DE1619169C2 - Process for felting and shrink-proofing textile material containing wool - Google Patents

Description

The invention relates to a method for felting and shrinkproofing of at least 30 ° / ₀ wool-containing textile material by treatment with Amidoaziridinen.

'To textiles containing wool certain properties various methods of treating them have been developed. Especially Processes and preparations used to improve wool are important for the wool processing industry Shrink resistance and felting of the wool fiber-containing textiles lead. But only relatively little Processes lead to satisfactory results in this regard. In addition, the known processes often the appearance, feel, strength and other properties of woolen textiles harmful or unfavorable. Accordingly, the object of the invention is to provide a new method to improve the properties of proteinaceous materials, especially those containing wool Textile materials; to create what the shortcomings and disadvantages that the known method does not adhere and leads to wool-containing textiles with good felt and shrinkage resistance.

The method is said to have appearance, feel, strength, and other desirable properties the textiles are not adversely affected. The treated textiles should be good after washing Surface quality, in particular minimal lintiness.

ίο The object is achieved by a method for felting and shrinkproofing of at least 30% wool-containing fabric duich treatment with Amidoaziridinen, which is characterized in that the / ₀ Wool-containing textile material is at least 30 ° with an at least about 0.5 weight percent - based on the weight of the wool - containing, a pH of about 0.3 to 9.0 and optionally containing polybasic acids or polyamine compounds containing a solution of an amidoaziridir.v ^ rbverbindungen of the general formula

—C — N — Q — N—

treated, in which R - (- O-) s- is an aliphatic or alicyclic polyol radical and R ₁ , R ₂ and R _{3 are} either hydrogen atoms or alkyl groups with 1 to 4 carbon atoms, Q is an optionally alkyl-substituted aromatic group with 6 to 18 carbons -Stoffatomen, and m represents the number 2 or 3, then the textile material of excess treatment

H H

I I

- C —N —Q —N-

I! ο

in which R ₁ , R ₂ , R ₃ , Q and m have the meaning given in claim 1 and R - (- O -) ^ is one of the following radicals

(I) - O (--CH ₂ CH = CHCH ₂ -) «O,

wherein u has a value from about 6 to about 100; (H) _ O [(CHa) _n - O - Cl (CHj) _n O -,

oj "

wherein η = 2 to 6 and ν = 3 to 80;
- (- OC _o H _2O -) r O - L - O (- C ₀ H ₂₀ O -) _r , c —n:

Il ο

R ₂
R ₃

averaging means liberated, if appropriate at a temperature between room temperature and about 163 ⁰ C dried and then either leaving several hours at room temperature or exposed to temperatures a few minutes 93-150 ⁰ C, and optionally washed out. The textile material is preferably treated with an amidoaziridine compound of the general formula

• c — n:

Il ο

, R ¹

R ² R ³

wherein x, y and ζ are between 1 and 100, a = 1 to 4 and M is a trivalent aliphatic group; and

(V) -O

55

where χ undy = 1 to 100, a = 1 to 9 and L is a divalent organic radical, so that the whole group has a molecular weight of about 500 to about 55C0.

(IV) - (- OCaH ₂₀ -) r O

M - O - (CaH ₂₀ O-) _F , where ρ is 2 to 6, # is 4, and r is 2 to 35.

Aziridinyl compounds suitable for the purpose of the invention can be obtained in several ways, such as B. according to the procedure described in the British Patent 919,861. Briefly described, the aziridinyl compounds that are defined by formula (1), are prepared by reacting an organic polyisocyanate with, preferably, an organic compound containing at least two hydroxyl groups to form one Intermediate product with at least two isocyanate groups. Then the intermediate with a

1,2-AlkyIenimin implemented to the desired product to obtain. It has been demonstrated that compounds falling within the framework of formula (1) fall, are extremely suitable for the treatment of wool-containing textile materials. When considering of the compounds to be used according to the invention it follows that the average molecular weight of the preferred compounds is im Range from about 1000 to about 6000. Such compounds are commercially available or can be ordered according to io (V) -O t can be manufactured from commercially available raw materials.

Typical examples of the group Q are phenylene, toluene, xylylene, diphenylene,

- C ₆ H ₄ - CH ₂ - C ₆ H ₄ -.

(this is the remainder of a linear polyester derived from a polymeric lactone with terminal hydroxyl groups, where η = 2 to 6 and the average value for ν is between about 3 and about 80);

. (CH ₂ ) J ₁ O - C (CH ₂ ), - C - O j

This group comes from the polyisocyanates used to make the desired compounds will. Examples are phenylene diisocyanates and tolylene diisocyanates.

Examples of suitable aliphatic and alicyclic polyol radicals R - (- O-) s-, applicable to formula (1), are the following, which include (a) divalent and (b) d-monovalent forms of R - (- O-) sr.

Ca) A divalent radical that, after removing the hydrogen atoms from two hydroxyl groups, becomes one Polyol with a molecular weight between about 500 and about 5500 remains, characterizes the remainder, when he's the shape

30 (this is the remainder of a linear polyester derived from a hydroxyl terminated polyester made from a diol and a dibasic acid, where /? Is preferably 2 to 6, q = 4 and r = 2 to 35);

r:

O.

35

has. Examples of the remainder in the form of a divalent Radicals are:

(I) - O (- CH ₂ CH = CHCH ₂ -) "O -

(this is the residue of a hydroxyl-terminated polybutadiene, wherein the value for u, the degree of polymerization, is between about 6 and about 100);

(II) -O

. (CH,) «- O - CI,

45 (III) - (- OC ₀ H ₂₀ -) _r O -L - O - (- CaH ₂₀ O-) _y -

(in which a starting compound HO - L - OH, in which L is a divalent organic radical, with χ + y molar parts of one or more "alkylene oxide types [C ₀ H ₂₀ O, a = 1 to 4, average molecular weight about 500 to about 5500] has been condensed. The value of χ and y can range from 1 to about 100).

In general, "L" can be an aliphatic, alicyclic or oxyalkylenic radical; z. B. - (C _& H ₂ 6O) -, where b - is 2 to 20, and alkylene in which the chain is interrupted by a heteroate din such as an oxygen, sulfur or nitrogen atom.

