CA1060138A - Threads, fibers and textile articles of halogenated acrylic polymerswith high dye affinity, and process for the preparation thereof - Google Patents

Abstract

The present invention relates to yarns and fibers based on halogenated modacrylic polymers, more particularly it relates to yarns containing 85-95% by weight of a halogenated modacrylic polymer consisting of 20 to 55% by weight of vinyl halide or vinylidene units , 45 to 85% by weight of acrylonitrile units and 0.5 to 3% by weight of a compound providing dye affinity for basic dyes and 5-15% of cyanoethylated polyvinyl alcohol. The yarns and fibers having a halogen level greater than 30% have improved light fastness and exhibit a reduction in mattification by treatment with water at a temperature greater than 80.degree.C. They find wide application in fields such as textiles, hosiery, weaving, furniture.

Description

1 ~ 60 ~ 3 ~
The present invention relates to yarns, fibers ~ base of halog8n modacrylic polymers having good affinity dye and a procedure to obtain them. It relates to also textile articles obtained from these threads or fibers.
Halog modacrylic polymer fibers ~ born very ~
commercially appreciated for their non-flammability however serious drawbacks:
- firstly, for halogen levels between 30 and 40 ~, they have an unsightly matt appearance during treatments in hot aqueous medium (~ from 80C) especially when tincture, and light fastness m ~ poor, -.
- on the other hand, unlike acrylic fibers containing more than 85% acrylonitrile, they have a low affinity dye vis-à-vis cationic dyes and this even if the polymers contain a significant percentage of acid sites.
This phenomenon can be explained by hydrophobia and crystal-such that these sites are in practice inaccessible to dyes.
He had ~ about ~ ~ ~, according to the French patent 1, 152.884 am ~ llorer tinctoral afflnity of fibers in po-lymers with ba ~ e of 0-100 ~ of acrlo ~ ltrlle and / or m ~ thacrylonitri-le and 100-0 ~ of vinyl chloride and / or vinylidene by addi-tion do 30-5 ~ of an acrylamide derivative polymer and ~ possibly-lement of a ~ utre monom ~ re such as vlnylpyridine.
But these flbres have a strong tendency to yellowing the heat.
It is also known according to the American patent 3,698,994 to prepare cryllic flbre from a mixture a polymer containing at least 70% acrylonitrile and 2-25%
by x contribution to the total polds of poi ~ mother of polyvinyl alcohol cyanoethyl ~ in order to improve luster, softness, . ... ..

106013 ~ 3 the hy ~ roscopiclt ~ and the antistatic qualities of the prepared fit r ~ es.
But the fibers3 obtained from these polymers do not do not have the advantage of being uninfIammable ~.
It has also been ~ proposed according to the French patent

2,108,395 a paper fiber made from a mixture of 15 3 90%
of a hydrophobic polymer which is a binary polymer and 10 to 85 of a copolymer comprising a llydrophobic part and a part hydrophilic chemically linked to the hydrophobic part, this copolymer ~ -re can be polyvinyl alcohol grafted with acrylonitrile. But this fiber has the qualities of a paper fiber i.e. strong fibrillation and good self-adhesion which are a ~ completely incompatible with textile use. In addition, the groups pes acrylonitrile fixed on the grafted polyvinyl alcohol click causing an unacceptable strong yellow color for a textile fiber.
Furthermore, it was proposed ~ according to the French patent ~ ais 2,120,601 to use polyvinyl cyanoethyl acetate ~ even-at least partially hydrolys ~ for enro ~ age of pi ~ ments, in proportions lnf ~ rleureg to 53, this m ~ mixture being intended n ~ ~ acetate or triac pigmentation ~ cellulose tate, or polymers ~ acrylonitrile base. But, used ~ at percenta-ges lnf ~ xieul ~ ~ 5X, polyvlnyllgue cyano alcohol ~ thyl ~ has no effect on afflnit ~ ~ inctorial ~ U polym ~ re with which it is m ~ lang ~.
It has now been ~ found ~ them ~ fibers, ~ ase of poly ~ ares modacryliq ~ es halogen ~ s de bonne affinlt ~ tinctoriale caract ~ ris ~ s ~ ar the fact that they are constituted by 85 to 95 ~ in weight of halogen ~ modacrylic polymers ~ s and 5 to lS ~ by weight polyvinyl alcohol cyanoethyl ~ having a degree of grafting of 1 approximately and that they are likely to fix at least 0.50 ~ in weight of pure cationic dye, by means of a dye bath . . '' .

