FR2531463A1 - PROCESS FOR IMPROVING THE SOLIDITY OF OPTICAL DYES OR BRIGHTENERS ON A MIXED SUBSTRATE OF POLYAMIDE FIBERS AND FIBERS CONTAINING HYDROXY GROUPS - Google Patents

Abstract

DEPENDING ON THE INVENTION, THE OPTICAL COLORANT OR AZURANT IS FIXED ON THE SUBSTRATE BY APPLYING TO IT: EITHER A. A POLYBASIC COMPOUND WHICH IS THE REACTION PRODUCT OF A MONO- OR POLYFUNCTIONAL PRIMARY OR SECONDARY AMINE WITH CYANAMIDE, DICYANODIAMIDE (DCDA), GUANIDINE OR BIGUANIDINE, IN WHICH UP TO 50 MOLES OF CYANAMIDE, DCDA, GUANIDINE OR BIGUANIDINE CAN BE REPLACED BY A DICARBOXYLIC ACID OR ITS MONO- OR DIESTER, WHICH PRODUCTS CONTAIN AT OF HYDROGEN REAGENTS BOUND WITH NITROGEN, OR B. A PRECONDENSATE FORMED BY REACTION OF A ABOVE WITH C. AN N-METHYLOL DERIVATIVE OF A UREA, A MELAMINE, A GUANAMINE, A TRIAZIONONE , URONE, CARBAMATE OR ACID AMIDE TO BE APPLIED TO THE SUBSTRATE IN COMBINATION WITH D. A CATALYST FOR THE CROSS-LINKING OF N-METHYLOL COMPOUNDS OF TYPE C ABOVE, THE ABOVE. APPLICATION OF PRECONDENSATE B AND CATALYST D FOLLOWING A FINAL STEP OF HOT VULCANIZATION.

Description

The invention relates to a method for improving the strength properties.

  dyes and optical brighteners on mixed textile substrates, The invention relates to a method for improving the strength of dyes or optical brighteners on a substrate

  consisting of a mixture of polyamide fibers and fibers containing

  of hydroxy groups, natural or synthetic, characterized in that one applies to the dyed, printed or azure (lightened) substrate: either A) a polybasic compound which is the reaction product of a primary or secondary amine mono or polyfunctional with cyanamide, dicyanodiamide (DCDA), guanidine or biguanidine, in which up to 50 mole% of cyanamide, DCDA, guanidine or biguanidine can be replaced by a dicarboxylic acid or its mono or diester , said product A) containing reactive hydrogen atoms bound to nitrogen, or B) a precondensate formed by reaction of A) above with

  C) an N-methylol derivative of a urea, a melamine, a guana-

  lead, a triazinone, a urone, a carbamate or an acid amide which is applied to the substrate in combination with D) a catalyst for the crosslinking of N-methylol compounds

of type C) above.

  When applying the precondensate B) and the cata-

  lyser D), a final vulcanization step is then implemented

hot.

  Component A) is preferably the reaction product

  tion of a monofunctional amine of formula Ia RRNH Ia or of a polyfunctional amine of formula Ib RRN Z -X t Z -NRR lb n in which each residue R is independently hydrogen or an unsubstituted C 1C 10 alkyl group or monosubstituted by

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  a hydroxy, C 1 -C 4 alkoxy or cyano group, provided that, in formula la, at least one of the residues R is other than hydrogen ;. n is a number from 0 to 100; Z, or each residue Z independently when N> O, is a C 1 -C 4 alkylene or hydroxyalkylene group; and Xe or else each X remains independently when N to 1, is -0-, -S or -NR o R is as defined above, provided that the amine of formula Ib contains at least one -N group 11 H or -NIH 2 reagent,

  with cyanamide, dicyanodiamide (DCDA) or guanidine.

  It is also preferred that component A) be the reaction product of a polyfunctional amine of formula Ib with cyanamide, DCDA or guanidine. In the amines of formula Ib, the residue R is preferably hydrogen or an alkyl group. or

  hydroxyalk'Cyle C 1-C each residue R is preferably hydro-

  gene The symbol N is preferably a number between O and 30, which may not be an integer and represents an average value. More particularly, it is preferred that N is an integer from 1 to 6 The remainder Z

  is preferably a 1,2-ethylene, 1,3-propylene or 1,3- (2-

  hydroxypropylene), X is preferably -NR-, very particularly -NS-. Particularly preferred amines are

  diethylenetriamine, triethylenetetramine and 6thylene poly-

  polyamines, polypropylene polyamines or poly (hydroxypropylene) -

  higher polyamines containing up to 8 nitrogen atoms, pre-

ference up to 6.

