amount of trioxane used

Pie reasons for this are not entirely clear. As possible Explanation can be assumed that the lack of the effect of trioxane in modifying cellulose fiber materials hence the fact that 1. trioxane shows a much lower activity, especially in relation to on the rate of ring opening and conversion of trioxane when in the presence of a acidic substance is heated, and that 2. trioxane has a much higher volatility, whereby it evaporates during the heat treatment by sublimation and evaporates from the fiber material.

The acidic compounds or acid catalysts used in the process of the invention are any substances that show acidity during the heat treatment given above, and finally, for example, inorganic acids such as hydrochloric acid, nitric acid. Sulfuric acid, phosphoric acid and others; organic acids such as formic acid, acetic acid. Oxalic acid, Tartaric acid, citric acid, benzenesulfonic acid, and others; Ammonium salt and amine salts of the above specified inorganic acids and organic acids; Metal salts of the acids specified above, preferably magnesium and zinc salts, such as magnesite chloride, zinc chloride, zinc nitrate, magnesium fluorate, Zinc fluorate and others. All of the acidic catalysts that have been used to date Cellulosic materials with N-methylol compounds, as previously indicated, can be modified in the present invention can be used. It can be single catalysts or mixtures of two or more can be used. The amount of catalyst can vary within a wide range and depends on the kind of acidic substance (or catalyst) and is generally in the range from 0.01 to 1000, preferably 0.1 to 1000, most preferably 0.1 to 100 parts by weight per 100 parts by weight of the total modifier that is used, for example tetraoxane and or pentaoxane.

The cellulosic fibrous material according to the present Invention used is any material in which at least a part, for example 10 to 100 percent by weight of the total fibers contain cellulosic fibers. Examples of cellulose fibers include natural fibers such as cotton, linen, and ramie, and staple fibers or filaments from such regenerated fibers as viscose rayon and copper rayon.

These fiber materials can only contain cellulose fibers or mixed with cellulose fibers one or several other types of staple fibers or filaments, e.g. synthetic Fibers such as polyamide, polyester, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, Polyolefin and polyether types. Protein fibers, such as wool and silk, and / or inorganic fibers such as glass fibers, graphite fibers and asbestos fibers. The fiber material can be in the form of staple fibers or filaments in woven or non-woven (connected) or knitted form or in any form of yarn. textiles are the preferred material.

The modifying agent according to the invention contains either tetraoxane or pentaoxane individually or both together. The tetraoxane used in the present invention can be prepared by suitable methods, various of which are known. For example, it can be prepared by decomposing polyoxymethylene in which the end group is stabilized (for example a polyoxymethylene in which the terminal hydroxyl group is acetylated, alkylated or bound to urea), the decomposition being produced at a temperature of above at least 100 ^° C. and under reduced pressure in the presence of a catalyst selected from alkali metal salts of persulphuric acid, acidic alkali metal salts of sulfuric acid, zinc chloride or picric acid (see Japanese Patent 500,317).

The pentaoxane made according to the present invention used can be prepared by suitable methods, various of which are known will. For example, it can be obtained from the residue obtained during the polymerization reaction of trioxane arises, or from the thermal decomposition product (in the presence of an acidic compound or catalyst) of the trioxane polymer (see K. H. B u r g st al, "Die Makromolekulare Chemie", 111 ·, 181 to 193 [1968]).

The modifying agent according to the invention can be one or more of the N-methylol compounds described above and contain compounds previously used as modifiers for cellulosic fiber materials were used, such as amino compounds and / or trioxane, together with the tetraoxane and / or pentaoxane.

Typical examples of the above-mentioned N-MethyJol compounds include the urea-formaldehyde resins such as dimethylolurea. Precondensates and the like, melamine-formaldehyde resin, dimethylolethyleneurea and dimethylolglyoxalmonourein and alkylated derivatives thereof. The ratio of N-methylol · compound to that total tetraoxane and / or pentaoxane is in the range from 50: 1 to 1:50 parts by weight. Preferably the amount by weight of tetraoxane and / or pentaoxane is greater than that of the N-methylol compound. For example, the total amount of tetraoxane and / or pentaoxane is 50 to 100%, based on the weight of the N-methylol compound, the tetraoxane and pentaoxane.

The above-mentioned amino compounds in the present invention are compounds, the at least one HN group, such as the amino group c. Imino group, amido group and, or contain the imido group.