1 ~ 6 ~ 38 having a content of pure cationic dye of 1.5 ~ by weight relative to the weight of textile material ~, the dyeing being effected killed for 1 hour at 98C.
The yarns and fibers according to the invention have in particular larity of being made of two incompatible polymers, forming a solution of less than two microns in solution, the phase demixed being hydrophilic.
The yarns and fibers according to the invention having a rate of ha-logene between 30 and 40% also have the advantage to do not ~ read matify by water treatment at temp ~ rature sup ~ rieu-re at 80C, for example when dyeing, for alcohol levels polyvinyl cyanoethyl ~ sup ~ laughing at 7%, and having a better light fastness.
The invention also relates to a process for obtaining of the above threads and fibers.
By halog ~ n ~ s modacrylic polymers is meant the polym ~ res containing 20 to 55 ~ by weight of vinyl halide ~ or of vinylidene, 45 to 85% by weight of acrylonitrile and from 0.5 to 3 ~
by weight of a compound providing the tinctorial affinity for basic dyes.
Among the compounds bringing tinctorial af ~ inite for the ~ basic dyes, mention may be made of the compounds ~ s to function carboxylic acids such as itaconic acid or has sul ~ onic acids such as vinyl sulfonic compounds, allyl- and m ~ thallylsulfonic acldes ~ aromatically derived ques sulfon ~ s such as styrene-sulfonic acids, vinyloxy-arane- ~ ultrasonic, etc ...
By polyvinyl alcohol cyanoet ~ lyl ~ means the pro-reaction product of acrylonitrile on polyvinyl alcohol in an alkaline hydroacetic medium.
The two polymers must pr ~ health between them a c4r-taine incompatibility: this if ~ nifies that the two copolymers, dis-SOU5 in a common solvent give a mixture of : ~ 60138 non homo ~ ene spinning; using ordinary means of testing, can distinguish the two polymer solutions which form a demixing also ~ ien in dissolved phase than in solid phase. The value of this demixing is measured by the size of the parts from the phase in the other. But this demix-tion must be less than 2 ~ so that the mixture of the two po-lymeres can be spun in good conditions. The value of demixtion is characteristic of the mixture. In particular, if we increase the proportions of the halog ~ monomer born in the mixture or if we increase the proportion of polyvinyl alcohol cyanoethyl ~, the demixtion becomes too large, the mixture becomes difficult-spinnable and the fibers obtained then acquire poor mechanical qualities.
The two polymers are then dissolved in a solvent common common which are polar organic solvents such as dim ~ thylformamide, dim ~ thylac ~ tamide, dimethylsulfo- - ~
xyde, N-methyl-pyrrolidone. Higher-grade polymers in halog ~ vinyl or vinylidene nure, that is to say containing more than about 50 ~ of halide are also soluble in acetone.
The solution of the two polymers can be spun dry in a known manner. The polymer concentration of the solution is generally between 30% and 35 ~ approximately, and the solution ~ is fll ~ e at a temp ~ rature of 60 to 80C pref ~ rence 65 to 70 about in a dry $ ilage cell in which the gases are my ~ ntenus ~ a temp ~ rature of 80 to 90C about to par-mettr ~ vaporization of the solvent. The ~ ilaments coming out of the cell lule are ensuita rep ~ s and ~ tir ~ s at a rate between 1.5 and 2 X in the air pUi8 again ~ shooting ~ s according to any known process ~
for example on rollers or in boiling water, in one or two phase at a temperautre between 100 and 160 C, has a rate between 3 X e ~ 7 X so as to obtain a draw overall between 8 X and 10 X for example.
Preferably, the filaments are then heat treated ~ 06 ~) 138 mi ~ uement to effect stabilization according to ~ out medium con-naked by a person skilled in the art, continuously or discontinuously, temperatu-re understood generally between 100 and 180C, the temperature function of the stabilization time ~ e ~
The solution of the mixture of the two polymers, of concent tration between 20-25%, can ~ galernent be spun to the humi-of according to a process well known to homr, the of art. Filaments are coagules in a bath consisting of a mixture of water and solvent for polymers, for example in proportions of 80% to 50 ~
water and 20% to 50% ~ e solvent, g ~ usually at 0-20C, then stretched preferably in the air at a rate of 1.5 to 2.5 X, washed with ma-usual, for example with water and preferably against current, stretch ~ s again at high temperature for example a boiling water around 100C has a rate between 2 and 4 X, so as to subject the filaments to an overall rate stretching between 3 X and 8 X.
The filaments can then undergo any treatment of-sir ~ such as stabilization, crimping, etc., under the conditions usual. The threads thus obtained are remarkably dyed well with the basic dyes and the yarns obtained from polymares having a halog ~ ne Rup ~ lower than 30 ~ present ~
a decrease in the matification by treatment in a medium each and even a total removal of this matification for de8 polyvinyl alcaol rate higher than ~ 7 ~ by weight. They also have a noticeable improvement in Yolidite 1 ~ light after dyeing.
They find wide application in all areas.
nes textiles, hosiery, weaving, furnishing, etc ...
In the following examples which are given as indicative and not limiting to illustrate the invention, the pros percentages are understood by weight.
The reference CI. Of the dye uses the east according to Co-lour Index- Edition 1971.