Suitable divalent radicals of the formula type (V) are obtained from alkoxylate type condensation products obtained from any of the exemplified starting compounds listed below

HO-L-OH

can be prepared by ethoxylation with about 10 to 125 mol parts of ethylene oxide, propoxylation with about 8 to 95 parts by mole of propylene oxide or alkoxylation with higher or mixed Alkylene oxides of a suitable molar ratio:

Output connections HO-L-OH Before the alkoxylation Ethylene glycol HO-CH ₂ CH ₂ -OH '■ Propylene glycol HO - CH (CH ₃ ) CH ₂ - OH Trimethylene glycol HO-CH ₂ CH ₂ CH ₂ -OH Decamethylene glycol HO - (CHu) ₁₀ - OH Diethylene glycol HO - CH ₂ CH ₂ OCH ₂ - OH 2-butene-1,4-diol • HO - CH ₂ CH = CHCH ₂ OH 1,4-cyclohexanedimethanol / CH ₂ CH ₂ ^
HO-CH ₂ CH ^ / CHCH ₂ -OH
XCH ₂ CH ₂ / 2,2'-thiodiethanol HO - CH ₂ CH ₂ SCH ₂ CH ₂ - OH Diethanolamines (HO-CH ₂ CH ₂ -) ₂ N -R, where R is H or alkyl with 1 to 5 carbon atoms and L. - CH ₂ CH ₂ N (R) CH ₂ CH is

(b) If trivalent, the remainder R has - (- O-) sr in Formula (1) the shape

Referring to Formula VI), M is the remainder

O —R.

-CH ₂

-CH,

HC-

in this case it is the trivalent radical that remains after removal of the hydrogen atoms from three OH groups of a polyol (other than a diol, of course) having a molecular weight between about 300 and about 5300. Examples of the radical R - (- O -) ^ in the form of a trivalent radical are shown duich the individual compounds by the general formula

(- OC ₀ H ₂₀ -) r

(- OC ₀ H ₂₀ -) _r O '

- 0 - (- C ₀ H ₂₀ O-VH

(VI)

after removing the three terminal hydrogen atoms; in the formula is the value for a - 1 to 4, while x, y and z, each between 1 to about 100, are molar parts of one or more alkylene oxide types (C ₀ H ₂₀ O) which are associated with a starting compound with three OH groups, (HO) ₃ M (M is a trivalent organic residue) 'are condensed. For example, a suitable trivalent radical of the type represented by Formula VI is derived from glycerin condensed with about 50 mole parts of propylene oxide. In this case (on and α is 3, while the sum of x, y and ζ is equal to 50, other, aliphatic starting compounds of the type (HO) ₃ M, which can be alkylated.

ίο (e.g. by CH ₂ CH ₂ O, C ₃ H ₆ O and C ₄ H ₈ O) are, for example, 2-methyl-1,2,3-propanetriol, butanetriols, hexanetriols, 2-alkyl-2 - (Hydroxymethyl) -1,3-propanediols (especially those which have alkyl groups with three or fewer carbon atoms), triethanolamine and 2- (dimethylamino) -2- (hydroxymethyl) -1,3-propanediol.

The m-valent radical R - (- 0 -) - _{m of} the formula (1)

can also originate from condensation products, which are also the alkylene oxide derivatives of many other starting materials than those specifically listed, the compound to be alkoxylated being a dihydroxy compound HO - L - OH or a trihydroxy compound (HO) ₃ M. Further examples of suitable starting compounds, corresponding to the types HO - L - OH and (HO) ₃ M, are described in British patent specification 919 861. Typical of the processes by which the aziridinyl compounds to be used according to the invention can be prepared is the process which is reproduced below in Preparation C; this describes the reaction of a polyol and an isocyanate and the subsequent reaction with the alkyleneimine.

Examples of the connections listed above are:

O-
Il ■ H ₃ C- < Il
NC
ι I.
NH ^ :> H
-NC- (OC ₃ H ₆ -) _{; 1Ö} -O-CH ₂
Il Il
O O
π -NC- (OC ₃ Ha) of ₅₀ - 0 - CH ₂
H

C-N:

^x HC-O (-C ₃ H _G O) ₅₀ -CN- /

-CH ₃

NH

Il

NH _n
H ₃ C- <

Il c-n:

HN

\ - NC-0 (-CH ₂ CH = CHCH ₃ -) ₆₀ OCN- / ^) - CH ₃

Il ο

NCO r (CH ₂ ) ₅ OC

N-C

HN

H C Z

.H H

> -NC- (OC ₃ H ₆ X ₀ -O CH ₂ CH ₂ -O (C ₃ H ₆ O) ₅₀ -CN

ο. ο

When carrying out the invention, the wool-containing Textile material in any suitable form, e.g. B. be present as fiber, yarn or fabric can be treated with the aziridinyl compounds of the formula (1) by using them in the usual manner a solution of these compounds are impregnated.

The solvent can be organic or aqueous. The treatment mixture of solvent and aziridine may be in the form of a solution, suspension, or emulsion. The textile material can sprayed, padded, dipped, soaked, brushed or similar with the aziridinyl compound in Brought into contact and then dried and cured. To make the aziridine compound insoluble to make, higher temperature can be used. The textile can also be after it has been brought into contact with the aziridinyl compound for a short period of time left until the state of insolubility is reached.

If desired, the treated woolen fabric can then be used to remove residual soluble chemicals which interfere with or affect the properties of the end product can have an unfavorable effect. Textiles made from wool that have been treated as described above have excellent dimensional stability. When washing after the for cotton and hydrophobic Fibers customary processes show textile materials made of wool which have been treated according to the invention are, as well as garments made from such woolen textile material, not worth mentioning Tendency to matting, no fluffy appearance, no shrinkage or other undesirable properties, which would have a detrimental effect on the quality of the finished garment.

The invention forms a significant advantage over the previously known in that the Treatment with the selected polyfunctional compounds the color, the handle and others aesthetic properties of the woolen textiles are not adversely affected and, moreover, the tensile strength, Tear strength, abrasion resistance and other important properties of the textile material are not significantly weakens.

In connection with a further preferred aspect of the invention, wool-containing textile materials with the aziridine compounds of the formula (1) in conjunction with the co-reactants as they are -Defined later, treated to even greater improvement in dimensional stability and others to achieve desired properties of the textiles. Suitable co-reactants are polybasic acids and polyamine compounds, especially saturated aliphatic dicarboxylic acids having 2 to 12 carbon atoms and polyalkylenepolyamines having 4 to 20 carbon atoms and 2 to 5 nitrogen atoms. Typical examples of Acids are succinic acid, adipic acid, sebacic acid, citric acid, tartaric acid, and polyacrylic acid. Examples of polyamines are diethylenetriamine, tetra-

ethylene pentamine, hydroxyethyl ethylenediamine, polyethylenimine a wide range of molecular weights, 1.3 diamino-propane and 1.6 diamino-hexane.

