DE1469507A1 - Process for the aldehyde treatment (formalization) of cellulose, cellulose esters and starch - Google Patents

Description

H69507

(3513)

Point Pepperell, Inc. * j J_yJ pYT ^ W ay lj t P oint Georj _t ^ i a / V. St.A. "" ——— I

Hamburg, 19 «Hai 1965

Process for the aldehyde treatment (formalization) of cellulose, cellulose esters . and strength

For the finishing of textiles and especially for the knitting-proof armor and for reducing the quollies and increasing the tensile strength and shrinkage, it is known to use aldehyde and especially formaldehyde in cellulose toxins in polyoxymethylene; in addition, in the presence of acidic catalysts, there is a crosslinking via methylene bridges and acotal ring formation with two neighboring hydroxyl groups. In general, these reactions only take place on the surface of the fiber without any profound fiber modifications In the formalization processes for the finishing of cellulose textiles, not aldehydes alone, but urea / aldehyde precoikdensates ₍ e.g. as 15 to 30% aqueous solutions, with the addition of organic acids or acidic salts by padding (padding) on the fabric to be finished e

BATH

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brought. According to zincm Ate uetaciitm doi · ü liquor &: "nücl> £ t at lower 'i'ar.i.-jeratuK * vargc" · <: dries and then aftercvrhitat "Daboi k jndeasiere ι eich" lie precondensates zv. vßraietzt-sr ^ w.ssar ·· and oll; aiiiui-. soluble resins. Ntsbe; · '. dar r-Iarzbildimg achieves auoli oino certain io.rasali'iiu.cuug the ^ at: c 111 _r so deiß also a reduction in dec tiiisllvarriiögsns iient »iious2d: lngs one tries xn ao.ieriaiiiitua"f; o: sälunt3ii "rovmaliszessenie. rch Vcvwenduiatj of .formaldehyde-releasing products instead of Γorraaldsiiydlö rods even iron-free equipment by beautiful ^ ren, Ba is also known to convert starch in the application with urine to L'f-formaldehyde precondensates or Pcr ^ auldchydspendern, which in the later dry finished fabric a more or less Ti-dependent fijcierurs of the. Effect starch finishing.

In all of these processes, however, it is difficult to determine the amount of formaldehyde that has accumulated in advance to be treated ο partially decompose, Öe: in a * normal formalization - only relatively small amounts of formaldehyde are actually removed from the cell and ose absorbed, while the rest is lost.

BATH ORIGINAL

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formaldehyde salivary that has become in the form of a pre-condensate of formaldehyde with alkylcorbamate _t z «B. FonBaldehydmethylcarbamat _t is sine bond instead of the nitrogen dos precondensate of ior Zolluloao, as evidenced by the strong nitrogen content of the thus treated cellulose compared to the relatively lower nitrogen content of the unbehande.lten cellulose. Such treatments result in unusable and partly narcotic equipment "

A new ancestor is now being used to remedy these disadvantages proposed, which is characterized in that the cellulose, Zelluloaeester oc.tr starch in the presence a catalyst either with an aqueous mixture of Alduhyd and a Carb.anic.tor general formula

WCOOR ₀

treated and then heated at temperatures up to 205 ° C or treated with an aqueous Gcatiech of preferably further aldehyde-containing, for this purpose known aldehyde-carbamate condensation products with a carbamate dor formula H ₂ NCOOR ₂ and then treated at temperatures of no more than 150 ° C, preferably from 80 to 150 ° C, wherein

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R. and R- are a hydrogen atom, an alkyl radical or a carbocyclic aryl radical and R _{3 is} an alkylreat or a carbocyclic aryl radical ·

The knowledge of the present invention is based on the fact that the new process is carried out under such conditions that the aldehyde is bound to the polymer in the desired sufficient and controllable amount, but that no nitrogen addition he follows. As has been recognized, this is suitable for that either a mixture of aldehyde and carbamate used, whereby the temperature in the later treatment can be increased considerably, and aswar to cu 805 ° C. In this case the carbamate apparently only serves as a carrier for the formaldehyde, so that "I have more aldehyde" it can connect to the cellulose ester. Or you use according to the other process variant, an aldehyde / carbamate condensation product, which is preferably still further May contain aldehyde, in which case a precisely selected temperature range, namely of not more than 150 ° C, and preferably 80 to 150 ° C, must be churned so that the binding of nitrogen to the cellulose, which is recognized as harmful, is avoided. Although the use of Aldehyde / carbamate condensation products for treatment of textiles - but at higher temperatures - is known, has not yet been recognized that by the

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Heating the material in the specified temperature range avoids a nitrogen bond and the desired Formaldehyde deposition is achieved.

Lower alkyl carbamates are preferred, in particular Methyl carbamate used «It is also useful if the carbamate in 0.1 to 5 # solution and the aldehyde, especially formaldehyde, used in amounts of 3 to 60 mol per mol of carbamate »

The products treated by the method according to the invention have excellent properties with regard to the Ironing resistance, color fastness, dirt repellency, Resistance to rotting and the like * Furthermore, the content of the deposited aldehyde can be determined by simple Set the existing aldehyde concentration uniformly and adjustable, with no Binding via the sticks »to ff done«

With the method according to the invention, cellulose, such as cotton, of-cellulose, regenerated cellulose or Rayon, copper amnon rayon or viscose rayon or paper, or cellulose sector, such as cellulose acetate, cellulose acetate butyrate and cellulose acetate propionate.