~ 60 ~ 38 Excmple 1 -Preparation of polyvinyl alcohol cyanoethyl ~ -We mix 0.580 kg of polyvinyl alcohol, 2.600 kg acetone, 0.530 kg of water and 0.023 kg of soda and left to rise pour polyvinyl alcohol ~ 60C for half an hour with reflux of acetone and then adding 1.060 kg of acr ~ ilonitrile, The reac-tion is carried out at 60 C for one hour. The polymer is re-cup ~ r ~ by precipitation in cold water in an acid medium. The al-cool polyvinyl cyanoethyl ~ has 57 ~ OH group cyano ~ thyl ~ s with a grafting degree close to 1.
We prepare s ~ par ~ ment a polymer containing 46% of acryl-lonitrile, 53 ~ vinylidene chloride and 1% sodium salt m ~ thallyl sulfonic acid.
0%, 5%, 7.5%, respectively, are added to this polymer.
10% and 12.5% of cyanoethylated polyvinyl alcohol pr ~ par ~ ci-above. 5 solutions A, B, C, D, E, respectively, are prepared in acetone corresponding to the various mixtures, the solutions B, C, D, having an average mix less than 1 ~, the solution E an average demixtion of between 1 and 2 1 ~.
The polymer concentration solutions are heated 30 ~ by weight at 70C pUi8 we dry ~ said solutions and we stretch the filaments in the alr at a rate of 1.6 X, pUi8 in boiling water at a rate of 2.2 X and finally on rollers at 160C
a rate of 3.0 X. The different wires are then stabilized in ~ tuve for half an hour ~ 130C.
The flames obtained ~ A, ~, C, D, E, are dyed with two different handles with CI Basic dye read 71.1 ~ bath has a dye content of 0.4% compared to Fibers to examine the rate of rise of the dye and 1.5%
to examine the amount of dye capable of binding to the fibers, In these qeux cases, the dyeing is carried out ~ e during ~, one hour ~ 98C.

_ 6 -

3 ~

We evaluated ~ on the different samples, the centering of dye mounted on the fiber, the rate of rise of the dye, and the exhaustion of the bath, We evaluated the solidity ~ at the light of the shade obtained (Xenotest) as well as the appearance of each sample. The results are given in the table below.
below.

% of color - Speed Depletion Solidity ~ Treatment rant mont ~ climb lu ~ iere 98C -as-Dect _ At 0.20 very slow not very 3 very dull drawdown B 0.74 rapid matifica-in one hour 3-4 tion l ~ g ~ -re C 1.42 5 no ma-tification D 1.44 very fast in 15 min 30% 5 steps 30 min 100% price E 1.33 "" very fast 5-6 There is an improvement in the light fastness.
2nd dyed thread. We also notice ~ ue the addition of al-cool polyvinyl cyanoethyle doesn’t change the point of colla-ge which is 190C for the ~ 5 tests. The measurements of the soli-says ~ ~ the light ~ have the object of the French standard approved ~ e NF G 07 067 ~ ISO Recommendation R 105 / V- 1969).