  In the reaction with cyanamide, DCDA, guanidiae or biguanidine, the amines can be in the form of the free base or of the salt, for example in the form of carbonate, and mixtures of amines can be used. preferred reagents

  are guanidine and DCDA, in particular DCD A and compounds

  sants A) preferred are the reaction products of diethylene-

  triamine, triethylenetetramine or 3- (2-aminoethyl) -

aminopropylamine with DCDA.

  Components A) are known and their preparation is described for example in British patent 657,753 and

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  U.S. Patent 2,649,354 Conveniently

  nableon reacts the reactants together in the absence of water,

  at elevated temperatures optionally in the presence of a sol-

  Before being preferably aqueous, the reaction is carried out in the absence of solvent, at a temperature of 140-160 ° C. and with evolution of ammonia. The reactants are preferably reacted in a molar ratio of 0.1 to I mole of cyanamide, DCDA, guanidine or biguanidine per mole of -NH or -TH 2 groups

  reactants and when reacting the DCDA with a polyalkylene

  polyamine, the molar ratio of the reactants is preferably

  2: 1 to 1: 2, a particular year of approximately 1: 1.

  The products A) are viscous liquids or almost colorless solids, of basic character, soluble in water either in the free base form or in the salified form,

  and contain reactive hydrogen atoms attached to nitrogen.

  The products are preferably miscible with water in all proportions. Before the reaction with the N-methylol compound C), it is preferred that the product A) is neutralized to a fold of 7-8, by

  example by addition of inorganic or organic acids, preferably

  hydrochloric acid or sulfuric acid, to an aqueous solution of A) It may be desirable, after neutralization with an acid, to concentrate the neutralized solution of A) before sdcdit'on of C); for example, product A) can be processed

  into a powder by a spray drying operation.

  Components C) are generally the compounds

  Water-soluble N-methylol which are known as cross-linking agents

  thick for cedlulose fibers and are used to give cellulosic fabrics an anti-crease finish The compounds may contain free N-methylol groups N-CH 20 H, or these may be etherified The preferred ethers are the alkyl ethers lower in C 1-C 4 Examples of suitable N-methylol compounds are given in British patent application 2 070 006 A. The precursors of reactive resins resistant to

  hydrolysis are particularly suitable, for example N, N'-

  dimethylol-4,5-dihydroxy or 4,5-dimethozyethyleneurée,

  N, N'-dimethylol-4-methoxv-5,5-dimethylpropyleneurée and, N'-

  dim 'thylolcarbamates, optionally in the etherified form The preferred ether forms are the methyl and ethyl derivatives The N-methylol compound C) is generally obtained in the form of an aqueous solution containing about 40-50% by weight of C) and can be used as it is in the reaction with A),

or be further diluted with water.

  The reaction between components A) and C) is carried out

  killed in an aqueous medium, for example by gradually adding compound C) in solid form or in the form of an aqueous concentrate to an aqueous solution of C), preferably containing 30-50% of C) and -70% in weight of water The preferred aqueous medium has a p H included

between 4 and 6.

  It is strongly preferred that catalyst D) is pre-

  during the reaction of A) and C) to form the precondensate B), It is suitably dissolved in the aqueous solution of C) before the addition of A) However, if A) and C) can react properly together in the absence of D), we can then add

  subsequently catalyst D) in the precondensate.

  The compounds A) and C) are reacted together, preferably with constant stirring, at room temperature or at temperatures up to 800 ° C., preferably 60-80 ° C., in particular 70-75 ° C. The condensation reaction must be stopped before the reaction product becomes insoluble in water and forms a gel; suitable reaction times are of the order of 30 min to 3 h The final product preferably has a viscosity at

  the ambient temperature of 50-200 m Pa s, in particular 60-150 m Pas.

  These viscosities apply to reaction products as they are

  obtains, that is to say containing 30-60% by weight of water.

