DE2413265A1 - NEW HAIRABLE ESTER MASSES - Google Patents

Description

■ Τ 49 333

Applicant: Γ WS Nominee Company Limited

Wool House, Carlton Gardens, London SW1, England

New hardenable ester masses

The invention relates to new curable ester compositions which are derived from esters of unsaturated aliphatic hydroxycarboxylic acids derive, and a procedure to use it to treat keratinous fibers.

It has been proposed to use polyisocyanates for shrink resistance treatment to use solid materials. These resins are usually dissolved in the form of prepolymers in organic solvents, because the prepoly * ■ meren, depending on which one is used, in different React extent with water. Some of the less reactive prepolymers can be used as an aqueous emulsion obtained by dissolving the prepolymer in a water-insoluble solvent and then the Solution dispersed in water with the help of a surfactant.

Known polyisocyanates first give wool materials a high degree of shrinkage resistance. However, it was found that they have poor lightfastness with the result that the materials treated with the resins their Losing shrinkage resistance when exposed to light are. It has also been found that the lightfastness of the treated materials is even worse when the treated materials are washed.

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The invention relates to polyesters (this term also includes diesters) of polyhydric alcohols and ethylenically unsaturated higher aliphatic hydroxycarboxylic acids, more precisely from acids containing more than 10 carbon atoms contain, "for example of ricinoleic acid (= ricinoleic acid), in which the residues of two or more converted hydroxyl groups of the acids are connected to other organic radicals by appropriate ester bonds each of which is an isocyanate group, a blocked one or masked isocyanate group or a thiosulfate group which allow the ester to be cured to form resin. The other residues mentioned contain usually an atom or group of atoms that facilitate the formation of ester bonds during ester synthesis or activate.

The invention also provides a method of making keratin fibers such as sheep's wool by using the above to treat defined esters or prepolymers. This treatment allows a wide variety of equipments that are in the are described below.

Various polyols can be used to form the polyricinoleates, for example ethylene glycol, glycerol or a sugar such as pentose or hexose, but the preferred ester is glyceryl tricinoleate. The ester can be used neat, although castor oil, which is commercially available, is generally quite satisfactory. Castor oil contains approximately 90% triricinoleate and the remaining 10? 6 consist of a mixture of highly saturated and unsaturated fatty acids.

In the first stage in the production of the new ester from a polyricinoleate, the ricinoleate is mixed with a carboxylic acid, whose carboxyl group is sufficiently reactive that esterification takes place, esterified. Generally are

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Carboxylic acids in which the carbon atom attached to the carbon atom is adjacent to the carboxyl group ", a halogen atom, a thiol group or a hydroxyl group is bonded or which forms part of an ethylene bond is most satisfactory.

A wide variety of carboxylic acids and their anhydrides can be used to convert castor oil to the desired ester intermediates; For example, mono-, di- and tri-chloroacetic acid (DL) - malic acid, citric acid, L ( ⁺ ) -tartaric acid, o-phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, benzene-1,3,5-tricarboxylic acid, fumaric acid, itaconic acid , Mesaconic acid, citraconic acid, tetrahydrophthalic acid, endo-ethylenetetrahydrophthalic acid, tetrachlorophthalic acid, 4,4-bis (4-hydroxyphenyl) pentanecarboxylic acid, succinic anhydride, cis-hexahydrophthalic anhydride, phthalic anhydride anhydride, tetrahydro anhydride, tetrahydro anhydride, tetrahydro anhydride, tetrahydro anhydride, tetrahedral anhydride, tetrahedral anhydride, tetrahedral anhydride, tetrahedral anhydride, tetrahedral anhydride, trimellitic anhydride, tetrachlorophthalic acid, tetrachlorophthalic anhydride, -Use maleic anhydride and tetrachlorophthalic anhydride. One can also use the bromine analogs of the above-mentioned chlorine-containing acids and anhydrides.

It has been found that in general maleic acid and its anhydride and chlorinated dicarboxylic acid and its anhydride (see formula in Example 3) give particularly good results. The ester formation can take place in a manner known per se, the reactants being dissolved in an inert, organic solvent, for example toluene, trichlorethylene or tetrachloroethane, and then under esterification conditions in the presence of 0.5 Ms 1.0 % by weight of an esterification catalyst, for example p-toluenesulfonic acid. The amount of carboxylic acid used in the reaction will depend on the number of hydroxyl groups to be esterified. Preferred

409839 / 1OS3

a slight excess of the acid is used to ensure the formation of as much of the triester as possible. The solution of the desired product can be washed with water to remove any excess of carboxylic acid and remove catalyst. The solution is then treated with a suitable drying agent, for example Magnesium sulfate, dried.