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The cellulose material to be treated can also with synthetic fibers, e.g. polyester fibers such as polyethylene terephthalate, Acrylic acid fibers, e.g. made of polyacrylonitrile or acrylonitrile vinyl chloride, polyhexeime ethylene adipamide fibers, polypropylene, propylene / ethylene mixed polymer and vinyl chloride / vinyl acetate fibers mixed be.

The main aldehydes are formaldehyde, but also Glyoxal, Methylglyoxal, Glutaraldohyd, Acetaldehyde, Propionaldehyde, butyraldehyde and hydroxyadipaldehyde in Consideration; here glyoxal is used to increase strength preferred «Instead of formaldehyde, other formaldehyde suppliers can also be used such as paraformaldehyde, trioxane and hexamethylenetetramine can be used. Serve, however, extend the duration of treatment due to the splitting off of formaldehyde

If alkyl carbamates of the general formula HgNCOOR are used as the carbamate, the alkyl radical can be methyl, ethyl, propyl, xsopropyl, butyl, amyl, hexyl, octyl, decyl, dodecyl, cyclohexyl or octadecyl Be thatch. Mixtures of the most varied of carbamates can of course also be used, such as, for example, an outectic mixture of 52 % ethyl acetate and 40 % methyl carbamate. ■ ". · ■

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Phenyl "the various ortho ··, meta- and parex-tolyl-, dar p-ButyJ.-phonyl-, the oC or ß-NaphthyJ- o <ler the B ^ i-Xylylcarbaoiat used will.

All N-hydrocarhyl-substituted carbamates of the general formula R-NHCOOR ₂₁ in which R _{1 and R 2 are} alkyl or aryl radicals can be N-phenyl-isopropyl-t N-phenyl-phenyl-, Np-tolyl-ethyl- ₁ N -Phenyl-roethyl-, N-phenyl-ethyl-, N-methyl-phenyl-, N-ethyl-phenyl-, N-methyl-methy1-, N-methyl-ethyl-, N-methyl-decyl-, N- Xthyl-methyl- _f N-ethyl-ethyl-, N-dodecyl-methyl- ₁ M-butyl-dycloheacyl-, Ν, Ν-diethyl-ethyl-, Ν, Ν-dimethyl-ethyl-, Ν, Ν-DiUtlTylmethyl- or the Ν, Ν-diphenyl-methyl-carbataate can be used,

In general, higher temperatures are required to activate aryl carbamates and N-hydrocarbyl carbamates, while, in contrast, the lower alk / carbamates such as methyl carbamate and ethyl carbanate require lower temperatures, so the latter are generally preferred.

Preferably been the aldehyde / alkyl carbamate Kondense.tionsprodukte used its mixture with aldehydes _t since the reaction uniformly proceeds urd shorter "ehandlungs- ·

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requires times _c The use of such Qetniscb.es also reduces the cost of the prior formation of the aldehyde / Alisylearbwuat-Kondenstttiicnsproduktesc The temperature control is essential, as at Ver-wend'ing of aldehyde / Alkylcar-baniat-Kondesisationsprodukten and Be. a treatment above 170 ° C does not form a coulensation product, which occurs with the formation of ammonia, carbon dioxide and alcohol in four sets of ₄ but in a fixed side reaction ext 1 «3;. Is the case in the case in question in the case at hand.

If one uses andci "jr; sei.ta a water mixture of an aldehyde and a" carbamate ", the temperature can be very much higher; sü.j5.i |:; or adjusted, vcrderi vxid one can work up to 205 ° C. This means that the conversion to the III: .dai »s des ·. M0thy.l0lc.2rtemat.es is relatively slow and <J.:ia dee Fcrüialdeliydes with the cellulose or the accumulation fast In these Tetaperaturbi-.i'c.chen the Carbcmat i'.börrascheiiderv / t 1;.: namely only acts as a tracer and supports the deposition of ri: r Forraaldehjrtiei; _{ti in} the J? cellulose, ear itself ijrgend · ■ as with the 7; e.7.1u3.ose su connectoTic D3.3 temperature indication ■■: ** refer to .-. uf the actual temperature to which the treated product has been heated to velcro and the pyromotrically dui'ch Bo itjnircung d «r upper surface \\ r ntemperatcir or

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determined according to the dom infrared method This temperature corresponds to a slightly higher oven temperature or temperature of the radiation source »

In order to better attach the aldehyde to the cellulose, should ·· -.? at least 0.1 and preferably at least 0.3 Gevr "? 6 methyl carbacate, 2" B. in aqueous solution or dispersion _r or the corresponding proportions in M> 1% or G.ew ₆ ? i for other carbamates », are used ο If less Carba: ..- ν is used, then the angular and garte Fcrmaldahydtiengu can be controlled worse, while up to a level of at least 0.5% οϊκεtall ausessai c ^ iete r-produzierbart ForiKaldehydunlagerunf; achieves wire. " Jöher-e Misngor.- which over the range from 1 to 5 % hir, .a ·. sgc; h. \: iXj ; * eb & n koiiier. Advantage ν

The aldehyde is usually used in the aqueous Sy item in amounts of 1 to 8 Gow, #> and at. A greater formalization can even be 10 to 1 % used . Preferably, the aldehyde is used in edges of at least 3 mol per mol of carbamate and up to 60 or even 100 mol per mol of carbamate. Lower aldehyde concentrations are preferred Process highlights over the known processes, whereby the annoying formaldehyde odor is limited .