  The relative quantities of components A), C) and -

  c Currently D) are within the limits of 5-40 parts by weight of A), 25-110 parts by weight of C), 1-30 parts by

  weight of D); calculated with respect to the active component present.

  The weight proportions of A: C: D are 1: 0.625-22: 0.025-6.

  Preferred ranges are 10-20 parts by weight of A), -75 parts by weight of C) and 5-15 parts by weight of D), or

  1: 1.75-7.5: 0.25-1.5; more particularly 1: 2-3: 0.5-1.

  The suitable catalysts D) are of the type used for the crosslinking of N-methylol compounds C) on cellulose, and examples are given in British patent application 2 070 006 A Preferred catalysts are nitrates, sulfates, chlorides and dihydrogeno - aluminum, magnesium or zinc orthophosphates, more particularly magnesium, in particular

  magnesium chloride, optionally in combination with a sul-

  alkali metal fate, especially sodium sulfate.

  According to the process of the invention, a substrate consisting of a mixture of polyamide fibers and fibers containing hydroxy groups, natural or synthetic, is firstly dyed or lightened, successively or simultaneously with dyes or optical brighteners suitable for each type of fiber, and then subjected to post-treatment with precondensate B), by

  presence of catalyst D) or by component A) alone.

  The polyamide component can be wool or a synthetic polyamide, for example polycaprolactam ("Nylon 6") or polyhexamethyleneadipamide ("Nylon 66") The component containing hydroxy groups is preferably a cellulosic fiber,

  especially cotton Preferred substrates have a poly-

  amide: cellulose between 20:80 and 80:20, more particularly

  50:50 The polyamide component is dyed with an anio-dye

  suitable picnic; the cellulosic component with a direct dye or a reactive dye The substrate can be dyed or printed by any of the conventional techniques used for these

  dyes; for example, dyeing can be done by dyeing

  ture by exhaustion from a dye bath, or by foula-r -

  dage followed by heat setting or cold fixing, or else in

  reactive dyes, by alkaline fixing.

  The process according to the invention is carried out on a substrate on which the dyeing or printing process, including

  including the necessary fixing step, is completed.

  the substrate can be dry or even wet, provided that it does not

  is not so wet that it can no longer absorb bath.

  When component A) is used alone, it is preferably applied in a process by exhaustion from a short bath

: 6

  or when in a long bath (bath ratio greater than 10:>), the amount of 1 component A) in the bath (me 3 urea in active substance s-hle) is preferably from 1 to 10 g / l, more particularly 2-5 g / l In short bath processes, quantities of 20-100 g / l may be necessary. The preferred application conditions are a temperature of 30-70 C and a p H of 4-5 for a duration of -60 min. When the precondensate B) is used simultaneously with the catalyst D), the post-treatment agent can be applied to the surface in aqueous solution by soaking, spraying, application of foam padding or other conventional techniques of application. The preferred application method is by padding

at room temperature.

  The quantities of the product according to the invention which are applied to the substrate strongly depend on the dye intensity which must be fixed. For dyes of a standard intensity 1/1, the quantities used are 30-200 g / 1 of the padding bath, when applied at a fixing rate of 70-100% of the dry weight of the articles Preferably, the quantity is

  70-130 g / l, based on the total dry weight of the substrate.

  After the application of the padding bath, the substrate is subjected to a hot vulcanization step, conventional for treatments with resins based on type B compounds. The substrate can for example be dried at 70-120 ° C. and finally crosslinked at a temperature of 130-180 C for 30 seconds at 8 min, or else dried and crosslinked simultaneously by heat treatment at 120-200 ° C,

  preferably 140-180 C for 5 S at 8 min, depending on the temperature.

  A preferred method is to treat the fouled substrate at 150-170 C

for 60 to 90 s.

  Direct and reactive dyes which are particularly suitable for use on the cellulosic component of the substrate are described in British patent applications 2,070,006 A and 2,093,076 A. The anionic dyes preferred for use on the polyamide component of the substrate, in particular for synthetic polyamides, are mono or polysulfonated dyes

253 1,463

  anionics with a molecular weight of 400-1000, optionally

  in the form of metal complexes Special dyes-

  most preferred have at least two sulfonic acid groups and a molecular weight of 600-1000, optionally as a metal complex, in particular, metal complexes having

  molecular weights of 800-1000.