In general, it has been observed that the co-reactants cause the aziridinyl compound to become insoluble accelerate in or on the wool and promote the polymerization reaction, so that they in completed in a shorter time.

The treatment mixture containing the aziridinyl compounds of formula (1) and a carrier therefor may take the form of a solution in organic solvents or water if possible is. The compounds can also be applied from aqueous emulsions, which by means of suitable Choice of solvents and emulsifiers that can be produced quickly. Solutions and Emulsions of the treatment agents to be used according to the invention can normally be used without special Precautions as they are stored at room temperature for relatively long periods of time remain stable.

According to a further particular aspect of the invention, wool-containing textile material can with either the aziridinyl compounds defined above

409 613/233

before or after staining because treatment with aziridines does not change or exerts a damaging influence on the dyeing properties of woolen textiles. Furthermore, there is no change in the Tones or adverse effects on the color fastness when the aziridinyl treatment of the textile na (h the dyeing is done.

When carrying out the process according to the invention and using aziridinyl compounds in connection with selected co-reactants defined above, the treatment in a single stage or separately. Due to their nature, it is possible that Aziridinyl compounds, as defined herein, in a single step together with other functional groups Equipment such as water and dirt repellent Agents in general and in particular with fluorine-containing compounds which impart these properties apply.

In general, in order to achieve optimum effects, the textile material can be 30 percent or more, preferably Contains 60 to ICO% wool fibers.

From the previous ending it can be explained that the wool present in the textile material for itself or in the Blends or mixtures with other natural fibers, such as cotton, or with. Synthetic fibers such as polyamides, Polyesters, polyolefins and acrylic fibers, can be present.

For most purposes, the aziridinyl compounds defined by formula (Ϊ) can preferably be used in amounts of about 0.5 to 10% based on the weight of the wool to be treated. In the case of lC0% wool z. B. Amounts of about 2, based on the weight of the wool to be treated, preferably to about 5 ° / _0, although it will be understood that even amounts may be used outside these ranges.

When combining the azindinyl compound with co-reactants, the amount of the co-reactants should be used be dimensioned so that about 0.5 to about 2.0 reactive groups of the co-reactants in the form of amino or Carboxyl groups are available for each aziridinyl group of the azindinyl compound of the formula (1). In other words, there should be about 0.5 to about 2.0 equivalents of the co-reactant, polyamine or polycarboxylic acid, be present for each aziridinyl equivalent.

The ziridyl compound can be applied to the wool-containing Textile goods are applied in Foim of a self-emulsifiable concentrate, which with water to the desired concentration is diluted before use. In any case, the co-reactant, Polyamine or polycarboxylic acid to which the azindinyl compound containing treatment solution or emulsion, or the co-reactant can in a separate working step from a solution prepared from the same solvent that is used for the Azindinyl compound was used, or another organic solvent or water applied will. If the co-reactant is in a separate working stage either before or after Treatment with the azindinyl compound is applied, the solvent which is on the woolen textile material is deposited with the solvent system with which the aziridinyl compound applied, be mixable or immiscible. It has been found that the pH of the treatment solution can fluctuate within a wide range. In general Very high and very low pH areas should be avoided because of extreme conditions Degradation of the wool can take place. Generally a pH range of from 3.0 to about 9.0 is preferably from 4.0 to 8.0, suitable for most purposes.

Then the woolen textile material is at temperatures ranging from room temperature to about 163 ° C, with the temperature range from 93 to

ίο around 153 ° C is particularly suitable when dried. It is note that the drying step is not essential to the overall effectiveness of the process. After drying, the treated textile material is hardened, either by being at for several hours Leaves room temperature or preferably heated to 93 to about 150 ° C. for a few minutes to complete the reaction to be completed to the point of becoming insoluble. The time required for curing varies with the specific reagent and the concentrations that will be used. It should also be pointed out that the hardening time depends on the temperature, higher temperatures make shorter hardening times necessary. It has been found that curing cycles of * 3 to 15 minutes at 120 to 150 ° C in most Cases give excellent results.

The following examples illustrate the process of the invention. Unless otherwise stated, parts mean parts by weight. The test methods used in the examples are as follows:

shrinkage

Measurement after washing according to the procedure described below: Samples of approximately 45.7 x 45.7 cm with 25.4 x 25.4 cm markings were made in a household automatic stirring paddle washing machine using 40 ° C, 2.26 kg load weight, household detergent and 15 minutes washing time washed. The washed samples were rinsed, extracted in the washer for an entire cycle, dried flat on a horizontal sieve, pressed flat for 5 seconds at 135 to 150 ° C. and conditioned at 65 ° / o atmospheric humidity and 21 ° C. for at least 12 hours. The samples were then measured in the warp and weft directions to determine shrinkage. Result given in% ^:

Flex wear

ASTM-D-1175-61T (fabric Flex Abrader, 0.23 kg head, 0.9 kg joint). Results in cycles up to Fraction indicated.

stiffness

Cantilever process. ASTM-D-1388-55T. Results given in mg / cm ³ .

Reflectivity

ASTM-E-97-55. 610 photovolt and viewfinder 6104, using the green tristimulus filter.

oil repellency

"Minnesota Mining and Manufacturing Bulletin on Fluorochemical, Appendix A, pp. 1 to 2". The test is based on the different penetration properties of two liquid hydrocarbons, Mineral oil and n-heptane, which can be mixed with one another in all proportions. The penetration properties of the various ones listed below Test liquids are proportional to the heptane content:

No. of the test liquid composition n-heptane
(° / o) or oil repellency value mineral oil
( ¹ Vo) 60 100 (+) 40 50 100 50 40 90 60 30th 80 70 20th 70 80 0 50 100

The sample to be tested is placed on a smooth surface placed, carefully applied a drop of the various test liquids, 3 minutes waited and the Trcpien then observes whether it remains clear and round, the pattern wets (becomes dark) cd: r penetrates. The number of the test liquid, which has the highest hexane content and does not penetrate is the oil repellency value of the sample viewed. Measured after washing (same washing procedure as indicated for shrinkage) and after cleaning (Minnesota Mining and Manufacturing Test Method for laboratory dra cleaning procedure, I.e., p. 4). Treating the samples with the Cleaning liquid in a rotating vessel at 26.7 ° C (± 2.8 ° C) for 3 hours. Taking out the sample and hanging in an oven for 20 minutes at 71 ° C (± 2.8 ° C) dry and let cool for 30 minutes

Tear resistance

ASTM-D-1682-59T, one inch release strip method, figures in kg / cm ² .