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Example levea sa l.nmi. when treating cotton wool,

Ot - Cellulose, iitaryke and paper i / a general aqueous solutions with buckets content of 1.25 to 4 wt. "I Use formal deliyi, vsia i>, 25 M ¹ SI ₁ 25% Forta" Ld.ihyd an dem Material ' to be deposited: cash *. -3.Treatment of Itaron and cellulose esters can t / Έ ssr.rgs F orinaldehydlö sangen with a content of 2.3 to β i'S varwer.det wa'lai, \? Ir, 0.50 to 2 _t 5 ^ i formaldehyde . r.3 is: .l ajf-r?.! »

If ei ti C ar bnsnr. t / AI d oh> -.-. i-condensa t: L o: isp ro duct is * sets, jua.i the solution is preferred fw-a: i: β so much aldahyd au that at least 3 hol aldehyde ( including the aldehyde contained in the condensation proiui? t per mole of Carberaat of the Kondenflatioasproduktes present ί.ΐηΐ.,

The mixture of Aldshyd "ad Al?" Ylcarbcjaafc can be used in d-2r. ysrschiodensten mixture arerhtiltni3s «» k and as. Relatively concentrated i / as aqueous solution must be sent, in order then to be able to use water before use:? rt & n geirin. ^ right content diluted to digest. For reasons of stability, the mixture is preferably sent neutrally, but it can also be alkaline or acidic.

The cotton or the material to be treated is generally passed through a bath * which is preferably one contains acidic or latently acidic catalyst,

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such as arieisic acid, hydrochloric acid, ammonium chloride, magnesium chloride, calcium chloride »zirconium nitrate, zinc chloride, zinc fluoroborate or mixtures of these substances» Since only a small amount of catalyst is required, this can also be made available by remaining acidic salts on the goods to be treated _t like z « B. Office donium chloride.

I> he formalization with an alkyl caibanmtt rager iat also in alkali a oh er. Baths possible, where Nai.T-iucx or potassium carbonate, sodium or potassium hydrogen carbonate or sodium baw _a Kaiiuaihydroxy are used , 1 to 2 Ss ..

In the bath, the Alkyloarbamat is preferably in amounts of at least etwe. 0 _t 5% existing The Molverhältriis of Foraaldehyd to alkyl carbamate is preferably from ^12.3: 1 * The baths may also contain conventional additives such as wetting agents, Wexchaachungsmittel, Scluuiermittel ^ contain optinchc brighteners and other Schützetoffe.

A major advantage of the inventive method :; also consists in the fact that the. usual Tcoitil finishing process strength loss occurring in

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in the present case is much lower. Up to now one had to reckon with a reduction in strength of 40 to about 50% , which could be compensated for with additional treatments or with more solid material. The Festigkeitβverlust is the erfiiidungsgemäßen process, usually only 15 to 25 5 _'t which is substantially probably due to the fact that in order to Aldehydanlagerung - requires only a relatively low temperature, and that, furthermore, also a - in contrast to the curing of resins at high temperatures low catalyst concentration is possible; It also plays a JRo 11 α, that you do not have to dry to the end point of the absolute dryness of the fabric o The method according to the invention gives excellent results if you dry up to a reed moisture * of 2 to k% , usually with a resistance moisture meter is measured. The very best results, however, are achieved with completely dry material. Furthermore, the process according to the invention improves the yellowing resistance and the swellability of cellulose fabrics and especially of viscose rayon or non-woven viscose rayon, which also increases the shrinkage resistance.

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example 1

In order to eliminate the greater shrinkage of the threads in towels compared to the middle area of a towel, the cotton yarns used for the towel edges were treated with an aqueous solution containing 1 % methyl carbainate s 0 _t 5 f » magnesia chloride hexyhydrate., 0.5 # formic acid, 1.2 % sodium chloride and 0.17 % of a dimethylpolysiloxane oil contained as a softening agent. Various Mongon formaldehyde was added to these baths, as can be seen from Table 1 below. After the bath treatment, the Baiamfollgarno were dried at 03 C and then woven into the edge areas of the cotton towels, the results listed in Table 1 below being achieved; The individual columns in this table have the following meanings: Column A - molar ratio of formaldehyde: methyl carbamate; Column B - Prosentic formaldehyde content of the yarn in the finished towel;
Column C - percentage of formaldehyde in the yarn

Towel washed 30 times; Column D - Percentage nitrogen of the yarn in the finished product

