DE2231834A1 - DIRT-REPELLENT PREPARATIONS FOR TEXTILES AND PROCESS FOR THEIR MANUFACTURING - Google Patents

Description

PATENT LAWYERS

DR. W. SCHALK DIPL.-ING. P.WlRTH DI PL.-I NG. G. DAN N ENBERG DR. V. SCHMIED-KOWARZIK. · DR. P. WEINHOLD · DR. D. GUDEL

6 FRANKFURT AM MAIN

CR.ESCHENHEIMER STRASSE 39

Wd / Ar / Be Case FDN-162

GAF CORPOIUTION

140 West 51st Street,

New York, H.Y., USA

Dirt-repellent preparations for textiles

and methods of making them.

3 0 9 8 0 7/1163

κ »

The invention relates to preparations and a process for their production which impart an effective dirt-repellent finish to textiles containing polyester fibers. The preparations contain partial alkyl and alkoxyalkyl esters and mixed esters of interpolymers of maleic anhydride with unsaturated compounds _/ as styrene and ethylene, with Polyvinylalkyläthern in which the percentage Gev / layer of the esterified interpolymers is kri-.tisch.

The invention relates to textiles containing polyester fibers and, more particularly, to preparations containing polyester fibers impart dirt-repellent properties after application to the textiles and hardening. In particular, the invention relates on preparations that are partially esterified interpolymers of maleic anhydride, and for use as dirt-repellent Serve finishes.

Clothing containing synthetic fibers has made great changes in the textile industry, partly because these clothing can retain originally ironed creases and partly because they can be water washed. Additional wrinkle retention is generally imparted to the textiles prior to the manufacture of the clothing by treating them with resins and curing the resins on the textiles after folding and ironing as desired, the so-called "wash" which is so abundant in the clothing industry -and-wear "^ (non-iron) and" durable press "(permanently ironed) clothing is created. However, "have pieces of clothing, the polyester fibers contain the disadvantage that they easily absorb dirt, particularly oily soils as clothing of natural fabrics. Moreover, polyester-containing clothes in the repeated washing in home washing machines increasingly laden with dirt, since dirt in Y / ash water is dispersed, redeposits on the washed clothes before the end of the wash cycle.

For this redo-position behavior, the oleophilic and hydrophobic Properties of the linear polyester fibers, which are normally • wisely mixed with cellulosic products such as cotton and rayon are responsible. The polyester fibers seem to absorb oily dirt from the washing water. Aminoplastharzo that

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Used in "durable press" finishes also have the tendency to hold back oil and water stains. The coordination of - fairly high ■ resin dosages and high polyester content results in a serious dirt retention problem with "durablepress" Clothing and other textile articles.

In previous attempts to improve the dirt-repellent properties of polyester-containing cellulose fabrics, nitrogen-containing resins have been used to increase the hydrophilic properties of polyester fibers. Were described Aminoplast resins in combination with a catalyst and a synthetic acid emulsion polymers based on acrylic acid, which have been applied to textiles that contain linear polyester fibers, whereby the dirt-repellent and "durablepress" properties have been improved. However, these new developments have not completely solved the existing problem.

There are currently various' textile finishes on the market, which counteract the tendency of polyester-containing fabrics to retain dirt. The two leading commercial ones Types of stain resistant finishes are of the AcrylemuMon type, such as "Rhbplex SR-Zf.88", and the fluorocarbon type, such as "3M Scotchgard ". The preparations of the invention are a third more advantageous Type.

An object of the invention is therefore a new preparation containing cellulose textiles * containing polyester to a high degree Conveyed resistance to pollution.

Another object of the invention is an easily controllable and reproducible method for producing the '' new dirt-repellent preparations.

Other objects and advantages of the invention will be apparent from the following description.

The invention therefore relates to new preparations containing certain partial alkyl and alkoxyalkyl esters and mixed esters of interpolymers of maleic anhydride or maleic acid with unsaturated compounds such as styrene and ethylene, and with polyvinylalkyl

* i.e. celluloid-like textiles

300807/1163 "DOW" "..

- * - 223183 /,

ether include. The new preparations are generally found below referred to as partially esterified maleic interpolymers.