E ~
We prepare a polymer containing 46 ~ acrylonitrile, 52 ~ ae vinylidane chloride and 2% itaconic acid and we pr ~ -against a solution of ~ i ~ age in acetone, consisting of 90 ~ in weight of said copolymer and 10 ~ by weight of polyvinyl alcohol cyano ~ thyle as p ~ par in example l. Concentration of the ~ olution is 35 ~ by weight of polymer and the ~ mixtion average is lower :,:. ; . ...

After ~ dry spinning according to Example 1, we ~ pull the filaments in the air at a rate of 1.5 X then on rollers 160 C at a rate of 5X. They are then stabilized on wheels.
leaux at 180C continuously for 20 seconds.
In a comparative manner, we prepare a wire having the same composition but without addition of cyano polyvinyl alcohol ethyl. By treatment with boiling water, it matifies considerably badly.
Both threads are dyed ~ with the same CI dye Basic Blue 71.
Color results performed in a shared bath at 1.5% dye are as follows:
~ mont8 dye witness 0.20 example 2 1.30 Example 3 -90% of a copolymer is mixed containing:
- unit ~ s acrylonitrile 69.3 ~ by weight, - "vinylid chloride ~ only 29.4% by weight - "potassium vinyloxybenzenesulfonate 1.3 ~ in weight ~ and 10 ~ of polyvinyl alcohol cyanoethyl8 obtained according to Example 1.
The polymer mixture is dissolved in a mixture of 98 ~ dim ~ thylforma ~ ide and 2 ~ water and solution, concen-tration in polymer 22 ~ and of average value of demixtion inf ~ -:
lower ~ 1 ~ (, is wire ~ e ~ wet through a die of,:
64 holes of diameter O, 08mm ~ in a coagulating bath containing 40 ~ dim ~ thyl ~ ormamide and 60 ~ water, maintained at 5C.
The filaments are 8tir8s in the air at a rate of 1.8 X
lav ~ s ~ counter current with water, at room temperature, then stretched in boiling water at a rate of 3.3 X, and finally dried on rollers maintained at 80 C.

Dyeing is carried out with the CI Basic dye Blue 71 for one hour at 98C, in two different ways:
on the one hand with a single bath at 0.4% dye compared to fibers to examine the rate of rise of the dye, and to go, in a shared bath at 1.5% to examine the maximum quantity male dye capable of attaching to fibers.
We collected the results on the one hand on ob-held from the above mixture, on the other hand on a fi
bre t ~ moin containing the same halogenated modacrylic polymer but without addition of cyanoethylated polyvinyl alcohol.
The results obtained are as follows:

0.4% bath 1.5% bath % of fixed dye% of fixed dye t ~ less 0.10 0.31 example 3 0.74 1.53 ,: - g _

Claims (7)

The embodiments of the invention about which an exclusive right of property or privilege is claimed are defined as follows: 1. Yarns and fibers based on modacrylic polymers halogenated with good dye affinity, characterized by the fact that they are made up of:
- 85 to 95% by weight of a halogenated modacrylic polymer, 5-15% by weight of cyanoethylated polyvinyl alcohol having a degree of grafting of? about, and that they are likely to fix at least 0.50% by weight of pure cationic dye, at by means of a dye bath having a content of cationic dye only 1.5% by weight relative to the weight of textile material, the dyeing being carried out for one hour at 98 ° C., the polymers forming a solution of less than 2µ in solution. 2. Yarns and fibers according to claim 1, characterized by the fact that the halogenated modacrylic polymer contains 20 to 55% by weight of vinyl halide or vinylidene units, 45 to 85% by weight of acrylonitrile units and 0.5 to 3% by weight a compound providing the dye affinity for dyes basic. 3. Yarns and fibers according to claim 2, characterized by the fact that the halogenated polymer has a halogen level more than 30%. 4. Yarns and fibers according to claims 2 or 3, characterized by the fact that the halogen monomer used in the composition of the polymer is vinylidene chloride. 5. Yarns and fibers according to claim 3, do not present as long as no matification by treatment with water at temperature higher than 80 ° C, characterized by the fact that they contain at least 7% cyanoethylated polyvinyl alcohol. 6. Yarns and fibers according to claims 1, 3 or 5, characterized by the fact that they have improved solidity in the light. 7. Textile articles prepared from yarn and fibers according to claim 1.