Hand towel;
Column B - Percentage nitrogen of the yarn in 30 times

washed towel;
Column F - enema in % of the towel washed 30 times;

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- 44 -

·: Ϋ. · ::. '3θ ».' Ki ^;:: .'3;. We f T f α h ere ei: / ice> .us is mitorscli: i "dAi.criOii 5 * ζ) \ ι ·>} Ά'ϊ -ί-'ί'.α _$; i>. 'i. d?: m rait 100! ϊιΐΐΛΐ: <. ρΙχί.: ^ Λί '" ^? .βη Viirl'ülivii /; -la; ·: - Di.xierensB from -.! ■■ · j ¹ VIrOl"? -' du .3 ^ "! C.riJ'i.xif.iri ^ iii.i the B ^ -eito -.los

2.5: 1 O, Table, ^ C. D. 0 E. F. 5.0: 1 O, B. 0.13 0 _r 03 0 3.1 Attempt a 7 ₅ 5: 1 O, 1% 0.30 0.05 0 , 05 -0.2 1 10.0: 1 O ₅ 28 0.56 0.07 0 , 07 .0.8 2 12.5: 1 It 56 0 _¥ ? 2 0.03 0 _t 0h -1.9 3 * 2 ^r »ϊ 1 0, 77 0.95 0.07 0 , 07 -1.2 V untreated
Control prob - 13th 0 _s l6 0.0% 0 , 03 1.6 5 Average value dee
treated yarn 16 - 0.03 0 , 07 6.3 6th 0.058 , 052 7th

In the box of sample 1, a pre-condensate of methyl carbainate and formaldehyde was used.

If the methyl carbamate had attached itself to the G & r: a , the nitrogen content, for example in a sample with 1.13 f * formaldehyde in the yarn (sample 5), was at least 0.26.

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The retention of the festive it dor yarns was drawn up tf.us and does not depend on the amount of the dam auigenonunonen formaldehyde, as the following table 2 shows, in which the individual columns have the following meaning:

A - Break-proof: if you want to garnish; in kgj column B - retention of strength (retention) in %; Column C - Break of the single thread in ks>

Table 2

attempt A. B. C. B. 1 I42 _t 5 76 ίί,; $ 6 69 2 135.0 72 2, dl 71 3 138.5 7k a, 54 7t 4th I43t5 77 2.72 72 5 143 »5 77 2..6? 75 6th 119.0 CA ? m 59 68 7 ~ control sample 106.5 - 3.72 - "-

The abovementioned four ex-te of the supplementary information on the strength are based on bleached, mercerized yarn, which was examined immediately before the treatment with methyl carhamet and formaldehyde. If the retention of the strength on unbtshandoltea _t alao un ^ eblciclvbes, inercerized yarn (3.16 kg breaking strength of the pumice thread)

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is obtained, the usual wan determining the yarn strength corresponds to the no Retemiionswerte are the yarns 80 to 86% _s

Example 2

Cotton yarn was treated in the liquor with an aqueous mixture with a content of 0.5 Ii magnesium chloride hexahydrate, 0.5 % formic acid, 0.3 % methyl carbanate and the amount of formic acid entered, whereupon the yarns under vacuum at 8 ° C to a maximum moisture content of 2 to 3 % . The following table 3 shows that the amount of formaldehyde accumulated in the yarn is usually around 20 to 25 % of the formaldehyde content in the aqueous mixture.

Column A - % formaldehyde in the mixture; Column B-Ji formaldehyde on the retained yarn; Column C - molar ratio of formaldehyde to methyl carbamate.

Table 3

Experiment A B C

1 2 3 4

1.5 0.37 12.5: 1 1.5 0.40 12.5il 2.5 0.52 20, StI 2.7 0.52 22.5: 1

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Example 3

An aqueous mixture with a content of 5 % formaldehyde, 1 % methyl carbamate and 1 % magnesium chloride hydride was applied to bleached canvas with a moisture absorption of 55 to 60 % , then dried slightly at 82 ° C to about 10 % moisture content and then for different lengths of time Treated at different temperatures The individual values are given in the following table k , the columns of which have the following meaning:

Column A - temperature in ° Ci Column B - treatment duration in minutes;

Column C-Jf formaldehyde accumulated on the fabric, the fabric being washed for one hour at 93 ° C in an alkali containing 0.25% soap and 0.50 H soda and then thoroughly rinsed;

Column P - % nitrogen on the fabric;

Column B- appearance of the substance, which was determined after five vials (E,) or after washing twice (E ₂ ) according to a standard scale (AATCC) from 5 (best value) to 1 (worst value); where the fabric was washed in a 4 kg washing machine at 40 ° C and then «?, dried in an automatic drying system;

ßAÜ OFUGiNAL

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Column F - shrinkage of the warp thread after the same five (F-) or zrtranzig-fold (F ₀ ) wash »

Table 4 ABCD E- E "FS F ₀

X dt Λ. ti

220 5 0.52 0.07 4.0. 3.5 4.3 4.1 260 3 0.47 0.08 3.0 4.0 2.8 2.5 300 2 0.50 O, O8 3.5 4.0 2.4 2.1 34O 1 0.57 O, O9 4.0 4.0 1.9 2.0 300 15th 0.58 0.09 3.5 3.0 3.3 3.5 Control O O4 8. 3 sample Example 4