Lint

Degree of matting of the surface

Change in the appearance of colored textiles caused by concentrated localized abrasion (Bending is not used when checking for dulling of the surface). The AATCC Gray Scale for Evaluating Changes in Color was used to establish the following rating scale:

ίο 1 major change,

2 significant change,

3 moderate change,

4 slight change,

5 no (or negligible) change.

Wash-and-wear grade AATCC 88A-1964T,

Test IIC1

Color fastness when washed ... AATCC-61-1962 When exposed to light, AATCC-16A-1964

With outgoing
Surface graining AATCC-8-1961

If exposed to perspiration, AATCC-15-1962

Example I.

3 ° A pattern of a plain woven 100 ° / _o by weight wool fabric was treated in the finished state with a liquid for dyeing trifunctional polymer of a PoIypropylenglykoläthers Propyleniminendgruppen with a molecular weight of about 3700th This product can be obtained by the condensation reaction of 50 parts by mole of bound propylene oxide with 1 mole of glycerol. The resulting propoxylate can then be treated with toluene diisocyanate and is then condensed with propyleneimine. The resulting product contains three aziridinyl radicals per mole, has an imine content of 0.65 to 0.76 milliequivalents / g of polymer, a viscosity of about 890 poises and is referred to herein as polymer A from now on. This material is dissolved in a solvent mixture consisting of benzene-dimethylformamide, 4: 1. The polymer A carries three of the following groups per molecule on a polypropylene glycol ether main chain:

The hairy appearance was determined after brushing the textile material on a testing machine for 10 minutes rated by the following scale:

1 heavy lint,

2 considerable lint,

3 moderate lint,

4 light fluff,

5 no (or negligible) lint.

- OCO-NH-

, .CH ₃ * NHCON:

, .C-CH ₃

The lint caused by washing was assessed after washing in the machine at 40 ^° C. and drum drying (twelve such cycles in Example XIII).

The solution contained 4 ° / ₀ Polymer A und.wurde the pattern using a Laborimprägniermaschine applied, wherein the rollers of the impregnating machine were placed on a pressure such that a moisture absorption was / ₀ assured by about 110 °.

The fabric sample thus treated was placed in a frame while maintaining its original sizes stretched and dried at 65 ° C, then hardened for 5 minutes at 135 ° C in a compressed air oven. The

cured fabric was then rinsed in toluene, dioxane and finally water. The pattern was again stretched in a frame based on its original dimensions and dried. The test results obtained were as follows:

'% applied
Reagent / weight VoGz. - K % 'Schrum
S. check after
K S. Flexural strength
Cycles up
to break Rcfljxion 4.4
Untreated
(Control) 3.9 1.5
18.0 2.0
14.5 1.5
20.5 2.5
17.5 550
625 59
. 60

Stgew. = based on the weight of the fabric.
% Gz. =% Weight gain
W = laundry; K = chain; S = weft.

Example II

Pattern of a smooth, 100% wool Fabrics were made in a state ready for dyeing with mixtures of the ones described in Example I. trifunctional polymer (polymer A) and Polyamines by padding from a benzene-dimethylformamide solution, 4: 1, treated. The equivalent ratio of the imine-terminated polymer to the amine co-reactant, the weight ratio was 1: 1 is given below. The treatment steps were described in Example I, except that the moisture absorption was about 120%.

sample

Amine

% Amine% polymer A

In the impregnation solution

total
Reag./Stgew.

% Gz.

B. C. D. E.

Tetraethylene pentamine
Ciäthylenetriamine
1,3-diaminopropane
1,6-diaminohexane

3.49
3.50
3.49
3.44

4.42
4.24
4.28
4.31

4.0
5.5
6.1
6.2

The properties of the treated specimen were as follows:

% Shrinkage ^s Stiff Bend off reflection sample f ung-10 W. 2.5 is called K use ^K 2.5 mg / cm ² Cycles K 57 · B. 1.5 2.0 223 825 57 C. 1.0 2.5 171 700 59 D. 1.0 14.5 172 625 60 E. 1.0 195- 775 60 Untreated 18.0 92 625 (Control)

7th K ο shrinkage S. 1OW K S. stiffness Flex wear re 35 patterns 1.0 kV 3.0 1.0 3.0 K mg / K Cyc flexion 1.0 2.0 2.0 2.0 cm ² len 62 F. 1.5 2.0 1.5 2.0 167 725 61 G 143 675 ■ 59 40 H. 167 650

Example III

Example II was repeated, but polycarboxylic acids were used as co-reactants in place of Amino co-reactants are used in the treatment solution.

Poly-
carboxylic acid Vo PoIy- ⁰ IO 3.42 % Total-
Reag./Stgew. % Gz. sample C3rbon-
acid polymer 3.40 In the mprä- 3.33 Lemons- gnier solution 4.17 5.3 F. Adipine 0.18 4.14 5.3 G Sebacic 0.20 4.31 5.5 H 0.27

The properties of the treated samples were as follows:

Example IV

Patterns of plain weave and twilled woolen fabrics and twilled worsted woolen fabrics were made treated with an aqueous emulsion of the polymer described in Example I.

The emulsion was prepared by mixing 120 parts of a 50 ⁰ / _O solution of polymer 63 A in xylene with 10 parts of the nonionic surfactant Isooctylphenylpolyäthoxyäthanol which was dissolved in 20 parts of water with stirring. The emulsion thus obtained was diluted with water to the desired concentration.

The swatches were treated with the diluted emulsion using a laboratory impregnation device, the rollers of the same set to pressure that ensured a fluid absorption of 80 to 100%.

The thus treated fabric samples were framed while maintaining their original dimension, and dried at 65 ° C, then cured for 5 minutes at 150 ⁰ C in an air pressure furnace. Hardened fabric; Samples were rinsed in an aqueous toluene emulsion (4% toluene, 0.4% isooctylphenylpolyethoxyethanol, 95.6% water) at room temperature for 5 minutes, then washed in water at 38 ° C for 15 minutes, rinsed with cold water and placed on frames. dried.