Isocyanates are obtained by adding the ricinoleate ester and a suitable diisocyanate in an inert solvent dissolves and then heats the mixture until the formation of carbon dioxide ceases.

Various diisocyanates can be used, for example the reaction product of 3 moles of hexamethylene diisocyanate and 2 moles of water [i.e. N, N'-bis (6-isocyanatohexyl) urea] (for example Desmodur N from Bayer). Dimer acid diisocyanates (D.D.I), isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1-methylcyclohexane-2,4-diisocyanate, Bis (4-isocyanatocyclohexyl) methane can also be used.

Aliphatic diisocyanates, especially hexamethylene diisocyanate, are most preferred because they have been found to give products that have greater durability show towards the yellowing.

The ricinoleate isocyanates prepared in this way can be different Modified ways to give them different properties. For example, they can easily are halogenated, with 2 halogen atoms saturating each of the ethylenically unsaturated bonds in the castor oil residue or in the radical which originates from the unsaturated ester group, if one occurs. If you use as halogen, bromine, the resulting compounds have a higher fire resistance than known polyisocyanates

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or other shrink-resistant resin agents. The halogen derivatives also make the treated woolen materials more resistant to attack by pests such as moths are.

The isocyanate compounds of the invention can also be formed by removing those in the ricinoleic acid residues existing hydroxyl groups with a thiol-containing organic acid, for example thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, D, L-mercaptosuccinic acid, o-mercaptobenzoic acid or cysteine, esterified, for example by adding castor oil and the thiol containing Acid in the presence of an inert organic solvent, for example toluene, heated to reflux.

The product is then further treated with an excess of diisocyanate reacted, whereby a derivative is formed which contains two or more isocyanate groups per molecule.

The isocyanates have the advantage that they can be converted into stable compounds, which are inert to moisture can be converted, but which nevertheless easily return to the original reactive isocyanate can be converted if they meet conditions that are customary in textile processes or processing methods occur, be exposed. These inert compounds are obtained by adding the isocyanate group masked by treatment with a large number of masking agents (= blocking agents), for example with tertiary alcohols, e.g. tert-butanol, secondary aromatic Amines, e.g. diphenylamine, mercaptans, e.g. butyl- ■ mercaptan, lactams, e.g. ε-caprolactam, and monohydric Phenols, e.g. phenol or cres oil.

Particularly good results are obtained when alkali metal, Ammonium or amine bisulfites, especially sodium bisulfite, are used, as the resulting masked

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bonds are cheap to make and require low temperatures to split off the protecting groups. For example, the process takes place very easily if a woven or knitted material with a compound masked with bisulfite is treated with steam ^{at 100 ° C. for a few minutes.} Another advantage of the bisulfite compounds is that they are in many cases water-soluble and so, in contrast to known, shrink-resistant isocyanate resins, can be used in the form of aqueous solutions.

Masked or protected compounds can easily be obtained by mixing the reactant solutions and ensures that while the implementation takes place, the mixture is kept under highly homogeneous conditions. Particular care must be taken when using the masking agent is a water-soluble bisulfite that is used in aqueous or alcoholic aqueous solution and the isocyanate, which is masked is dissolved in a water-insoluble solvent.

Ricinoleate esters can easily be converted into thiosulfates by a two-step process in which a halogen-activated carboxylic acid is reacted with a ricinoleate ester. The resulting ricinolea halogen ester is then treated with an alkali metal, preferably sodium, thiosulfate, the halogen atom being replaced by the thiosulfate group. The first stage of the process is usually carried out by heating a mixture of the ester and the acid dissolved in an inert solvent, for example toluene, under conditions in which the water formed is removed. The reaction mixture is then washed with water and washed with a water-soluble organic solvent, for example 2-ethoxyethanol, and an aqueous solution of sodium thiosulfate. The mixture is then heated at a temperature of 60 to 100 ^{° C. for 30 minutes to 6 hours.}