Mercerized and bleached cotton cloth was treated with an aqueous solution containing 2.5 % formaldehyde, 1.0 % methyl carbide and catalyst. The moisture absorption was 60 Ji. The fabric was slightly dried at 82 ° C to a humidity of about 10 % and then warmed to 127 ° C for 3 minutes. The following table 5 confirms that again only traces of nitrogen could be found in the treated fabric However, the carbamate was not present on the towel immediately after your heating. This: .st presumably an indication of the reaction mechanism, <can be the carbanate

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Obviously through the blackening certetzi :, waK also through other investigations could have been confirmed. In the following table 5 mean:

Column A - added formaldehyde according to egg. natural «washing at 93 ° C in a 0.25 Ά soap and 0.150 % soda washing solution, as well as after thorough rinsing;

Column B - percent nitrogen content before (B ₃ ) bsrw, after (Bg) washing;

Column C - Crinkle Resistance, measured in the re-setting of angles (W +.?) In dry (C ₁ ) and na.? β en (C ₂ ) states

catalyst 4M ₁
% HCOOH ο Table 5 ] ^B l ο ³ 2 ⁰ I. 246 1?
1 5C1 _o '6H _o 0 0 » 0 , 07 ₂₅₂ 234 sample 1? * HCOOH 0 A. 0 , 05 0 , 06 259 242 ¹ ι ,1 % NH ₄ Cl 0 .T. 0 , 02 0 , 02 ? A5 159 2 Control
sample mm mm r70 0 , 08 0 , 10 257 3 ♦ 70 0 , 02 , 04 127 k , 70

At the rehearsal Mr. k is the content a; a KH.C1 estimated · The bath was neutral; the NH ^ Cl residues came from the previous treatment of the substance.

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Example 5 -

Bleached, uercerisiortes building scrap is treated "with an aqueous solution containing 2.5% formaldehyde, 1.36% sodium chloride, 0.5 % Magueeixuncbloridhexahydrat, 0.5% formic acid, O ₁ I 5" DiiaethylpolyeiJ.oxnnöl and the specified amounts Contained methyl carbawate. The material was then dried at 82 C. In the following table 6, the individual columns mean:

Column A - molar ratio of formaldehyde to methylcarbasiet; Column B - Percentage. Methyl carbataate; Column C - Pros containing accumulated formaldehyde "

Sample A B

1 ^, 5: 1 0.1 0.30 20.8: 1 0.3 0.52 3 8.9: 1 0.7 0.76 4th 6.25: 3. 1.0 0.20 5 12.5: J. 0.5 0.33

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Example 6

Bleached, orcerized cotton yarn was treated with an aqueous solution containing 1.3 % sodium chloride, 0.5 % magnesium chloride hexahydrate, 0.5% formic acid and 0.1 % diethylpolysiloxane, 0.3 % motocyclic carbamate and the specified amounts of formaldehyde The yarn was then dried at 82 ° C. In the following table 7, the individual columns have the following meanings:

Apalte A - molar ratio of formaldehyde to carbaate Column B- Percentage of formaldehyde in solution Column C - Percentage of formaldehyde accumulated

A. Tabel 1 7th B. C. sample 2.5: 1 0, .J 0.05 1 7.5: 1 0.9 0.2'i 2 12.5: 1 ItS ο, ho 3 17.5: 1 2.2. 0.3 '* 22.5: 2.7 0.52 VJi Example 7

Mercerized cotton yarn was treated with various products in various amounts in aqueous solution

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and then dried at 93 ° C. The Methylceirbataat-Formal dt -hyd-Vo.rkondenaat is a condensate ic ne product from 2 * 5 mol foraldehyde to 1 mol Methylcarbainai and is in the first. Column with MC-? "Furthermore, in the aqueous solution there are 0.5 % polyethylene softening agent and 0.1 % of an alkylphenol-ethylanoxide condensate""present as a wetting agent".

L. Tabfclls ^ 8th Pr ob 3
3 H % - % material 1 J. 2 % $ % MC-F % 8 % 1 »;> % 1 78% MgCl ₂ -H ₂ O X ei ι ΐί
/ Q X. / υ ..... 1 Zn (BF ^) ₂ 0, ■ ι, ■■ ff *
a »;>.» j O, HCOOH e / τ '.ν
/ 0x4 $ 1.029b 5 »CH„ O attached 63? Ί 1.93%

Example 8

Both bleached, ma-cerized yarn and carded, bleached cotton yarn were treated in a bath with an aqueous solution containing 2 % methyl carbamate form & ldehyde precondensate with a molten ratio

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of 1: 2.5, furthermore 2.1 % free formaldehyde, 0.5 % magnesium chloride, 0.5% formic acid, 2.5 % sodium chloride, 0.2 % sulfonated tallow (plasticizer) and 0.025 % dimethylpolysiloxane. The yarns were dried at 93 ° C, whereby the circularized yarn was found to be. 0.72% formaldehyde accumulated and the carded yarn took up 0.70 % formaldehyde.