  A preferred group of dyes is constituted by the acid dyes of the Color Index (CI, Acid Dyes) which are exhausted on the polycaprolactam to a degree of at least 50% from an aqueous bath containing twice the quantity necessary for give a standard dye intensity of 1/1, at a bathing ratio of

  1:30 after 60 min at p H 3-11 and at a temperature of 30-98 C.

  Suitable acid dyes are described in the following patents and patent applications: Patents of the Federal Republic of Germany 1,644,356, 2,013,783, 2,153,548; patent applications of the Federal Republic of Germany published

  (DOS) 2,202,419, 2,400,654, 2,631,830, 2,729,915, 3,034,576;

  French patents 7,506,109 and 7,624,658.

  The polyamide component can also be dyed with conventional reactive dyes for use on

polyamide fibers.

  Although these post-treatment agents are known for fixing dyes on cellulose: it is surprising that they also give improved fastness properties for dyes on the polyamide component of the mixed textile substrate,

  although the substrate and the dyes used are quite different

  rents chemically Improved fastness properties include wet fastness, i.e. fastness to washing, fastness to perspiration and fastness to water, as well as

  in some cases, improved light fastness.

  The following examples illustrate the invention without however limiting its scope. In these examples, the parts are

  - percentages are all by weight.

  Preparation of post-treatment tendencies (according to British patent application 2 070 006 A) A i) 103 parts of diethylenetriamine and 84 parts of dicyanodiamide (DCDA) are slowly heated to 100-110 C. When the evolution of ammonia ceases, temperature rises to 160 C

  and the mixture is reacted for 6 h at this temperature

  ture The reaction mass is cooled, it is neutralized

  with dilute sulfuric acid and dried by spraying

  tion. ii) 25 parts of the product of A i) are mixed with 15 parts of Mig Cl 6 20 and 100 parts of a 50% aqueous solution of

2 '1 2

  dimethyloldihydroxyethylenéeée and the mixture is reacted for 1 h at 70, to obtain a liquid miscible with

water into a cloudy mixture.

  B i) Repeat preparation A i) using 175.5 parts of

  3- (2-aminoétiyl) -aminopropylamine instead of diethylene-

  triamine, reacting at a temperature of 120.

  ii) Preparation A ii is repeated using 25 parts of product B i) o C i) Preparation A is repeated i) using 120 parts

  ethylenediamine instead of diethylenetriamine.

  ii) Repeat the preparation of A ii) using 25 Darties

of the product of C i).

EXAMPLE 1

  A mixed textile fabric consisting of 20 parts of polycaprolact & me and 80 parts of

  cotton, using Acid Red CI 128 for the poly component

  amide and the dye of formula V II of the British patent application

  pic 2,070,006 A for the cotton component, both at the intensity

standard 1/1.

  The dyed fabric is then fouled with 80% absorb-

  tion with a padding bath containing 12% of product Aii) and 0.5% of 80% acetic acid, and the fabric is dried and then vulcanized to

  hot for 40 S in air at 180 The dye subjected to the post-

  treatment has improved resistance to wet, washing and

with chlorinated water.

EXAMPLES 2-4

  The procedure of Example 1 is repeated using

  reading Acid Blue Co I 113, Acid Red C i 399 or Acid Blue C I 310, respectively: for the polyamide component instead of Acid Red C Io 128 We obtain similar good results,

  including improved light fastness.

EXEMILE 5

  Example 1 is repeated using the same padding bath with the addition of 4% of a cationic softener and 0.1% of a nonionic surfactant. Results are also obtained.

EXAMPLE 6

  A mixed textile substrate consisting of 50 parts of polyhexamethyleneadipamide and 50 parts of cotton is conventionally dyed with Blue Adide CI 296, Blue Acid CI 225 and Blue Direct CI 251 and the dyed substrate is subjected to post-treatment as described in Example 1 L; s dyes on the polyamide component and on the cotton component show

  improved properties of resistance to wet and washing.

  EXAMPLES 7 and 8 Example 6 is repeated using products B ii) and C ii), respectively, in place of product A ii) We obtain

equally good results.

EXAMPLE 9

  A mixed textile substrate consisting of 50 parts of polyhexamethyleneadipamide and parts of cotton is conventionally dyed with the Red Acid C I 119 dye and the dye of formula VIII of British patent application 2,070

2,070,006 A.