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The compounds or prepolymers used according to the invention for keratin fibers such as wool can be used in amounts which vary widely, for example from 0.5 to 15% by weight, based on the wool present, although the best results are usually obtained when using from 1 to 4 wt. $ 6. The compounds can either be used in solution in an organic solvent, for example a chlorohydrocarbon such as trichlorethylene, or as an aqueous solution or emulsion, depending on whether the compound is masked or unmasked and whether it has sufficient stability in the presence of water or moisture that it can be applied before condensation occurs. The beneficial effects of the compounds only develop once they have been cured. This procedure takes place in 1 to 10 days at ambient temperatures. The process can, however, be shortened considerably by treating the treated materials ^{with steam at 100 °} C. for 5 to 60 minutes or by treating the materials in an autoclave for 5 msec for 15 minutes. When using a polyisocyanate as the prepolymer, it is desirable to ensure that moisture is present to allow the compound to hydrolyze and condense.

The following examples illustrate the invention without restricting it.

example 1

Castor oil (102 g) is dissolved in toluene (200 g) along with a slight excess of maleic acid (42 g) and p-toluenesulfonic acid (1g) solved. The mixture is heated to reflux and the released water is plugged into a Dean-Stark tube removed. The acid slowly dissolves as the reaction proceeds. After which the theoretical amount of water is removed (5.8 ml), the mixture is washed three times with water,

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to remove excess maleic acid and p-toluenesulfonic acid, and then dried over magnesium sulfate.

It is assumed that the implementation proceeds as follows:

CH OCO (CH) CH = CH CH ₀ CH (CH) CH

I 2 2 7 ** I <4 p.>

OH

CH OCO (CH) _ CH = CH CH CH (CH _O ) _ CH "+ 3 HOOC-CH = CH-COOH -P-

2 7 ^ l * J>

OH

CH ₀ OCO (CH) CH β CH CH ₀ CH (CH) CH

2 ύ ( ώ j <ä ->>

OH

CH OCO (CH) CH rx CH CH CH (CH) CH

2 ct f <ä J £ Z> S>

OCOCH β CH COOH

CH OCO (CHj_ CH β CH CH ₀ CH (CH _O ) _ CH + 3HO 2 7 ^ l "P ^"

J · OCOCH = CiI COOH CH _n OCO (CH) _ CH = CH CH. CH (CH _O ) _ CH

2 c, f a I «ip P

OCOCH = CH COOH

The washed maleic acid ester (A) of castor oil (134 g) is dried azeotropically with toluene (200 g). After cooling, a small excess of hexamethylene diisocyanate (60 g) is added. The mixture is ^{heated at .80 0} C with continuous stirring for about 4 hours. After this time, the formation of carbon dioxide has ceased and it is believed that the reaction has ended, with an isocyanate-terminated prepolymer being formed. The toluene and the excess hexamethylene diisocyanate are removed on a rotary evaporator.

It is assumed that the reaction in the second stage proceeds according to the following scheme:

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CH OCO (CH ₀ ) .. CH = CH CH. CH (CH ₀ ) CH

2 af ύ Ι Δ \) J

A + 3 OCN (CH J.NCO ■ OCOCH a CH CONH (CH) .NCO

CHZOCO (CI!) _ CH = CHCH ₀ CH (CH _O ) _ CH «d I <! ι & j ρ

CCOCH = CH CONH (CH ₀ ) .NCO + 3C0

2 ο «2

CH OCO (CH) CH = CNCH ₀ CH (CH) CH 2 2 7 2 j 2 ρ Ρ

OCOCH β CH CONH (CH _o ), NC0

2 O

Example 2

Castor oil (100 g) and a small excess of maleic anhydride (33 g) are heated together until the temperature reaches the melting point of the anhydride (50 ^° C.). The heating stops, but the temperature rises to 85 to 90 ^° C. in the course of about 30 minutes. The temperature is kept at 85 to 90 ^° C. for a further 11/2 hours.

It is assumed that the implementation proceeds as follows:

CH (CH ₂ ) ₅ C OCOCH = »CHCOOH

Il

OCO (CH ₂ ) ₇ CH = CH CH ₃ CH (CH ,,) _? CH ₃

CH-C _x
Castor oil + 3 | 0->

CH-c'CH OCO (CHj _n CH = CH CH ₀ CH (CH ) _r CH

11. 2 7 <* I <* ->■>

0 I OCOCH e CHCOOH

CH OCO (CH ₂ ) CH β CH CH ₃ CH (CH ₃ ) CH ₃

OCOCH = CHCOOH

The product B (134 g) is dissolved in toluene (200 g) and treated with hexamethylene diisocyanate (60 g) as described in Example 1 implemented, being a prepolymer with terminal isocyanate groups receives.