The preparations according to the invention are produced as follows:

Λ) Reacting and interpolymerizing maleic acid or maleic anhydride with a monounsaturated compound that is terminally unsaturated and corresponds to the following formula:

H ₂ C = CH-R

in which R can mean:

1. an alkoxy group with one to about seven carbon atoms, preferably a metboxy group,

2. hydrogen,

3. an alley group with 1 to 1 carbon atoms and 1 a aryl group with a total of 6 Ms 11 carbon atoms, in which the aryl group is a phenyl or naphthyl group or their alkyl-substituted derivative;

B) Esterification of the resulting interpolymer with an alcohol of the formula: R ₁ OH, which can be:

1. a monohydric allyl alcohol in which K- = a Alkyl chain has 1 to 7 carbon atoms, such as methanol, Ethanol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol and the like can be.

2. an alkoxyalkyl alcohol, in which R ₁ = corresponds to the following formula: R _{; j} ~ (0-C ₀ II ^ -) _m , in which R _p = an alkyl chain with 1 to about 30 carbon atoms and m = an integer from 1 to about 10, such as methoxyethyl (Methylccllosolve), Methoxypolyäthyleno-yäthyl, Ethoxyäthyl, Polyäthylenoxyäthyl, Propoxypolyäthylenoxyäthyl and

3 · mixtures of 1 and 2; and

C) rehydrolyzing the resulting esterified cn Int ΐτροΠ.γι.ϊον.-ϊ; with an ester content of 10 to ¹ JOX ₁ and preferably lyric and 50% carboxy groups that can be separated from the water during the esterification.

1 CY 3

BATH ORIGINAL

Y'.T-jn er soluble, linear, resinous interpolymers of alkylvinyl "them, monoolefins or arylolofins with maleic anhydride! . GoZ ff ancestors he rc e r> described are divided Dierje reactions can be leads in the manner ausi% 'that substantially molar ratios of 1:. of starting materials are used 1 and mild in bulk or solution in the presence of Friedel-Crafts is polymerized catalysts at temperatures of 0 to 100 ⁰ C. compounds which can be used for reaction with maleic anhydride are vinyl alkyl ether, such as methyl vinyl ether, ethyl vinyl ether and the like, olefins such as ethylene, propylene, butylene and the like o'lor aryl olefins such as The resulting polymeric products styrene. have molecular weights of about 156,000 to about 1+ 000 000.

JJAu structure of this inter polymer can be represented by the following formula interpreted:

CH

■ CH CH-

O = C.

CH-C = O

has the value of about 1000 to 25000, and R = an alkoxy group (prepared with an alkyl vinyl ether), alkyl group or hydrogen (produced with a mono-olefin) or aryl group (prepared with an aryl olefin, such as styrene) can mean - in the η. Such products are usually characterized by their specific viscosity, which is considered to be the most accurate index available for identifying polymers. The products corresponding to the above formula have iii.no spoi-.ifische viscosity (n.; P-word) from about 0.1 to about 3, ^c >, h "\ i, v ;; \\ pl () ,;. ' to 1, ^c j (measured at a concentration of one Ur · -.mm in ti;.! thylHthy .keton at ^1> ° C?).

Ί 0 <) ^f ) U 7 / t 1 ß)

^ßAD

These products have then been esterified in accordance with step (B) by reacting them with one of the alcohols or Alkoxyalkyl alcohols, preferably with an excess, by Warming to an elevated temperature, usually under reflux reacts until complete dissolution has occurred in the alcohol or alcohol isification. At this point it owns a sample of the alcoholic solution has little dispersibility in water.

At this point in the reaction, the half-ester is an intermediate stage enpolymeres, which can be described by the following formula:

CII

CH CH

CH

O = C C = O

I I

HO OR

ra

in which η and R have the abovementioned meaning and R »= an alkyl or alkoxyalkyl radical of the formula:

is, in which R- ^{un (} l ^{m have} the meaning given above.

The esterified polymer is hydrolyzed by heating in the presence of water and optionally in the presence of an acidic or alkaline catalyst then in step (C), is zurückhydrolysiert until a part dos ester. The resulting product can be described by the following formula:

rir.

CH ₁ -CH

CH

O = C HO

I I

C = K)

OR ₁

- CH ν CH,

CH CH-

I I

I I

OH OU

7 / I 16 y

in which Ή and R. have the same meaning as above, the sum of χ and y is 100, where χ et v / a 10 to 50 fi-jv / ichi · .-% and y mean the remainder. In the product, therefore, χ the who! vi>_; about 10 to% by weight of the total product and y the value of about 90 to 50% by weight.