  The dyed fabric is subjected to post-treatment by

  a process by exhaustion at a bath ratio of 1:20 to 50 ° C.

  for 20 min, in a bath containing 0.1% of product A i) and 0.025% of glacial acetic acid (relative to the weight of the bath) to give

a p H of 4.5.

  The post-treated fabric is rinsed and dried; she pre-

  feels improved resistance to perspiration and water.

EXAMPLE O 10

  A mixed textile substrate like Example 9 is printed with a conventional printing paste containing the clingers from Example 1 and subjected to post-treatment, as described in Example 1. Good results are obtained. .

EXAMPLE 11

  A mixed textile substrate consisting of parts of wool and 50 parts of cotton is dyed, according to a conventional single bath process, at a bath ratio of 1:30 in a dye bath containing 0.025% of Green Direct CI 69, 0.027 of Acid Green CI 105

and O 0006% of Acid Blue C Io 225.

  The dyed and rinsed substrate is subjected to post-treatment.

  ment at the same bath ratio in a bath containing 0.1% of product A i), 0.05% of glacial Pcetic acid at p E 5) and 0.05% of Na Cl The post-treatment is carried out at 30 -60 for 20-30 min and finally rinse the substrate and dry it The dye after post-treatment

  has improved wet strength properties.

EXAMPLE 12

  A mixed textile substrate of 30 parts of wool and 70 parts of cotton is dyed in a dye bath containing 0.01% of Yellow Direct CI 162, 0.08% of Red Direct CI 83, 0.02% of Red Acid CI 399 and 0.01% of Violet Acid CI 128 as in Example 11 The dyed and rinsed substrate is fouled as in Example 1 with a padding bath containing 8% of product A ii) and 0.27 of acid acetic (at p H 4.5-5) and finally it is dried and subjected to post-treatment with AO 0-160 C for 3-6 min The substrate

  treated has improved wet strength properties.

  EXEM Ls E 13 Example 12 is repeated, using in the dye bath O, 008% of Direct Yellow CI 162, 0.03% of Direct Brown C I. 240, 0.03%, of Direct Blue C i, 251 and 0.05% of Acid Black CO 1 2922 with the same post-treatment agent Properties of

  also good wet strength.

EXAMPLE 14

  A mixed textile substrate consisting of

  parts of polycaprolactam and 50 parts of cotton in a pre-

  1st step at a bath ratio of 1:20 with a weak bath

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  alkaline containing 0.07% orange Reagent CI 64 and 0.035% Red Reactive CI 159 for dyeing cotton In a second step, the polyamide component is dyed at the same bathing ratio, with a neutral to weakly acidic bath, containing 0 , 03% CI 64 Reactive Orange and 0.02% CI Reactive Red, 159

  and we fix the dyes in the classic way.

  The dyed substrate is subjected to the post-treatment as described in Example 9 with the product A i), giving

  improved wet strength properties.

EXAMPLE 15

  The dyed article of Example 14 is subjected to the post-

  treatment, as described in Example 1, using product A ii).

  Equally good results are obtained.

  It is understood that the invention is not limited to

  preferred embodiments described above By way of illustration

  and that those skilled in the art can make various modifications and modifications without however departing from the scope and

the spirit of the invention.

Claims (21)