Typical examples of a suitable amino compound include aminotriazines. like melamine; Guanidine compounds such as dicyandiamide and guanidine; Urea compounds such as urea, thiourea and N.N'-dialkylurea; cyclic urea compounds, such as ethyl urea, propylene urea, 4,5-dihydroxyethyl urea, 5-hydroxypropylene urea, Acetylenediurein, urone, 5-alkyltriazone and 5-hydroxyalkyltriazone; Carbamate compounds, like methyl carbamate. Ethyl carbamate, isopropyl carbamate, Butyicarbamate, hydroxyethyl carbamate, methoxyethyl carbamate, 2-hydroxypropyl carbamate and ethylene glycol dicarbamate and their alkylated derivatives, d. H. their N- or Ν, Ν'-alkyl-substituted derivatives, Hydantoin compounds such as hydantoin and 5,5-dimethylhydantoin; Carbamoylethyl compounds, like tris- (2-carbamoylethyl) -amine and bis- (2-carb-

946

»MgyläthylValkylamin; Amide compounds of unsaturated organic acids, such as acrylic blue., 4 and Methacrylamide.

Reaction products of the amine compounds mentioned above of N-methyl compounds and thus the forroaldehyde conversion products of each of the Amino compounds given above can be used as N-methylol compounds in the manner described above can be used. Furthermore, alkylated derivatives, d. H. the reaction products of an alkanol ίο with the N-methylol compounds, described in the above Kind be used.

The ratio of the amino compound to the total amount of tetraoxane and / or pentaoxane is generally from 1 to 100 parts by weight per 100 parts by weight of the total amount of tetraoxane and / or pentaoxane.

One way of operating in accordance with the present invention is described below. A cellulosic fiber material becomes with the modifier and the acidic compound at the same time or impregnated one after the other. It is required that the modifying agent and di ', acidic substance are simultaneously present in the fiber material at the time when this is heat-treated.

During impregnation of the fiber material with the modifying agent and in the heat treatment in the presence of an acidic compound, the heat treatment temperature is preferably about or at least about 100 ⁰ C. because, when the heat treatment is carried out at a temperature of below about 10O ⁰ C, improve the wrinkle resistance and the smoothness in drying the fiber material is not fully realized and it would take a long time to achieve these effects, and hence the reproduction of such effects would be poor and insufficient for practical use.

To avoid degrading influences on the cellulose fiber material itself, the temperature is that is used for the heat treatment is generally well below 230 ° C, and it is preferably in the range of about 130 to about 180 ° C.

According to the present invention, the fiber material with the modifying agent and the acidic Connection impregnated at the same time or one after the other. A method of impregnation that is practical and is suitable is the following.

Either a ·? or both of the modifying agents and the acidic compound (catalyst) is or are dissolved in a suitable solvent or dispersed to form a treatment bath and the material to be treated is with the obtained by a suitable method, such as padding, dipping, covering or Spraying, impregnated.

The following solvents are suitable for use in preparing the treatment bath: for example water, aliphatic alcohols such as methanol, ethanol and isopropyl alcohol; aromatic Hydrocarbons such as benzene, toluene and xylene; aliphatic and aromatic nitro hydrocarbons, such as nitromethane, nitroethane, nitropropane and nitrobenzene; aliphatic halogenated hydrocarbons, Like trichlorethylene, tetrachlorethylene, Dichloroethane, tetrachloroethane and chloroform; aliphatic and alicyclic ethers, such as diethyl ether and Dioxane: ketone, such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Acetic acid esters, such as methyl acetaf and ethyl acetate, and mixtures of two or more of these solvents,

The concentration of the total amount of tetraoxane and Pentaoxsn in the solvent ider in the liquid phase is not in the narrow area «cntiscn and can be from about 0.1 to about 90%, preferably from about 0.5 to about 30%, based on total weight the solution or dispersion, vary. The total amount of tetraoxane and / or pentaoxane, which is applied to the fiber material is not narrowly critical, and it can be over wide Ranges vary, for example from about 0.1 to about 50%, preferably from about 0.5 to about 15%, based on the total weight of cellulose in this material.

Furthermore, a method for modifying cellulosic fiber material with formaldehyde alone has been used up to now in which 1. formalin, 2. gaseous formaldehyde or 3. paraformaldehyde or trioxane is used as the formaldehyde-forming compound. However, in such earlier modification treatments, the pungent odor of the formaldehyde emanates during the treatment step and from the finished fiber material after the treatment step. The feasibility of these known treatments is very poor from an industrial point of view; since formaldehyde is a gaseous substance, it is difficult to obtain the same levels of crease resistance and smoothness upon drying, and the strength of the treated fibrous material is low. Therefore, these prior art methods have essentially not been commercially recognized.