15th 16

The properties of the treated swatches were as follows:

tissue

% Polymer / weight

% Gz.

% Shrinkage.

5W K [S 1OW
KIS

stiffness
mg / cm ²

Flex wear cycles

Smooth wool fabric, ready to be dyed

Untreated, ready to be dyed

Twilled wool fabric ..

Untreated

Twilled wool fabric dyed green

Colored untreated

Twilled worsted fabric

Untreated, ready to be dyed

3.7 3.6 3.6 3.2

3.1 2.7 2.9 2.5

2.5

19.0

1.5

20.0

5.0 23.5

3.5 33.5

Example V

Patterns of twill fabrics ₀ passed to 100 ° / wool were having in the finished dyeing condition with mixtures of a polymer containing terminal imino groups of an average molecular weight of about 2600 and a Aziridinylgehalt of about 0.65 meq / g, and polyamines such as shown in the table, treated as co-reactants. The polymer is a linear polyester (molecular weight about 2100, made from a diol and dicarboxylic acid of the formula V type), which has the following imine groups on the main chain

17.5 2.0 18.5

5.5 20.0 3.5
30.0
bundle contains:

- OCH —NH-

2.5

28.5

1.5

27.5

6.5
30.0

3.0

26.0

2.0

26.0

6.5
25.5

136

103
203
164

171
105

176
165

_/ CH ₃
NHCON: '

600

475 775 575

400 525

3400 4150

/ C-CH ₃ "

^N CH ₂

It is referred to as polymer B below. A 5: 4: 1 dimethyl toluene acetone solution was used to prepare the treatment solution used. The equivalent ratio of the imine endgrouped Polymer to polyamine was in each case 1: 1, with the weight ratio as given below.

The treatment was carried out in the same way as described in Example I.

example Tetraethylene pentamine
Diethybntriamine
1,3-diaminopropane
1,6-diaminohexane % Amine impreg
gnier solution Polymer B
7o % Total-
Reag./Stgew. »•" Gz. B.
C.
D.
E. 0.11
0.10
0.11
0.16 3.7
3.7
3.7
3.6 4.9
4.9
4.9
4.9 6.3
3.3
1.8
1.7

The physical properties of the treated samples were as follows:

example 2.0 2.0 Flexural wear K cycles • Stiffness K mg / cm ² B. 3.0 2.5 1225 460 C. 9.5 11.5 1100 439 D. 11.5 10.0 - - E. 19.5 15.5 - - Untreated 575 164 Comparison sample

Example VI

Example V was repeated, but instead of the polyamines, polycarboxylic acids as co-reactants used together with polymer B.

example Polycarboxylic acid % Polycarboxylic acid
in the impregnation bath Polymer B
° / o. 7o total
Reag./Stgew. % Gz. A.
F.
G
H none
Lemons
Adipine
Sebazine 0.18
0.20
0.27 3.8
3.62
3.60
3.53 4.8
5.0
4.9
4.9 1.9
1.9
1.8
1.9

409 613/233

17 18

Manufacturing instruction A

Production of a polyfunctional compound with a polyester chain as the main chain and terminal ones

1-aziridinyl residues
• O - O

N —C —O -r- (CH ₂ ) "O - C-1- (CH ₂ )" 0 - C - N—

ο 1 ο Jv ο

Polyesters with terminal isocyanate groups. in which ν = 3 to 4 and η is about 6. "O

HN

H
NCOP- (CH ₂ ) Jr-OC-

O ■ L
1-aziridinyl-terminated polyesters.

The isocyanate-terminated polyester used as the starting material had an isocyanate content of 9.5%.

In a 1-1 three-necked flask, which is equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel, 100 g (0.23 equivalent, based on the isocyanate content) polyester containing isocyanate end groups, in 100 g Methylene chloride was dissolved, given. Ethylene amine (10.7 g, 0.25 equivalent), in 100 ml of methylene chloride dissolved was added dropwise to the solution at 25 to 28 ° C with stirring. Ice addition was after 1 hour ended and the reaction solution obtained homogeneous. The mixture was stirred for a further 5 hours. then

(CH ₂ ) "O — C —N

became solvent and unreacted ethyleneimine distilled off in vacuo, after which the addition product, the ethyleneimine end groups bearing Polyester, as a waxy substance remained.

The product was analyzed for its aziridinyl content using the modified Allan and Seaman method (see Anal. Chem., 27, p. 540 [1955]). An aziridinyl content of 1.73 MHIi equivalent / g was found, compared with 2.06 milliequivalents / g as a theoretically possible value. The Umsetzurg related to the aziridinyl activity was 84 ° / _0th The product was readily soluble in toluene and N, N-dimethylformamide.

Manufacturing specification B

Production of a polyfunctional compound with a polyester chain as the main chain and 2-methyl-

1-aziridinyl end groups

Polyester with isocyanate end groups as in manufacturing instruction A.

"H * · HO 'OH

C-CH ₂ - ^ H ₃ CC _x ; · ■ II / C-CH ₃

N-C - (bound as in manufacturing instruction A) C - N

CH ₂ H ₂ C

Polyesters with propyleneimine end groups.

In a 1-1 three-necked flask fitted with a stirrer, thermometer, reflux condenser, and Was provided with a dropping funnel, 14.2 g (0.26 equivalent) of propyleneimine, dissolved in 50 ml of methylene chloride, brought in. 100 g (0.23 equivalent) of the isocyanate-terminated polyester in 150 ml of methylene chloride dissolved, was added dropwise with stirring at 25-28 ° C. (The isocyanate end groups Supporting polyester had the same composition as that in Preparation A as the starting material was used, but both the order of addition and the alkyleneimine were different different according to manufacturing instruction A.)

CH,

The addition was complete within 1 hour, and the reaction solution obtained was homogeneous. The stirring was continued for another 5 hours. Then solvent and unreacted propylene

imine is distilled off in vacuo, the addition product, Polyesters bearing propyleneimine end groups remained in the form of a waxy substance.

The product was investigated according to the analytical method specified in manufacturing instruction A.

and found 1.60 milliequivalents aziridinyl nitrogen / g. As a result that the reaction to 80 ° / _o was ig. This product was readily soluble in toluene and in N, N-dimethylformamide.