Example 3

This example illustrates the use of chlorinated dicarboxylic anhydride the formula

ei 0

^ II

Cl

Cl 0

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24132S5 - ίο -

explained. Chlorendicarbonsäureanliydrid (102 g) is reacted under stirring with castor oil (200 g) until the temperature of 60 ⁰ C was reached. The temperature continues to rise to 185 ^° C. due to the heat of reaction. After cooling further Chlorendicarbonsäureanhydrid (120 g) is added and the temperature is raised for 2 hours at 130 ⁰ C. The cooled product is very viscous and its IR spectrum shows the absence of hydroxyl groups and the presence of a carboxyl group.

The reaction product is dried by distilling off excess water as an azeotrope with toluene (200 g) and adding a slight excess of hexamethylene diisocyanate (119 g). The mixture is at 90 ° C for 3 hours heated, during which time a strong formation of carbon dioxide occurs. The IR spectrum shows the disappearance the broad carboxyl band and the appearance of a sharp one Isocyanate peaks at 2270 cm.

Example 4

500 g of the maleic acid ester of castor oil, prepared as described in Example 1, are dissolved in toluene (200 g). The solution is then continuously stirred while bromine (304 g) is slowly added over the course of 1 hour. The mixture is chilled in ice / salt to keep the temperature below 50 ° C. The amount of bromine added is sufficient for the conversion of approximately 75% of the double bonds present. The product is washed with water until the pH of the aqueous extract is 5-6 and then dried over calcium chloride.

The partially brominated product (500 g) is then azeotroped with toluene (200 g). After cooling, a small excess of hexamethylene diisocyanate (140 g) is added and the mixture is stirred at 80 ^° C. during

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heated for about 4 hours. The mixture is then stirred at room temperature overnight. Both toluene and excess Hexamethylene diisocyanate is removed on a rotary evaporator.

Example 5

In this example, the production of a castor oil polyisocyanate is explained, which by treatment with Sodium bisulfite is masked.

100 g polyisocyanate, produced according to the process, which is described in Example 1, are dissolved in a mixture of 2-ethoxyethanol (500 g) and toluene (50 g). A solution of sodium meta-bisulfite (19 g) is added to this. in water (70 g). The mixture is stirred at room temperature, further alcohol or water is added as is is required to get the polymer and the bisulfite in solution to keep. The toluene and other solvents are removed by distillation. The resulting product is soluble in water and when it is analyzed by IR spectroscopy, represents it is found that the isocyanate peak is absent at 2270 cm.

Example 6

100 g of isocyanate derivative brominated castor oil, prepared according to the procedure of Example 4, are dissolved in a mixture of 2-ethoxyethanol (5 ⁰ O g) and toluene (500 g). A solution of sodium meta-bisulfite (15 g) in water (50 g) is added to this. The mixture is stirred, additional alcohol or water is added as needed to keep the polymer and bisulfite in solution. The reaction mixture is kept for 2 hours, after which the solvents are removed by distillation. The IR spectrum of the dried and solvent-free sample shows the absence of the free isocyanate peak.

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E.g. example 7

Castor oil (93 g) is dissolved in toluene (200 g) together with thioglycolic acid (10 g) and toluene-p-sulfonic acid (1 g). The mixture is heated to reflux and the water released during the reaction is removed azeotropically with toluene with a Dean-Stark tube. After approximately 4 hours the theoretical amount of water for complete conversion (5.4 ml) was removed. The mixture is washed three times with water, then the aqueous extract, the pH was increased to 6 to 7, which indicates that excess Thiogl3 ^r kolsäure and toluene-p-sulphonic acid were removed. The product solution is dried over anhydrous magnesium sulfate overnight, filtered and the toluene is removed on a rotary evaporator, giving a yellowish viscous oil with a solids content of 86? O.