Example 9

Ir Merceriaiertee cotton yarn was a bath with an aqueous solution treated which C ^1, 5% Ätbylcarbaciat, 2.1 54 Formaldehyde (MoIverhältnie formaldehyde to Carhamat: 12.5: 1), and 0.5 S * magnesium chloride and 0.5 56 contained formic acid. The yarn was then dried at 93 ° C * in order to deposit the formaldehyde on the yarn. The ability of the carbamate-formaldehyde process of the invention reduces the swellability of the fabrics, as can be seen in the following examples of treating nonwoven rayon fabrics that have been attached by pins.

A fabric, which consists of a non-woven, 230 g viscose rayon web (Avril) and was connected to a 45 g polypropylene fabric with needles, passed through orphans and it was smoothed out. There was an objectionable tendency to swell and an increase in biokens during the N & ß treatment.

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These disadvantages can be partially avoided by that one is a combination of polypropylene fiber and viscose rayon For da3 fabrics Da used the polypropylene thermoplastic is, this fiber combination can be hot calendered and smoothed in the fabric, so that the strength The base fabric is reduced and also the ability to swell and decreased the strength increase during the pre-immersion. Such a cloth, however, still swells and does not swell Thick when you wet ea. In addition, the processing of polypropylene fibers a relatively costly elimination or reduction of the specified Trouble.

Example 10

In the following example the following substances were used:

a) a 230 g viscose rayon (Avril) fabric, which with a 46 g polypropylene gauze material was processed;

b) a fabric * consisting of 60% polypropylene and 40 per viscose rayon of 230 g each, which was processed with a 28 g polypropylene core material

c) a 92.4 g material made of <> 0 % polypropylene and 40 % viscose rayon, which was processed with a 28 g cotton gauze material.

The fabrics. a), b) and c) were all needle-finished,

8AD ORIGINAL ₁

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calendered and smoothed. An aqueous mixture (mixture A) was applied to cLiess substances, which contained 1 % methyl carbamate, k% formaldehyde, 0.83 % methyleneurachloride _1, 0.83 % formic acid and O ₉ 2 % nonylpfceirrol-ethylenoscyd adduct as a wetting agent

This mixture A was applied at 50 ° C with a "Laboratoriumsauftragegerät" whereupon the substances a) and b) in a continuous oven at 121 ° C vmd vurden dried the substance c) in an oven at ⁰ C IO5. The fabrics were then rolled up and kept in a XJmvalBofen 1 1/2 hours at 105 ⁰ C to the conditions mimic the boitn hot rolling of webs in conventional manufacturing processes occur. With The nno el air ante in the fabric rolls, the temperature could be determined as follows:

When placed in the oven f> 2 ° C

After 25 meows 77 ° C

After 45 minutes 65 ^° C

After 90 minutes 93 ° C

The strength of this cloth was before unc. after treatment measured with a micrometer and also determined after wetting in water. In the following table the individual columns have the following meaning:

Column A - percentage of formaldehyde accumulated; Column B - thickness when dry in mm; Column C - starch saturated with water in

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Table 9

Untreated substance a) Treated substance a)

Non-diapered fabric b) Treated substance b)

Unb "Aa" d "older substance c) Treated substance c)

O 66 1 , 02 1 , 73 ο, 1 , 14 1 , 50 0 51 1 , 02 1 , 04 ο, 0 »Θ6 0 «FX 0 56 0 * & • 74 0, 0 θ

The treated prolie each had an adequate thickness in the moist state and also resulted in an already serine swellable substance b) a further swelling or less swelling ^ The total weight of the substance calculated in this "" and in the following examples.

Xf

Bs has been needled a 2-3O g viscose Ray on web on "Inen 8% g Polypropylengazestreifen, kalaadriert and smoothed. Mixture A (according to Example 10) was applied to one area of this cloth using a laboratory applicator. A section of this area was extracted under vacuum between the top roller of the applicator and the take-up assembly, while the second section was not extracted under vacuum. «Another section of the fabric was left untreated» The material was

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continuously dried in a laboratory oven at 121 ° C, the material temperature measured with a radiation pyrometer at the oven exit for the material extracted under vacuum was 105 ° C and for the material not extracted under vacuum was 103 ° C. The results of the swelling tests are shown in the following table 10 _t in which the individual columns have the following meaning:

Column A - percentage of accumulated formaldehyde; Column B - thickness of the dry material in mm; Column C - Strength of the material saturated with water

in mm;
Column D - Strength of the material saturated with 10% NaOK in now.

r I

Table 10

A. 51 0 B. 1 C. 1 D. Not treated 0 68 1 , 99 1 , 27 .78 Treated O. 1 , 22 1 «19 1 Extracted under vacuum O. .24 _f 22 .52

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The small increase in strength in the two treated Substances is irrelevant, since the results are calculated from the average values of 10 readings and the Error range is approximately -0.05 »nw.