19 20

Manufacturing instruction C

Production of a polyfunctional compound with a polybutadiene chain as the main chain

and 1-aziridinyl radicals as end groups

First stage
/ NCO

20CN - <(VCH ₃
HO (- CH ₂ CH = CHCH ₂ -) _U OH > polybutadiene with hydroxyl end groups (w = 60 ± 5).

OCN _x

> _x H 'H

H, C - <V - N - C - O (- CH ₂ CH = CHCH ₂ -) «O - C - N

O O

Isocyanate-terminated polybutadiene.

Second step

C-Νζ HN ^ ¹

H H /

■ NC-0 (-CH ₂ CH = CHCH ₂ -) _U OCN- /> _ CH ₃

Il Ii V _ / ^

O O

1-aziridinyl-terminated polyesters.

The hydroxyl used as starting material was kept at ^{20 ° C.} After the addition, the polybutadiene bearing the end groups was stirred into a Hy solution at 25 to 28 ° C for 8 hours,
droxylf ehalt of 0.80 milliequivalent / g, an iodine number. Then the second stage, the addition of the

of 395 and an average molecular weight of 40 1-aziridinyl residues. Ethylene imine (12.9 g, of 3250 ± 250. Before its use, the 0.3 mol), dissolved in 100 g of methylene chloride, was the Resin was added dropwise to solution in vacuo in a gently rotating flask with stirring. the Treated for several hours to remove moisture. Zugabs was finished after 2.5 hours while distant. this time the temperature of the reaction was up

The first stage of the manufacturing process consists of 45 being held at 25 ° C. The solution was stirred for a further 4 hours to convert the hydroxyl end groups. Then the solvent was lowing polybutadiene in the isocyanate end groups and the unreacted ethyleneimine in a vacuum ablating polybutadiene. In a 2-1 three-necked flask, distilled. The product (223 g) that remained was that of a stirrer, thermometer, a light brown viscous liquid.
Gas inlet tube and a dropping funnel provided 50 The Procu'ct was according to the manufacturing process, 200 g of the hydroxyl end groups carrying method A were analyzed and the polybutadiene, dissolved in 200 g of methylene chloride, 1.00 milliequha! Ent aziridinyl / g determined, filled. 43.6 g of toluene diisocyanate (0.25 mol of compared to the theoretical amount of 0.97 milli-2,4- and 2,6-isomers in the ratio 80:20) were equivi lent / g. The product, polybutadisene with ethylene added slowly while a nitrogen stream in 55 imine end groups, was readily soluble in toluene, benzene, the solution was bubbled and the temperature set to tetrahydrofuran and carbon tetrachloride. .

Manufacturing specification D

Production of a polyfunctional compound with a polybutadiene chain as the main chain and 2-methyl-

1-aziridinyl radicals as end groups

H HO OH

/ C-CH ₃ H ₃ C-C _x Η,,,. ... ".., II / C — CH ₃

CH2 H ₂ C ■ CH ₂

Polybutadiene with propyleneimine end groups.

First, 85.3 g of polybutadiene bearing hydroxyl end groups, dissolved in 50 g of methylene chloride, were introduced into a 503 ml flask equipped as described in Preparation C. 18.5 g of toluene diisocyanate (0.16 mol of 2,4- and 2,6-isomers in a ratio of 80:20) were slowly added while a stream of nitrogen was passed into the solution and the temperature was kept at 20 ^° C. After the addition, the solution was stirred at 25 to 28 ° C. for a further 16 hours.

- Then 6.7 g (0.18 mol) of propyleneimine, dissolved in 50 g of methylene chloride, were added dropwise within added to the stirred solution for 3 hours. The solution was stirred for a further 4 hours. Then the solvent and unreacted propyleneimine were distilled off in vacuo. The one left behind The product was a light brown liquid.

The product was analyzed according to the method specified under manufacturing instruction A and found that it was 0.90 milliequivalent aziridinyl nitrogen / g . compared to 0.97 milli-equivalent / g than the theoretically possible amount. The product, polybutadiene with propylenimine end groups, was easily soluble in toluene. 2 ·;

Example VII

Improvement of the surface properties of a fabric made of viscose rayon wool, 70:30, by Polymer bearing imine end groups

A smooth woven fabric made from a mixture of highly tear-resistant viscose rayon and wool, 70:30, was treated with polymer bearing propylenimine end groups according to Example I, so that 4% of the reagent, based on the weight of the substance. The fabric sample treated in this way was under Keeping its original dimensions, framed, dried at 65 ° C (in about 10 minutes) and then cured at 135 ° C for 6 minutes. The cured fabric was made with an emulsion made from 4 parts of toluene, 0.4 parts of isooctylphenyl polyethoxyethanol and 95.6 parts of water, rinsed. Then became the fabric sample again framed and dried while maintaining its original dimensions. The results, which are given below in comparison with an untreated control sample, clearly show that the treatment improved surface properties and even strength slightly increased.

lint Tear resistance Flex wear Degree Cycles (head kg / cm ² weight 0.45 kg (2.54 cm Gag 1.81 kg Stripes, S) Voltage, K) Treated 4th sample 4.27 585 (warp direction) Untreated Control 2 sample 3.92 260 (shot By S direction) pi el VIII

Controlled improvement in the shrinkage and lint of a viscose-rayon-wool fabric (50: 50) due to imine end groups

polymer
30th

A plain woven fabric, woven from a mixture of wool and viscose rayon, 50:50, was made treated with the polymer carrying propylenimine end groups, as described in Example I, so that 3.5% based on the weight of the substance, the Reagenz2S. The conditions regarding Framing, drying, hardening, rinsing, reframing and re-drying were the same, as in the example VII described. The following results,

dij on this and an untreated control sample show that the treated pattern was far more satisfactory for shrinkage and lint Values were given as the control sample.

IW

Shrinkage,%
Drum dry at 40 ^° C
¹ 5W

K! S.