The main resin component of the oil is believed to be a compound of the formula

) CH = CHCH CH (CH ₀ ) _CH

7 <i | «4 P >

OCOCH SH

CHOCO (CH_) _ CH = CHCH

2 7 «M "■>

OCOCHSH

CH ₂ OC0 (CH ₂ ) _? CH = CHCH ₂ CH (CH ₂ J ₅ CH ₃

OCOCH SH 2

This thiol resin (100 g) is dissolved in toluene (130 ml) and a small excess of hexamethylene diisocyanate (44 g) is added dropwise. The mixture is 90 minutes heated to reflux and towards the end of this time, the toluene and excess hexamethylene diisocyanate are reduced Pressure evaporated to give a pale yellow, viscous liquid containing free isocyanate groups. A sample of the product forms a gel on standing in air and is believed to have the formula

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CH-OCO (CH ₂ ) CH = CH CH ₂ CH (CH ₂ ) CH

I OCO CH S CONH (CH ₀ ), NCO

CH OCO (CH ₂ J ₇ CH η CH CH = CH

₂₅₃

OCO CH ₀ S CONH (CH ₀ KNCO

2 «ti

OCO CH _n S CONH (CH ₀ ) ^ NCO

owns.

Example 8

Castor oil (200 g) is azeotropically dried with toluene (200 g) and the water is removed with a Dean-Stark tube. After cooling, chloroacetic acid (12.2 g) along with p-toluenesulfonic acid (1 g) is added and the mixture is heated to reflux until complete reaction between the castor oil and chloroacetic acid took place. This is determined by looking at the amount of water that is at the esterification (2.3 ml) is released with the Dean-Stark tube measures. This procedure then follows for the addition of another 4 aliquots of 12.2 g of chloroacetic acid (61 g in total) repeated. By adding the chloroacetic acid in this way, the hydrolysis of the chloroacetic acid (with Water, which is released during the reaction), whereby acetic acid is formed, avoided. The complete Esterification is carried out without the need to to use an excess of halogen acid. In an experiment in which the chloroacetic acid only through a single Addition was only 75 ° o of the theoretical .Amount of water removed after refluxing for a long time had warmed.

The chloroacetic acid triester of castor oil is washed with water, until the pH of the aqueous extract is 5. The product (250 g solid material, dissolved in 50 g toluene) is dissolved in 2-ethoxyethanol (1000 ml), an excess is added of sodium thiosulfate pentahydrate (180 g), dissolved in

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Given water (200 g). The mixture is heated to 70 to 8O ⁰ C with vigorous stirring for about 2 hours. After this time approximately 500 ml of water is added in 100 ml aliquots at 15 minute intervals. It has been found that adding the water in this way, after the reaction has partially progressed, increases the rate of conversion of the chloroacetic acid ester into the water-soluble trithiosulphate, due to the increasingly polar nature of the solvent mixture.

Example 9

Castor oil (200 g) is azeotropically dried by adding it with Toluene. (200 g) heated to reflux. After cooling, use trichloroacetic acid (106 g) along with p-toluenesulfonic acid (1 g) are added and the mixture is heated to reflux until the theoretical amount of water (11.6 ml) removed azeotropically with a Dean-Stark tube.

The resulting trichloroacetate ester is then used on such V / eise treated as described in Example 8, and a water-soluble product is obtained which is sufficient Contains thiοsulfate groups, so that the material under formation an insoluble resin can be cured.

Example 10

A simple jersey wool material is based on 4% by weight on the weight of the material, a polyisocyanate compound prepared by the method of Example 1 became. The application takes place with a lack of pressure or lack of padding with a solution of the resin in trichlorethylene is resolved. After application, pieces of the treated material undergo different curing conditions subject.

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The shrinkage resistance (under this expression in the present application the expression "shrinkage resistance" fall) of each of the material test pieces was determined by placing them in a 15 liter test washing machine, sold under the trademark "Cubex". A liquid / material ratio is used for this purpose of 15: 1 and a pH of 7 are used, the liquid being a mixed mono- and disodium phosphate buffer contains. The test pieces are then washed for 1 hour, the shrunk area becomes with the area of one a similar test piece of untreated jersey material used as a comparative sample.

% Shrink area

Untreated material '43

treated but not cured material 49 cured for 2 days at ambient temperature 5 with steam at 100 ^° C. for 15 minutes

treated 3

1 minute airflow + 2 days at ambient temperatures 2

Example 11

A simple jersey material made entirely from wool is treated with 4 % by weight of a compound masked with bisulfite, made as described in Example 5. The compound is applied as an aqueous solution and pieces of the treated material are dried and subjected to various curing conditions and then the shrinkage resistance test described in Example 7 is carried out. The following results are obtained.