Example 12 The following substances were used:

a) a 230 g viscose-rayon web, which with a 46 g Polypropylene gauze material was processed, calendered and smoothed;

b) a web consisting of 60 % viscose rayon and 40 % polypropylene which was processed with a 46 g polypropylene gauze material;

c) a web according to b), which, however, was calendered and smoothed.

The mixture A) from Example 10, a mixture B) and a mixture C) were used as treatment solutions; the latter two differed from mixture A by a content of 8 % formaldehyde, or in mixture C by a content of 2 % methyl carbamate and 8 % formaldehyde. The mixtures were all applied to the fabric with a laboratory applicator at room temperature and then extracted under vacuum. Oar fabric would be dried in a continuous drying system at 127 ° C. D * r treated with mixture A.

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The fabric had a surface temperature of 111 ° C, the with the mixture B treated one of 101 ° C and the old of mixture C treated one of 99 ° C. This temperature difference also influenced the amount of the deposited Formaldehyde.

After drying, the fabrics were treated with sodium bisulfite solution to remove the formaldehyde odor; the fabrics were then treated with an aqueous mixture containing 0.83 % MgCl ₂ and 0.83 % formic acid. The fabrics were then dried, smoothed after Väschen and this catalyst treatment in a 15O ⁰ C oven on a twin-roll mill hot calendered at 120 ° C and then in sswei passes at 127 ° C on a drum of a two-roll Kottpressions-Schrumpfvorricbtung.

The swelling effect was determined as in Examples 10 and 11 by examining the substance in the dry state, saturated with water or saturated with NaOH solution. The source properties were before or ' after calendering and after calendering and smoothing, _{t is} determined, the values being listed in the following Table 11, in which the one-and-one columns have the following meaning: Column λ - added formaldehyde in %; Column B - thickness when dry in mm; Column C - thickness of the substance saturated with water in mm;

Column D - Strength of the substance saturated with 20% NaOH in mm.

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treated with before the before the before the Tabel O 11 B. 1 C. 1 P. mixture Kaiandern Calendering Calendering 0.72 1 1 et ott unbeharxdel t kai andr i er t kala & driert kaiandered A. 1.07 , 37 , 78 A. fcalandered calendered k »landri.ert .... 1.19 1 , 22 1 .47 a) and smoothed and smoothed and smoothed 0.77 1 1 α) A. before desa untreated o, 9i , 19th , 37 A. Calendering A. 0.60 0.91 1 , 14 1 , 37 a) kaiandered a) B. calendered A. l _ä l4 1 »19 I. , 47 and smoothed A. o _s 47 1 1 a) B. before the 0.91 , 19th , 35 B. Calendering O _t 56 0.81 1 , 12 1 .42 a) kai andr i. he i a) C. kaiandri ert __ i ₉ i4 1 , 19th 1 .45 and smoothed 0.45 1 1 a) C. untreated. 1.14 , 19th , 37 C. A. 0 0.86 1 , 19th 1 , 57 a) O _p 44 1 1 a) A. 1.57 .47 , 73 A. -_ 1.35 1 , 40 1 , 37 b) o _t 46 1 1 H) 1.02 , 09 , 14 0 1.02 O , 02 1 , 19th H) O _% 53 O O b) 0.71 , 81 , 07 0.76 O , 76 O ₈ 91 c) 0.46 O O c) 0.71 , 74 , 86 0.64 "66 , 89 c) c)

The values clearly show that the tendency to swell has been considerably reduced both in water and in 20% NaOH is. The untreated substance b) wins you over

SAO ORIGINAL

ft Λ Γ »rt / V i i« i <■> Γ * λ

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high value for the strength in the dry state, since this fabric was particularly fluffy * If it had been pressed in the usual way, like the other fabrics, it would have a thickness of much less than 1.47 mm. Iranians see a significant reduction in the swellability of the substances when they contain considerable amounts of cellulose fibers, for example 10 or usually at least 20 % as the lower Grenas value.

Example 13

In this and in one of the following examples, the

The ability to process the material is shown, as well as the very rapid implementation that takes place under good conditions.

3 samples of a light white fabric with a content of 65 % polyester fibers and 35 V * cotton fibers were used. an aqueous mixture treated which "0% methyl carbamate, 6.0% formaldehyde, 0.83% magnesium chloride, and 0.83% formic acid and 0.5% acrylic polymer, namely, ethyl acrylate, methyl methacrylate, _t acrylic acid and acrylamide (Rhoplox E-32 ), as well as 0.25 % polyvinyl alcohol and 0.2 % nonylphenol-ethylene oxide coxidation product as wetting agents. The material was then dried.The three different types of fabric were:

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a) a 125x72 count “fine cloth with a weight of 3.3Om / 450g;

b) a 96x84 count batiste weighing

c) a 94x80 steel batiste weighing 3.90m / 45O g.

In the substances a) and c) the polyester content was off Oacron and in the fabric b) from Kodel. The Peuehtigkeita uptake of these substances ranged from 35 to 40 tf. It was dried with an air dryer set to 166 ° C set «rar. The working speed was 100 m / min, and the swelling of the fabric JLa dryer, was 14 seconds. The fabric temperatures measured with an infrared pyrometer were in the range of 118 to 184 ° C.