For rehydrolysis, the Eaters of the formula Yi are suffered in the presence of water, preferably in the presence of a catalytic amount (for example 0.01 to 5% by weight) of a sam · ',: * catalyst to form the partial ester of the formula III: - " . until the resulting product in V / ater dispersible Saur ·:.!.!. catalysts that can be used are boispielnweise licfthnnsulioiiaäure, p-toluene sulfonic acid and mineral acid, such as / olive folic acid / JaIzsäure, etc. Also, the Säurvzrhl of the product are of course always higher, in this lieulehun, ¹ "it should be noted that the acid number necessarily decreases because of the bo '; ondei \ - ■ -, starting material used, if there ;; The molecular weight of the half-ester increases.

In general, however Rückliydi-olly should:. ·: · You lr.hge until the product is wasserdispergtorbar and dio SLUirezahl least 3% higher than the theoretical / Khu-ezahl the full Ilalbesters be leading. However, llydrohyria should preferably be terminated when less than 10% of the sein-egruj / pon remain esterified.

After the reaction has ended, the partially hydrolyzed half-esters of the formula III in water have a pH in the Borcich of 2.2 to 2.9%, but many of the fabric softeners used with "permanently prcn." ], na '· π ¹ Om material, it is usually oirpi'ehlon ;; v; ort to add sufficient amounts of a base (e.g. NalriuMhyrtro: -,] d) to make the pll-V / ert aui el v / a ^ to bring 0. IUi dirr.nm pH-V / ert the product with all currently ru "permanent pro ;;;" - formulations added materials is to be tested ^: only.

It is important to note that the orii? If3ni /; : ■; oniüi? .En products only by esterification and then '. "Iiiickh.vdrolyoe-Technik befj-jedlgeiid hm (vr, \ f-111 wci d-ni kchinen.

'< (ι Ί 8 0 7/1 1 6 3

^BATH

vinyl ether / maleic anhydride interpolymer with an nsp-V / ert of 0.1 to 0.5 by using small amounts of alcohol for the esterification in an inert solvent (e.g. acetone) so that at least 1 + 0%> but less than If 1% of the acid groups were esterified, there were no satisfactory products.

Attempts to determine the x-value by transesterification of a complete half ester from a malcic anhydride / polyvinyl methyl ether interpolymer Bringing a non-esterified polymer in the range of 1- ^ 0% is not a satisfactory product.

In the following examples, for the sake of simplicity, the following Trade names and abbreviations used:

Dacron: polyester fiber made by

EI duPont de ffemours & Co. Methylcellosol ve: HO-CH ₂ -CH ₂ -OCII ₇ Aerotex 101: A modified aminoplast resin from

Flyoxal type manufactured by American Cyanamid Co.

Magnesium-based resin catalyst manufactured by GAF Corporation. Anionic surfactant manufactured by GAF Corporation. Textile Carbeiminate-IIarz by Kefined Onyx Division, Millmauter Onyx.

Acid salt catalyst manufactured by Refined Onyx Division, Millmaster Onyx.

Catalyst MI:
Alipal Co-433:
Karas et 1 Zf 52:

Catalyst 341:

The following k examples illustrate processes for the preparation of the partial esters according to the invention, starting from a methyl vinyl ether / maleic anhydride interpolymer with an nsp value of 0.1 to 0.5, which is hereinafter referred to as methyl interpolymer.

7/1163

example

The reaction was carried out in a k 000 ml flask equipped with a thermometer, a reflux condenser and a mechanical stirrer. The flask was heated by hot water. M> 8 S methyl interpolymer and 900 g of methanol were added to the flask. The resulting slurry was stirred and slowly heated to reflux (67 ° G). The slurry became very viscous and then dissolved. The temperature was held at reflux for 3 1/2 hours. At this point, the product would not be able to be dispersed in water, but would absorb water. (At this point the product was a partial Monoecter, in which the CIL group as IL, Gruppo was more than ij.0% by weight.) 700 g of water were slowly added to the solution with continued stirring and heating. The solution was maintained for 1 1/2 hours at reflux temperature (78 ⁰ C). The product could not yet be diluted with water at this point. A further 600 g of water were added and the mixture was refluxed for a further 11/2 hours. The dilutability of the mixture with water was not yet satisfactory. At this point 0,0δ% methanesulfonic acid (70 ⁰ C) was added and heated for a further hour under reflux. At this point the product was water-dispersible and compatible with aminoplast / catalyst systems.

The acid value (found) was = 318.5

Example 2

The reaction was performed in a l \ 000 ml flask equipped with a thermometer, a reflux condenser and a mechanical stirrer. To the flask were added lf68 g of methyl interpolymer and nZfif g of methyl cellosolve. The resulting slurry was stirred and slowly heated to 90-98 ° C. The slurry became viscous and then dissolved. Was heated for 3 hours at 90-98 ⁰ C. At this point, the product was not soluble in water but took V / ater on. 55 μg of water were added at TOO C and the mixture was heated for a further 1 1/2 hours. At this point

309807/1163

the product was water-dispersible and with aminoplast / catalyst systems compatible.