In the method according to the invention for modifying cellulose fiber materials, in which Tetraoxane and / or pentaoxane is used as modifying agents, flows from the fiber material no formaldehyde odor during or after the treatment, and exist in the workmanship no difficulties.

Furthermore, according to our own investigations, cellulose fiber materials have, according to the invention Procedures were modified to have a formaldehyde content more than twice as high as that Materials treated with the known formaldehyde treatment methods given above became. It is therefore assumed that the crosslinks between the modified cellulose materials are longer than in the known process, in the case of formaldehyde is used.

It is believed that the tetraotane and pentaoxane rings open in the process according to the invention and react immediately with the cellulose molecules without decomposing to formaldehyde, and form cross-links between the cellulose molecules. It was found that the difference in the length of the cross connections to the strength of the treated cellulose fiber material Can have influence.

It is believed that the cross-connections which are formed in the cellulose fiber material according to de. ' present Invention formed v / ground, are longer and that the cellulose molecules of which the cellulose fibers consist, have a greater degree of freedom of movement and that thereby the treated fiber material greets e strength is bestowed as if one

946 075

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m
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being
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works with formaldehyde or formalin, gaseous formaldehyde or paraformaldehyde or trioxane.

If in the process according to the invention tetraoxane and / or pentaoxane and an N-methylol compound are used at the same time, it is believed that the rings of tetraoxane and / or pentaoxane are opened and the product of the ring opening the cellulose fiber materials modified while it was with the N-methylol compound reacted. As a result, there are improvements in crease resistance and smoothness when drying the fiber material considerably larger than in the case when, as with the known Method using N-methylol compound alone. Furthermore, damage from chlorine destruction is avoided, as is the amount and direction of the Methylolation of the N-methylol compound can be substantially reduced to prevent the formation of Avoid formaldehyde odor during and after the modification treatment.

In the method according to the invention in which the the above amino compounds are used together with tetraoxane and / or pentaoxane, the rings of tetraoxane and / or pentaoxane open and the product of ring opening is modified the fiber materials while it is with the amino compound that opposes the acid catalyst shows a buffer effect. Accordingly, the present invention is particularly useful when such a buffering action is needed to prevent the color or white color of the fiber material from changing changes. With the simultaneous use of the amino compound, the crease resistance and smoothness are increased improved to a technically acceptable level in drying the fiber material.

In the process according to the invention, in which trioxane together with tetraoxane and / or pentaoxane is used, the ring opening of the trioxane is accelerated by the tetraoxane or pentaoxane, the rings of which are likely to be opened more easily than that of trioxane, and as a result will the crease resistance and smoothness when drying the cellulose fiber material improves on one level, which is sufficient from a practical point of view compared to the modification of the fiber material, using trioxane alone. However, if you have the same modifying treatment as the Processes according to the invention and only trioxane as a modifier instead of tetraoxane and / or pentaoxane are used, the remarkable effects, crease resistance and smoothness when Drying, not obtained according to the invention.

Additives, as they are generally used in the modification used by cellulose fiber materials become, like plasticizers, means to reduce starch loss, water repellants, water wheel oil repellants, body repellants, antistatic Agents, humectants and agents for adjusting the pH can be used simultaneously with the modifying agents of the present invention are used, for example in the treatment baths, containing the modifying agents.

The remaining acid catalyst and the unreacted compounds in the fiber material after Remaining after the heat treatment can be removed as in the known method, for example by immersion in an aqueous solution, the an anionic surfactant, a nonionic surfactant or an alkaline one Contains substance, and by washing. But on the other hand, if the present invention is at such processes, such as post-curing

S in the manufacture of permanently pressed owands, is used, soaking and washing need not be carried out.

In the present invention, mechanical forming such as embossing, calendering or folding is used

ίο the cellulose fiber fabric before the termination of the If heat treatment is applied, the second effect obtained is that this is mechanical shaping the completion of the heat treatment has durability. Furthermore, the inventive Process and modifier used in permanent pressing methods such as the post cure method where the heat treatment is carried out after the mechanical molding together is carried out with the cutting and sewing. For example, cellulose fabrics with the inventive Modifying agents are impregnated, the impregnated fabric can then be dried, the dried fabric can then be cut and sewn into clothing, the garment can then be pressed and cured to form a permanently molded garment.