After drying, the fabric was washed through sulflt solution to avoid the not implemented · t © r «aid» hyd and remove the unpleasant odor old ^

and the hat rial was then washed and A disregard for disputes based on PettsKure was treated, troubled and then led by an ear-hull precharge. ; ■ ^ ■■ '% ■'

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The substances had a fixed formaldehyde content, which remained essentially constant even after numerous washes. This can be seen from the following Table in which the percentage of formaldehyde, is given based on the total weight of the substance; the individual columns have the following meaning:

Column A - a material that takes one hour until

Treated boiling in a 19iigen soda solution became;

Column B - a material which has been washed 5 times in a household washing machine, namely after AATCC Test Method 88-1964T;

Column C - the material was sanforized 5 times for one hour, starting at boiling point, washed;

Column D - the material was applied 5 times in the usual way

Washed 71 ° C, subjected to chlorine bleaching and treated with calcium fluoride, namely 'in a 37 minute wash five times

A. Table 12 C. 50
56
62 0 Swatch 0.62
0.59
0.62 B. 0,
O,
O. 0.53
0.52
0.61 a)
b)
c) 0.56
0.36
0.61

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These fabrics had excellent properties with respect to Ironing strength and waxing even after numerous Vases unchanged in terms of both handle and color. There was no loss of whiteness established. When washed together with Bunt wache, untreated items of laundry showed discoloration, while the treated material discolored only slightly under these conditions.

example

The three types of material of Example 13 were passed through sin Geadsch, which contains 1.0 % methyl carbaaiat, 4.0 % formaldehyde, 0.83 % magnesium chloride, 0.83% formic acid, 0.5 % acrylic polymer (Rhoplex E-32) Containing 0.7 % of an emollient based on fatty acid and 0.2% of ilonylphenol-ethylene oxide condensation product as wetting agent. The fabrics were dried as in Example 13 at a web speed of 80 m / min and a fabric temperature of 120 to 127 ° C and treated with a bisulfite and a plasticizer, but the mixture now still contains 1.4 % MgCl ₀ and 1.4% Contained HCOOII. After applying this mixture, the fabric was carefully dried to avoid major acid losses.

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The fabrics so treated had similar properties to those obtained by the procedures of Example 13; They also retained the very sharp creases even after washing them several times, for example in an ironing machine for 15 seconds

ο permanent ironing with a steam pressure of 7 »03 kg / cm was obtained.

Example 15

A heavy, previously mercerized and dyed cotton twill (250g / 0.84m) was passed through a bath containing 1.0 % methyl carbamate, 4.0 % formaldehyde, 0.83 9 MgCl ₂ , 0.83 Jt HCOOH, 1, 0 % acrylic acid polymer (Rhoplex E-32), 0.5 Ji polyvinyl alcohol and 0.2 % nonylphenol / ethylene oxide condensing agent. The fabric was dried in a forced air oven at 166 ° C, the dwell time was 21 seconds and the web temperature was measured at 110 ° C. The fabric was then passed through an aqueous, buffered catalyst mixture which contained 0.83 % 0.83 % HCOOH, 0.50 % Na ₂ S ₂ Oe and 2.5 % emulsified tallow as whitening agent Circulation oven dried at 181 ° C with a web temperature of 88 ° C

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Creases were ironed into these fabric sections using a steam ironing machine, _t with an ironing time of 15 seconds and a steam pressure of 7 kg / cm. The samples were taken six minutes in an oven at I65 ⁰ C · After several Vaschen the fabric sections showed no change in appearance of creases. The same results are achieved if the subsequent heat treatment is carried out for 6 minutes at 135 ° C. This example also shows that it is advisable to add more catalyst to maintain the ironing resistance in order to compensate for catalyst losses that occurred in the first heating period when drying the with formaldehyde treated substance occur. The crease resistance is imparted after the fabric has cured for the first time «

Of course, the present invention can be modified within the scope of the ability of a person skilled in the art.

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Claims (2)

1. Procedure for aldehyde treatment (formalization). Cellulose, cellulose esters or starch, characterized in that they are either in the presence of a catalyst a) with an aqueous mixture of aldehyde and one Carbanate of the general formula R ^R l NCOOR ₀ treated and then at temperatures up to au 205 ° C heated or b) containing with an aqueous mixture of preferably further aldehyde, known for this purpose in itself aldehyde Carbaiaat condensation products treated with a carbamate dor Formal H ₂ NCGOB ₂ and subsequently at temperatures of not more than 150 ⁰ C _t preferably from 80 to 150 C are heated, where R ₁ and H- denote a hydrogen atom, an alkyl group or a carbocyclic aryl group and R «denotes an alkyl group or a carbocyclic aryl group« 909804/1250 ' -X- 2. The method according to claim 1, characterized in that that a lower alkyl carbamate, especially a Methyl carbamate, is used ο 3 · The method according to claim 1 to 2, characterized in that that the carbamate in 0.1 to 3? »iger solution; and the aldehyde, especially formaldehyde, is used in amounts of 3 to 60 moles per mole of carbamate. tie: ro 9Ό9804 / 1250