1OW

Lint level

Treated pattern,

Untreated control sample

4.0
14.0

4.0
16.5

5.0
19.5

4.5 5.5

2 4th

Example IX

Dimensional stabilization of wool fabrics by

Treatment with ethyleneimine end groups bearing

Polybutadiene

Mu £ t2r of smooth woolen fabrics in for dyeing finished state ■ were mixed with various concentrated solutions of the preparation method C prepared reagent, namely polybutadiene with ethyleneimine end groups treated. Concentrations and further details can be found in the following table. When making certain patterns Tetraethylene pentamine (TEPA) was also used in the impregnation bath. The solvent was toluene-dimethylformamide (1: 1). The solution was applied to the fabric samples using a laboratory impregnation device (Scoring device) applied. After impregnation the fabric was framed while maintaining its original dimensions and dried at 65 ° C. All samples were cured for 5 minutes. The hardened fabric was treated with toluene, then with paradioxane and finally rinsed with water containing 0.4% isooctylpolyethoxyethanol. The patterns were then framed and dried while retaining their original dimensions. It was excellent Dimensional stabilization achieved as shown by the results below:

Status Treated
Fabric length Liquid
admission, ° / o wear
Cycles
(1 x 4, wet) Shrinkage from washing S. ash, 4O ⁰ Q
weakly tense
1OW 1.5 (15 cm markings, i, o K I S 3.5 • Composition of the
Tissue Colored 35 52 ■ 650 . Mach
Drum drying
5W 3.0 1.0 0.5 control untreated 525 K 0.5 1.5 "1.5 55 ° / ₀ polyester fiber / Uncolored 35 51 775 1.0 1.0 1.5 3.5 45 ° / ₀ wool Colored 35 50 875 1.5 2.0 0.5 control untreated 775 1.5 0.5 3.0 10 ⁰ I ₀ polyester fiber / Uncolored 60 50 1050 0.5 1.5 0.5 4.0 30 ° / ₀ wool Colored 50 56 650 0.5 3.5 2.5 2.5 control untreated 525 ■ 0.5 2.0 2.5 1.0 55 ° / ₀ acrylic fiber / Uncolored 50 55 725 1.5 0.5 1.5 2.5 45 ° / ₀ wool Colored 50 57 575 2.5 2.5 1.5 1.5 control untreated 425 1.0 1.0 2.5 70 ° / ₀ acrylic fiber / Uncolored 50 59 500 1.5 1.5 30 per cent wool 2.5 1.5

Example X

Dimensional stabilization of wool fabric by treatment with polybutadiene with propylenimine end

groups .

A. Impregnation Bath Solvent: Toluene-Dimethylformamide (1: 1)

Samples of a smooth woolen fabric ready for dyeing were concentrated with various concentrations Solutions of the reagent which had been prepared according to manufacturing specification D, namely Polybutadiene with propylenimine end groups. For some samples the treatment was with Tetraethylene pentamine (TEPA) made as a co-reactant.

The treatment was carried out as indicated in Example IX.

The results, which are summarized in the table below, show that this polymer with terminal Imine groups give excellent shrinkage resistance.

sample % of Bac
Reagent weight
TEPA Liquid
admission, % Total allowance
% on weight
of the fabric Hardening temperature
⁰ C (time = 5 Wed
grooves) Shrink!
5W
KS 2.0 ung, o / _o
1OL
K j S 2.5 A-I 5.0 127 6.3 135 1.0 1.5 1.5 1.5 A-2 5.0 126 6.3 163 1.0 1.5 1.5 2.0 BI 5.0 0.5. 123 6.1 135 1.5 3.0 1.5 3.0 B-2 5.0 0.5 120 6.0 163 0.5 2.5 1.0 3.0 C-I 3.0 122 3.7 135 1.5 1.5 2.0 2.0 C-2 3.0 - 118 3.5 163 1.5 2.0 2.0 2.0 D-I 2.9 1.0 123 3.6 135 1.0 1.0 1.0 1.5 D-2 2.9 1.0 120 3.5 163 1.5 22.5 1.5 29.0 Untreated 25.0 32.0 Control pattern

B. Impregnation bath solvent:
Toluene-dimethylformamide (5: 1)

It was proceeded as described under Part A, except that the weight ratio of toluene to dimethylformamide was now 5: 1 instead of 1: 1 and the reagent was used in lower concentrations in order to be effective than To determine shrink-proof finishing agents. As above, the shrinkage resistance was very pronounced, What. also reveal the following ■ results:

° / o of the bath weight TEPA Fluid- Total on Hardness temperature * SchrumDfune. ° / " K W. S. 1OW K I s Bend off stiffness Sample ' _ KCIldclLlL
would take% recorded "" temperature ⁰ C 2.5 1.5 2.5 1.5 use IVl UoLUl Reagent " - 127 Weight of (Time = 5 Wed 5 2.0 2.5 2.0 3.5 0.23 x 0.90 kg mg / cm 3.0 - 123 Tissue grooves) 2.5 2.5 2.5 3.0 (Chain) (Chain) P. 2.0 0.6 121 3.8 135 1.0 2.0 1.0 2.5 900 585 Q 1.0 0.4 128 2.5 135 3.0 2.5 3.0 2.5 850 515 R. 3.0 0.2 123 1.2 135 6.5 6.0 8.5 7.5 715 270 S. 2.0 121 3.8 135 24.0 20.0 30.0 27.5 875 620 T 1.0 2.5 135 900 270 U Untreated 1.2 135 950 145 Control pattern 675 90

Example XI

Dimensional stabilization of woolen fabrics by treatment with ethyleneimine end groups polyester

Pattern of smooth wool fabric in ready for dyeing

Solutions of the reagent prepared according to manufacturing instruction A, namely ethyleneimine end groups load-bearing polyester, treated. When treating some specimens, a co-actant was found, viz Tetraethylene pentamine (TEPA) is used. The procedure described in Example IX was followed. Excellent Shrinkage strengths were achieved what

Condition were shown with different concentrated values as shown below.

sample % of the bath
weight TEPA Liquid
admission * Weight on
recorded%
Weight of Hardening temperature
rature ⁰ C (time Shrinks
5W Young,%
1OW 2.5 Reagent Tissue = 5 minutes) K) 'S K: S ■ 2.0 A-I 5.0 133 6.6 135 1.0 '2.0 1.5 3.0 A-2 5.0 .0.5 133 6.6 163 0.5 j 2.0 1.0 3.0 BI 5.0 0.5 133 6.6 135 1.5 J 3.0 2.0 3.5 B-2 5.0 - 131 6.5 ■ 163 1.0; 2.0 ' 1.5 3.5 C-I 3.0 - 132 4.0 135 1.5: 3.0 2.0 4.0 C-2 3.0 0.5 130 4.0 163 1.0, 3.0 1.5 4.0 D-I 3.0 0.5 134 4.0 135 1.0! 3.0 2.5 29.0 D-2 3.0 130 3.9 163 1.5. 2.5 2.0 Untreated 23.5 I 22.5 30.0 Control pattern :