In the following examples are; unless otherwise stated, parts and percentages are by weight and the temperatures are given in degrees Celsius.

Examples 1 to 10

Aqueous solutions containing the types and amounts of modifying agents shown in Table I were prepared and used as treatment baths in the following manner. In each case, 1.2% Zn (NO ₃ ) ₂ -6H ₂ O catalyst, based on the weight of the treatment bath, was used

In a usual manner desized, gebeuchteter, bleached and mercerized garment fabric of cotton was immersed in each treating bath, squeezed to 70% B 4 mins * H 8O dried ⁰ C with hot air, further heat treated for 4 minutes at 150 ⁰ C in a tenter, then at SO ⁰ C in water containing 0.2% soda ash and 0.2% neutral detergent, post-treated for 1 minute and then rinsed well with water and dried

For each of the resulting pieces of fabric, the crease resistance (cf. the column "at the beginning" in the table I) determined by the Monsanto method, and the

The smoothness when drying after SmaBgem washing at home was determined according to the method of AATCC 88 A 1964T. The crease resistance was also determined after the five above-mentioned washes at home according to the Monsanton method. The finished clothing was also immersed in an aqueous solution at 100 ° C for 40 minutes which contained 0.05% soap powder, then ^{rinsed with water at 6O 0} C, dried nad chlorinated and then scorched according to the method of AAT-CC 92 - 1967 and

the resistance to chlorine when fibet * ever one was observed, dua ·.;. Degree of discoloration determined. The results of these experiments are given in Table I.

409 616/317

TeKi
oxane 9 Treatment bath I.3-dimethylol
4,5-dihydroxy
2-imidazolidinone Propylene
urea 1 946 075 To
5 home
washes [ P. 10 of the finished fabric Resilience Remarks 4th Modifying agents 297 compared to chlorine Content in percent by weight of the table 292 smoothness no discoloration Examples according to the invention 3 Trioxane properties 296 at the the same I. Anti-crease 289 dry
(Apply
tion) the same at stability 285 5 the same game Pen ta -
oxane in degrees 187 5 the same No. 3 2 1 to
Beginning 288 5 the same Verlekltsbeispiel I. 4th 2 1 301 199 5 the same inventive example 2 i 4th 299 4th Discoloration under Comparative examples 3 I. 4th 303 262 I. Brown color 4th 4th 2 3 0.4 295 292 4th the same S. 291 2 no discoloration inventive example 6th 193 7th 292 4th 8th 218 5 9 276 IO 297

Examples 11-18

Aqueous solutions containing the types and amounts of modifying agents and acidic compounds (catalyst) shown in Table II were used as treatment baths. Cotton twill fabric which had been sized, moistened, bleached and mercerized in the usual way was dipped into the treatment bath, as described in Examples 1 to 10, squeezed off so that there was an uptake of 65%, ^{dried with hot air at 80 °} C. for 4 minutes and then cut and sewn to pant legs. Each pant leg was steamed for 3 seconds, then ^{pressed at an upper temperature of 150 °} C. and a pressure of 1 kg / cm ^{2 for} 10 seconds in order to obtain folds. Each pressed pant leg was placed in an oven so that the folds were vertical, and then heat-treated ^{at 160 ° C. for 5 minutes.} The dry smoothness and crease resistance of each pant leg was determined by using the AATCC 88A or 88C method used. Also, the crease resistance and the resistance to chlorine were examined by the same methods as described in Examples 1 to 10. The smoothness of the leg. Drying and crease resistance ratings were 5. In the chlorine resistance test, none of the treated fabrics was discolored. The values of the crease resistance are given in tables.

Table II

υ ■ Modification Tetra
oxane Salary in - Percentage by weight of the treatment bath Acidic substance , AI (SO ₄ I ₃ -18H ₂ O Anti-wrinkle To
5 home washes game Penta
oxane Mg (BFJ ₂ • 6H ₂ O ability in degrees 288 No. 3 MgCl; H ₂ O ZnCl ₂ At the start 284 11th 3 4th 292 291 12th 3 2 1 0.4 289 290 13th 3 3 296 289 14th 3 294 285 15th 3 4th 293 288 16 3 2 1 0.4 288 289 17th 293 18th • 295

Examples 19 to 21

Aqueous solutions containing 4 percent by weight tetfaoxane and 1.2 percent by weight magnesium fluorate hexahydrate were used as treatment baths. Clothing fabric from BaurttWöDe; Waifäe in 65-each treatment bath, as described in Examples 1 to 10, immersed and hi the same way as described in Examples I to 10, squeezed and dried, then divided into three parts, and the three types of heat treatment, as they are listed in Table III below, applied to them in a tenter.
Examples I to 10 are determined and given below Table III.