Example 3

The equipment described in Example 2 was used. 68 g of methyl interpolymores, 8-6 g of methanol, and 228 g of methyl cellosolve were added to the flask. The resulting slurry was heated to a reflux temperature of 68 ° with stirring. The slurry became very viscous and slowly dissolved. The mixture was heated for 3 1/2 hours at reflux temperature (68 ⁰ C). The flask was then readied for distillation and 309 grams of solvent (mainly methanol) removed. At this point the product was not soluble in water, but did take up water. 300 g of water were slowly added with stirring and the solution was refluxed at 80 ° -85 ° C. for one hour. The solution was then cooled and 200 g of additional water were added. The resulting solution was dispersible in water and compatible with resin / catalyst systems.

The acid value (found) was = 28O, Zf.

Example Zf

The reaction was carried out in a Zf 000 ml flask equipped with a thermometer, a reflux condenser and a mechanical stirrer. The flask was heated by hot water. 700 g of methanol, 200 g of methyl cellosolve and / + 68 g of methyl interpolymer were added to the flask. The resulting slurry was stirred and heated to reflux temperature (68 ° C). The slurry became very viscous and then dissolved get up slowly. The mixture was on for a total of if 1/2 hour Maintained reflux temperature. At this point 1ZfOO g of water and 2 g of methanesulfonic acid were added. While stirring, the Temperature increased to 82 C and held at this level for 2 1/2 hours. The reaction product was then cooled to room temperature. At this point the product was wanserdispersible.

The acid number (found) was = 2 & f.8.

3.0 9 807/1 163

The following four examples illustrate the effectiveness of the products according to the invention when they are based on polyester Cellulose textiles are applied and cured and Standard pollution tests are subjected.

B ο i s ρ i e 1 5

(Use of the partial ester preparation prepared according to Example 1.)

The one made dirt-repellent by the preparation described above To>: til becomes TO seconds at around 1 / f9 to around 316 ° C dried and hardened for about 20 minutes.

Tuchsiufilor of a white 50/50 Dacron cotton fabric and a yellow-brown 65/35 Dacron cotton fabric were dabbed off with solutions of the following compositions (percent by weight): 25% Aorotex 101, k% catalyst MI, 20% the preparation prepared according to Example 1 of 21% Solids content (omitted in the control experiments), 0.5% Alipal Co-433 and 69.5 - ^ - 9.5% water.

All Tuchrauster were getrpck.net and then gehörtet 2 1/2 minutes at 171 ⁰ C. The cured fabrics were then f with mineral oil, lipstick, runslccher sauce, benutztem crankcase oil, mustard, and "Y / s."; ^N -Oil on soiled. The spotted samples were allowed to stand for about 2 hours at room temperature and then washed, rinsed and dried at 6O ⁰ C in a Rührwaschmaschine (Kenmore) using "Tide" -WaGchmittol. In all cases, the samples treated with the preparation prepared according to Example 1 had noticeably less stain residues than the comparative ones.

All Mu "tor were then rinsed in another four wash cycles at 60 ⁰ C gewasc.Vm, respectively and dried. All swatches were then again ;; as previously spotted, conditioned and still-IrK) In olvor washed in step at 60 ⁰ C. In all cases, the preparation prepared according to ßolüpiel 1 had less stain residues than the comparative

30 9 8 0-7 / 1163 ^ß * D 0 & K3INAL

example

4 Z

Instead of the Aero tor 101 and catalyst used in Example 5 MI Karaset 1452 and Catalyst 341 were used. All samples were dried in the same wine, hardened, soiled, washed five times, rinsed, dried, re-soiled, washed, rinsed and dried again. The one with the Prepared according to the invention treated, fabric samples showed conspicuously less stain residue than the comparison samples.

Example 7

The material and method were the same in example 3, but that of example 3 was used instead of the preparation according to example 1. After soiling, washing five times, rinsing and drying, noticeably less stain residues were found in the treated swatches than in the comparison swatches.

Examples

Materials and procedures were the same as in Example 5 with the exception that the preparation of Example 1 was not included in the first swab solution for test and comparison purposes. After hardening, the test samples were rinsed with simple water, dried and then dabbed with a mixture of 80% water and 2.0% of the preparation according to Example 1. The spotted test samples were dried and then cured for 1 1/2 minutes at iyi ° C. Comparative samples were additionally cured at ^{171 ° C. for 1 1/2 minutes.} Beschmutzungsund wash cycles were the same as in Example ^l j. Noticeably fewer flakes were found in the test samples than in the comparison samples.