R E V E N D I C A T I O N S   1 Process to improve the solidity of colo-   rants or optical brighteners on a substrate consisting of a mixture of polyamide fibers and fibers containing hydroxy groups, 'natural or synthetic, characterized in that one applies to the dyed, printed or azure substrate: either A) a polybasic compound which is the reaction product   a primary or secondary mono or polyfunctional amine-   with cyanamide, dicyanodiamide (DCDA), gua-   nidine or biguanidine, in which it is possible to replace up to 50 mol% of cyanamide, DCDA, guanidine or biguanidine with a dicarboxylic acid or its mono or diester, said product A) containing reactive hydrogen atoms bound to nitrogen, ie B) a precondensate formed by reaction of A) above with C) an N-methylol derivative of a urea, a melamine, a guanamine, a triazinone, a urone, a carbamate or an acid amide which is applied to the substrate in combination with D) a catalyst for the crosslinking of the Nmethylol compounds of type C) above, provided that, when the precondensate B) and the catalyst D) are applied, a final stage of hot vulcanization is used.  2 Method according to claim 1, characterized in that component A) is preferably the reaction product of a monofunctional amine of formula Ia RRNH la or of a polyfunctional amine of formula Ib RR Z -XZ -NRR Ib n in which each residue R is independently hydrogen or a C 1- C 10 alkyl group which is unsubstituted or monosubstituted by 253 1,463   a hydroxy, C 1 -C 4 alkoxy or cyano group, provided that, in formula Ia, at least one of the residues R is other than hydrogen; n is a number from 0 to 100; Z or each residue Z independently when N> 0 is a C 1 -C 4 alkylene or hydroxyalkylene group; and   Xor each remains X independently when N? 1, is -O_, -S-   or -NR oh R is as defined above, d provided that the amine of formula Ib contains at least one reactive -NH or -NH 2 group,   with cyanamide, dicyanodiamide (DCDA) or guanidine.   3 Method according to claim 2, characterized in that component A) is the reaction product of a polyfunctional amine of formula Ib in which R is hydrogen or a C 1-C alkyl or hydroxyalkyl group, N is a integer of   1-6 and X is the remainder -NR-, with cyanamide, DCDA or gua-   nidine 4 Method according to claim 3, characterized   in that component A) is the reaction product of ethylene-   diamine, triethylenetetramine or 3- (2-amninoethyl) - aminopropylamine with DCDA.   Method according to any of claims 1 to 4, characterized in that component A) is applied   alone by an exhaustion process.   6 Method according to claim 5, characterized in that the application is carried out at 30-70 C and at a p H of 4-5 for 10-60 min.   7 Method according to claim 5 or 6, character-   laughed at in that the application is made from a long bath   containing 1-10 g of component A) per liter.   8 Method according to any one of the claims   1 to 4, characterized in that component C) is N, N'-di-   methylol-4,5-dihydroxy or 4,5-dimethoxy-ethylenated, N, N'-   dimethylol-4-methoxy-5,5-dimethylpropyleneurée, un N, N'-dimethylol-   carbomate or one of their methyl or ethyl ethers.   9 Process according to any one of the claims   1 to 4 and 8, characterized in that catalyst D) is chosen 253 1,463   among the nitrates, sulfates, chlorides and dihydrogen-orthophos-   aluminum, magnesium and zinc pates.   Method according to claim 9, characterized   in that component C) is W, N'-dimethylol-4,5-dihydroxyethyllne-   urea and catalyst D is magnesium chloride.   il Method according to any one of claims   1 to 4 and S to 10, characterized in that the precondensate B) is prepared   by reaction of components A) and C) in an aqueous medium, pre- sence of catalyst D).   12 Method according to any one of claims   1 to 4 and 8 to 11, characterized in that the weight proportions of A: C: D are 1: 0.625-22: 0.025-6.   13 A method according to any one of claims   1 to 4 and 8 to 12, characterized in that the precondensate B) is applied   qué to the substrate by padding at room temperature.   14 Method according to claim 13, characterized in that the padding bath contains 30-200 g / l of precondensate B) and it is applied at a fixing rate of 70-100% of the dry weight articles.   15. Method according to any one of the claims.   1 to 4 and 8 to 14, characterized in that the hot vulcanization step is carried out by heating to 150-170 C for 60 to 90 s;   16 Method according to any one of the claims   above, characterized in that the substrate is a mixture   cotton with wool, polycaprolactam or polyhexamethylene-   adipamide in a ratio of 20:80 to 80:20 by weight.   17 Method according to claim 16, characterized in that the cotton is dyed or printed with a direct dye or   reactive and the polyamide is dyed or printed with an anionic dye.   1 ú Method according to claim 17, characterized in that the polyamide is dyed with an anionic dye having at least two sulfonic acid groups Iques and a molecular weight of   600-1000, optionally in the form of a metal complex.   19 Method according to claim 17, characterized in that the polyamide is dyed with a chosen anionic dye 253 1,463   among the acid dyes of the Color Index (C Io) which are depleted on caprolactam to a degree of at least 50% From an aqueous bath containing twice the amount necessary to give a standard dye intensity of 1 / 1, at a bath ratio of 1:30 after 60 min at p H 3-11 and at a temperature of 30-98 C. e