■ Example XII

Dimensional stabilization of woolen garments in a load-bearing condition by means of shrink-proofing agents, applied from perchlorethylene solutions
Identically knitted woolen sweaters were impregnated with perchlorethylene solutions of the polymer bearing imine end groups, as indicated in Example I and referred to below as polymer A. Excess impregnation solution was removed from the sweaters by centrifugation. Processing details are listed in the table below, followed by the values for the shrinkage during processing and repeated washing.

pullover
sample % Shrinkage
fixing
medium in
Perchlorethylene Centrifugation
time,
Seconds liquid
recorded,
% Solids,
%, based
on weight
of the fabric drum
drying
(Hardening)
Time, minutes Other treatments before
Measure shrinkage W.
X
Y 10%
. Polymer A
10%
Polymer A
10%
Polymer A 7th
8th
5 154
103
234 15.4
■ 10.3
23.4 60
60
60 15 minutes in toluene water
(4:96) ^{washed at 4O 0} C,
then dried in the drum
as with W
washed at 6O ⁰ C, then in
Drum dried

xsanu Machining shrinkage,% Width on sleeve Upper Shrinkage from washing after ten washes
and tumble drying% move Width on sleeve Upper 12.7 move other end length expanse "Thu / 4 length other end length expanse 10.7 length none 5.6 none ttana. 2.4 +0.8 2.4 none W. 5.7 10.6 none 5.6 none none 2.4 none 2.4 none X - 9.9 - 2.3 +0.7 none 2.3 - +3.5 none Y 4.3 - - - 1.4 33.3 - 20.4 - Untreated - 27.2

Example XIII

60

Improvement of dyed acrylic-wool fiber mixtures by imine end-group-bearing polymer, especially with regard to lint and abrasion resistance ^6s

Each of three 27.43 m long, colored fabrics made of different compositions, in the

Acrylic wool fiber mixtures given in the following table was impregnated with a dispersion prepared as follows. First was Polymer A (the polymer carrying imine end groups, which is described in Example I) dissolved in the same amount by weight of xylene and a thick emulsion through Mixing 80 parts of this emulsion with 20 parts of a mixture of water and isooctylphenyl polyethoxyethanol 2: 1 made. The concentration

of polymer A in this thick emulsion was 40 ° / _0th Then, an about 3.9 ° / _o strength prepared by mixing Polymer A dispersion of 40.8 kg of this thick emulsion and 378.5 1 water.

The liquid uptake was about 50 ° / ₀ , the pad pressure 16 t and the speed 22.86 m / min. For the combined dry-cure step, the conditions were 149 ° C for 4.83 minutes. First, the lengths were purified at 38 ° C. for 15 minutes in a dispersion prepared from 4 parts of toluene, 4 parts of a nonionic dispersant, nonylphenyl polyethoxyethanol, and 95.6 parts of water. The lengths of fabric were then rinsed until no more foam appeared. After drying, the goods were given a drying finish by shearing off the lint and semi-decorating (steam was pressed between two pieces of fabric.) The results obtained with the treated acrylic-wool fiber mixtures and with untreated control samples are tabulated below. The values show a considerable improvement in lint level compared to the corresponding untreated swatches, both before washing and after twelve washes. The wash-and-wear properties were not adversely affected. The resistance to flexural wear and matt values of the. The surface either remained unchanged or was improved by the treatment.

is

Composition of the dyed fabric

Degree of lint No. W I 12 W.

Dull the
surface

(1.13 kg,
1200 cycles)

Resilience to
Bending wear (head 0.45 kg
Gag 1.81)

Chain I weft

55 ° / ₀ acrylic / 45 ° / ₀ wool fibers

the same, untreated control sample

65% acrylic / 30% wool / 5% viscose rayon

the same, untreated control sample

70% acrylic / 30% wool fibers

the same, untreated control sample

Claims (2)

Claims: 5 3 3 - 4 1 4 2 4 3 3 1 4.5 4.5 4.3 4.5 3.5 3.5 3.5 3.5 3.0 3.5 3.5 3.5 4 3 5 5 525 500 225 150 375 275, 800 800 525 300 575 475 1. A method for felting and shrinkproofing of at least 30 ° / ₀ wool-containing textile material by treatment with Amidoaziridinen, characterized in that at least 30% wool textile material containing 'with an at least about 0.5 weight percent - based on the weight of the wool - A solution of an amidoaziridine compound of the general formula containing, having a pH of about 0.3 to 9.0 and optionally containing polybasic acids or polyamine compounds H H c — N-Q- N — c — n: R ¹ R ²
R ³ treated, in which R - (- 0 -) - _{m is} an aliphatic or alicyclic polyol radical and R ₁ , R ₂ and R _{3 are} either hydrogen atoms or alkyl groups with 1 to 4 carbon atoms, Q is an optionally alkyl-substituted aromatic group with 6 to 18 carbon atoms leaves, and m is the number 2 or 3, then released, the fabric of excess treatment agent, optionally at a temperature between room temperature and dried about 163 ° C, then either several hours at room temperature or exposed to several minutes temperatures from 93 to 150 ⁰ C and if necessary washes out. 2. The method according to claim 1, characterized in that that the textile material with an amidoaziridine compound of the general. formula H H —C — ν — Q — ν — c — n: ji O , R ¹ R ²
R ³ 29 30 treated, in which R ₁ , R ₂ , R ₃ , Q and m have the meaning given in claim 1 · and R - (- O -) - is one of the following radicals . (i) - O (--CH ₂ CH = CHCH ₂ -) "O". - wherein u has a value from about 6 to about 100;
(II) - O - UCHJ _n - O - C --I (CHJbO - L O J « wherein η = 2 to 6 and ν = 3 to 80; (III) - (- OC ₀ H ₂₀ -) * - O - LO (—C ₀ H ₂₀ O—) jr- where χ and y = 1 to 100, a = 1 to 9 and L is a divalent organic radical, so that the whole group has a molecular weight of about 500 to about 5,500. (IV) - (- OC ₀ H ₂₀ -) * - O _x \ _M - O - (C ₀ H ₂₀ O-) _r - (- OC _O H _2O ) _Z - 0 ^/ wherein x, y and ζ are between 1 and 100, α is 1 to 4 and M is a trivalent aliphatic group; and (V) - O - ₁ - (CH 2) PO - C _{- (CH 2} ) _ff --COT (CH ₂ ) - OOJ _r
where ρ is 2 to 6, q is 4 and r is 2 to 35.