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% Shrink area Untreated material 55

Material without hardening the resin

dried 54

Material with steam at 100 ⁰ C during

15 minutes treated 9

Material in an autoclave at 115 ^° C

treated for 5 minutes 6

Example 12

This example illustrates the ability of the chlorinated compounds of the present invention to be both a woolen material Shrink resistance as well as fire resistance properties to rent.

An easy-knitted or -gewirktes Jersey woolen material was treated with 5 wt.% Of the chlorinated compound described in Example 3, by applying a solution of the dissolved compound in trichlorethylene. The treated material is then ^{treated with steam for 10 minutes at 100 °} C. in order to harden the resin. The shrinkage resistance of the material is then determined by measuring the percentage of the shrink area after the test pieces of the material have been subjected to the washing treatment described in Example 7. The following results were obtained.

fo Shrink area

Untreated material 45

treated with resin '2

The fire resistance properties of the treated material were then determined in the following manner. Pieces of material Measuring 12 "3" (30.5 cm by 7.6 cm) were vertical Position held in a frame. A small flame was then allowed to strike the lower end of the test piece for 12 seconds. The flame was then removed. The length of the char was then determined after the burning or smoldering Material was deleted. A similar attempt was made

409839/106 3

24132S5

performed with a non-chlorinated resin from Example 1 and also with an untreated material and with material which is shrink-resistant with 5% by weight of a known polyisocyanate Resin sold under the name "Synthappret LKF". You got the following results.

Length of char

Untreated wool 22.8 cm (9 ")

Ex 3 chlorinated resin 7 "(17.7 cm)

unchlorinated resin from Bps. 1 30.5 cm (12 ")

Synthappret LKF 30.5 cm (12 ») ⁺

⁺ The test piece was not extinguished, but 'burned the entire length.

Example 13

In this example it is illustrated that a plain knitted or knitted jersey material, when treated with 4% by weight of bromine compounds prepared according to Examples 4 and 6, is imparted both shrink resistance and fire resistance properties. These compounds are applied from a solution of trichlorethylene on a pad mangle. Separate test pieces of treated material are then cured by drying at ambient temperatures or ^{treating with steam at 100 °} C. for 15 minutes. The fire resistance properties of these compounds are compared with the non-brominated compounds of Example 2 and with Synthappret LKF.

% Shrink area

Shrinkage resistance drying when treated with steam - _; Ambient temp. b.IQO ⁰ C for 15 min.

Untreated material 48

Compound of Example 4 0 6

Compound of Example 6 6 4

0 9 8 3 9/1053

Fire resistance
Compound of Example 4 Compound of Example 6 Non-brominated resin of Ex. 2

Synthappret LKF
untreated material "

Char length 12.7 cm (5 ") 13.9 cm (5 1/2»)

30.5 cm
(12 »)

30.5 cm
(12 »)

burned the entire length of the test piece

22.8 cm (9 ")

From these results it can be seen that, unlike other shrink-resistant resins, it is actually the natural one If the wool's fire resistance deteriorates, the bromine compounds actually improve it.

Example 14

A simple jersey wool material is mixed with a solution in Perchlorethylene padded the resin compound of Example 7, giving a resin uptake of 4% by weight, based on the weight of the material. The padded material is then dried and one sample lasts 24 hours, the other stored in the autoclave. The material is then washed for 1 hour as described in Example 7 and the shrinkage resistance results, which are obtained are the following.

sample % matted Schruriroffläche

Not treated

treated with resin / cured in air

treated with resin / autoclaved

Example 15

Pieces made of different wool materials are made with 4% by weight, based on the material, polythiosulphate treated as in Example 8, and 0.2% by weight, based on the material, of sodium carbonate. The connections will Applied on a padding machine in the form of an aqueous solution with a pH of 10 and the pieces of material are then dried and autoclave for 6 minutes at a

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Pressure of 1.27 kg / cm (18 psi) and treated at 100 ° C to to harden the resin. The test pieces are then subjected to the washing test under the conditions described in Example 10 subjected to determine their entanglement shrinkage.