The preparations described herein are novel aqueous dispersions of partial alkyl and alkoxyalkyl esters of maleic acid interpolymers, which are compatible with aminoplasty and in combination with it, polyoster-containing cellulose textiles

7/1163 _ßAD

lien improved folding tone retention (dimensional stability) and additionally give improved dirt repellency.

309807/1163

Claims (13)

Claims 1. Preparation containing polyester on inchulosic textiles imparts dirt-repellent properties, characterized in that that en partial alkyl and alkoxyalkyloster contains the following formula: HC CH CH CHH I I O = C C = O I I 0 0 CH, CH CH CH O = C C = O I I O O I I H H in which mean: R = hydrogen, an alkyl group with 1 to about Zf carbon atoms, an alkoxy group with 1 to about 7 carbon atoms or an aryl group containing a total of about 6 to 11 carbon atoms, in which the aryl group is a phenyl or iTaph thyl group or a Is an alkyl substituted derivative thereof; R, - an alkyl chain with 1 to about 7 carbon atoms, an oxyalkylene chain of the formula: where R ₂ ⁼ an alkyl chain having 1 to about 30 carbon atoms and m is an integer from 1 to about 10, or mixtures thereof; χ = more than about 10 percent by weight; y = more than about 50 percent by weight and less than about 90 percent by weight; and χ + y = 100 percent by weight. 2. Preparation according to claim 1, characterized in that χ is between about / | Ό and ^ O weight percent. 309807/1163 3. Preparation according to claim 1 or 2, characterized in that its pH-VJer-t in water in the range from about 2.2 to 2.9 and
with the addition of alkali between about 2.2 and 7.0, "preferred
is about / +. / |. Preparation according to any one of claims 1 to 3 _? characterized in that the preparation is water-dispersible. 5. A preparation according to claim l \ -, characterized in that the
The acid number of the preparation is at least about 5% higher than that
acid number of the corresponding monoester preparation is. 6. A preparation according to any one of claims 3 to 5 _5, characterized in that Ii = a methoxy group, R., = an ethyl,
Isopropyl or butyl group, m = 0, and the pH = 4.0
is. 7. A method for producing the preparation according to claim 1, characterized through the following stages: (a) Esterification of a water-soluble, linear, resinous Interpolymers of the following formula: CH CH CH- O = C C = O V / in which mean: η = don value from about 1,000 to 25,000, JR = hydrogen, an alkyl group with 1 to about / + carbon atoms, an alkoxy group having 1 to about 7 carbon atoms or an aryl group having a total of about 6 to 11 carbon atoms, in which the aryl group is a phenyl or naphthyl group or is an alkyl substituted derivative thereof, 3 0! 3 H 0 7/1 1 G 3 by dissolving this interpolation in an alcohol with the formula: R ^ OH, which is a monohydric alkyl alcohol in which R .. is an alkyl chain of 1 to about 7 carbon atoms, an alkoxyalkyl alcohol in which R., the formula Rp- (O- CpH-) means in which R ₂ = an alkyl chain with 1 to about 30 carbon atoms and m = an integer from 1 to about 10 and / or mixtures of the monohydric alcohol and the oxyalkyl alcoholj (b) heating the solution obtained after step (a) under reflux until the solution absorbs water ("accepts"); (c) adding water; (d) Re-hydrolyze by refluxing until dissolution is complete and the solution is water-dispersible is. 8. The method according to claim 7 »characterized in that as interpolymers such with a molecular weight of about 156,000 to about 4,000,000 is used. 9. The method according to claims 7 or 8, characterized in that that the rehydrolysis is ended before χ is less than about 40 percent by weight. 10. The method according to any one of claims 7 to 9 *, characterized in that that methanesulfonic acid is added as a catalyst when heated under reflux. 11. The method according to any one of claims 7 to 10, characterized in, that methanesulfonic acid in an amount of less than about 0.1 percent by weight, based on the interpolymer, is added. 12. Polyester-containing textiles, characterized in that dasr. by applying the preparation according to claims 1 to 6, • Drying and hardening have been made dirt-repellent. 309807/1163 13. Textiles according to claim 12, characterized in that they about 10 seconds to; have been hardened. about 10 seconds to 20 minutes at about .149 ° to 316 ⁰ C. ■ ORIGINAL INSPECTED 309807/1163