Table III example Heat treatment conditions

temperature ("C)

time (Min.)

Knitte egg resistance (in degrees)

at the start

after 5 home washes smoothness while drying

Remarks

90
140
180

5
5
1.5

183
289
311

1
4th
5

Comparative example
according to the invention
Examples

Examples 22 to

Aqueous solutions containing the types and amounts of modifying agents shown in Table IV were used as treatment baths. In each case the treatment bath contained 4% MgCl ₂ -6H ₂ O catalyst based on the weight of the bath. Conventionally desized, moistened and bleached cotton garments were treated with the treatment liquid in the same manner as described in Examples 1 to 10 to 10, and the tear strength was determined with an Elmendorf tear strength tester. The measured values are given in Table IV. Resistance to chlorine

is was also carried out in the manner described in Examples 1 to 10 is determined, and it was found that the treated cloth was at all not discolored. In Examples 24 and 25 where formaldehyde was used as a modifier was, the implementation of the reaction was different Stages due to the pungent odor of the formaldehyde during the preparation of the treatment bath and dipping, squeezing, drying and heat treating the fabric are very difficult.

In Examples 22 and 23, no such odor was observed.

Table IV

example No.

Tetraoxane

Content in percent by weight of the treatment bath

Modifying agents

Pcntaoxane

24 4

25 *) 4

*) Repeat example 24.

formaldehyde

Acidic substance

MgCl ₂ • 6H ₂ O

4th
4th

4th
4th

Own sound of the finished fabric

(Chemical resistance in degrees

to Beginning

example

To 5 home washes

288
288

264
276

smoothness at the dry (Evaluation)

4th
4th

Tear Remarks strength· mg 634 invention 629 appropriate Examples 603 Comparative 582 examples

An aqueous solution that has 10 weight percent te- 45 ability and the smoothness on drying (appearance) traoxan and 3% Zinkniirathexahvdrat was contained in the treated tissue were in the same used as a treatment bath. In the usual way, as described in Examples 1 to 10, Desized, moistened and dyed melange- measured, and it was found that the initial fabric, which was suitable for the tropics and 35% knee resistance, was 305 ° and the viscose rayon made from tmd contained 65% polyester was given a 5 »visual rating of 5.

the treatment bath is immersed to 75%.

squeezes and dried heat-treated and the valuation of the untreated fabric is 273 '

the same type as in Examples 1 to 10 and 4. Since it was a dyed fabric, the

wrote, post-treated The crease resistance resistance to chlorine not tested

example

An aqueous solution containing 10% by weight of tetraoxane and 3% by weight of zinc nitrate hexahydrate was used as the treatment bath. Conventionally sized, moistened and bleached copper rayon taffeta cloth was immersed in the bath, squeezed to 130%, dried, heat treated in the same manner as in the examples 1 to 10 described, post-treated The crease resistance and 6 $ appearance rating of the treated fabric were measured in the same manner as described in Examples 1 to 10, and bath 264 "and 4. When tested for chlorine resistance on dii in the same manner as described in Example 1, the treated fabric was not decolored at all

The crease resistance and the rating of the appearance of the untreated fabric were measured, and found to be 123 ° and 1, respectively. The resistance to chorus of the untreated tissue was the same as that of the treated tissue. Furthermore, it was noted that the treated fabric nicfc pulled in more than J ■ '.landelt tissue during the HciV.wäsche comprising _H,.'. Usynnnefi hang with the Areseh testing were felt.

Claims (4)

Patent claims: 1, Method of modifying cellulosic fibrous materials by applying a solution or dispersion of a cyclic ether and subsequent heat treatment at at least 100 ° C in the presence of an acidic catalyst, thereby it indicates that the cyclic ether is tetraoxane, pentaoxane or their Mixtures used, 2. The method according to claim I, characterized in that that trioxane is also used. 3, method according to claim I, characterized in, that a customary modifier is also used, selected from Class of organic compounds that contain at least one HN <group, and the N-methylol derivatives thereof. 4. Means for performing the method according to claim 1, characterized in that it from an aqueous solution or dispersion of tetraoxane, pentaoxane or mixtures thereof and an acidic catalyst