Total% shrink area after "Cubex" - washing

1 H. 2 hours. 3 hours. Simple jersey
serge
Doctor flannel 4th
3
1 8th
4th
2 9
4th
2 Example 16

In the following example, the superior light fastness of the compounds according to the invention is explained, which with a commercially available shrink-proof means which is also a polyisocyanate.

Different pieces of simple ¥ ¥ ¥ olljerseymaterial are treated with 4% by weight of different compounds according to the invention and with Synthappret LKF. The resin is applied from a solution in perchlorethylene. "A water-soluble Bisulfitderivat of Synthappret is also used in the form of an aqueous solution. The treated pieces of material to be treated and then dried at 100 ⁰ C with steam to cure the resin.

The test pieces are then irradiated by a Xenon arc lamp is emitted, exposed until each has received the same amount of light, determined by Scale 7 of the Draft Proposals of the International Standard Organization (I.S.O.) Recommendations R 105 - 1966.

The test samples are then test washed according to the method described in Example 10 and the Reduction in length is determined.

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% Shrinkage in length of the test pieces

link LKF not expired
tet exposed up to
Standard 7 example 1 "- bisulfite
derivative 3 3 Example 5 2 2 Synth player 0 35 Il 0 38

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Claims (17)

Claims 1. A curable composition containing a polyester polyhydric alcohol and an ethylenically unsaturated higher aliphatic hydroxycarboxylic acid, in which the radicals of zv / ei or more reacted hydroxyl groups of the acid in each case via corresponding ester bonds with corresponding further organic residues are connected, each of which is an isocyanate or contain thiosulfate group, the composition being curable to form resin. 2. Curable composition according to claim 1, characterized in that the hydroxycarboxylic acid contains ricinoleic acid. 3- Curable composition according to one or more of the claims 1 and 2, characterized in that the polyester used is glyceryl triricinoleate. 4. Curable composition according to one or more of the claims 1 to 3> characterized in that the polyester is in the form of castor oil. 5. Curable composition according to one or more of claims 1 to 4, characterized in that it is the reaction product of castor oil, a thiol-containing organic acid and then an organic diisocyanate is. 6. Curable composition according to one or more of the claims 1 to 5, characterized in that it is the reaction product of castor oil, maleic acid or anhydride and then an organic diisocyanate. 7. A hardenable composition according to one or more of claims 1 to 6, characterized in that it contains the reac 409839/1053 tion product of castor oil, chlorinated dicarboxylic anhydride and then an organic "diisocyanate. 8th; Hardenable composition according to one or more of the claims 1 to 7, characterized in that the other organic groups are bisulfite-masked isocyanate groups contain. 9. Curable composition according to one or more of claims 1 to 8, characterized in that it is the reaction product of castor oil, a chloroacetic acid and then a water-soluble metal thiosulphate. 10. Curable composition according to one or more of the claims 1 to 9i characterized in that die.unesät taken aliphatic hydroxycarboxylic acid is saturated by halogenation. 11. Curable composition according to one or more of claims 1 to 10, characterized in that as
Halogen bromine used. 12. Process for the preparation of a curable composition according to one or more of Claims 1 to 11, characterized in that a polyester of a polyhydric alcohol and an ethylenically unsaturated higher aliphatic hydroxycarboxylic acid is reacted with an organic acid or an anhydride which has a further functional atom or group in its molecule contain or provide to esterify at least two of the hydroxy groups of the unsaturated acid, and then the functional atoms or
Groups further reacted with a further compound which is capable of introducing isocyanate or thiosulfate groups into the mass. 409839/1053 13. The method according to claim 12, characterized in that that the further functional groups are carboxyl groups and the further compound is an organic diisocyanate is. 14. The method according to one or more of claims 12 to 13, characterized in that the further functional Atoms are halogen atoms and the further compound is a water soluble metal thiosulfate. 15. The method according to one or more of claims 12 to 14, characterized in that the further functional groups are thiol groups and the further compound is an organic diisocyanate. 16. The method according to one or more of claims 12 to 15, characterized in that the isocyanate groups masked by reaction with a bisulfite. 17. A method for the treatment of keratin fibers or textile material, characterized in that one is on the Fibers or the material uses a curable mass according to one or more of claims 1 to 11 and the mass on hardens the fibers or the material. Dr.T / Wt / My 409839/105 3