EP0016907B1 - Produit antifeutrant pour laine - Google Patents

Produit antifeutrant pour laine Download PDF

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Publication number
EP0016907B1
EP0016907B1 EP80100297A EP80100297A EP0016907B1 EP 0016907 B1 EP0016907 B1 EP 0016907B1 EP 80100297 A EP80100297 A EP 80100297A EP 80100297 A EP80100297 A EP 80100297A EP 0016907 B1 EP0016907 B1 EP 0016907B1
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EP
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Prior art keywords
mol
radicals
radical
groups
atoms
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EP80100297A
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German (de)
English (en)
Other versions
EP0016907A2 (fr
EP0016907A3 (en
Inventor
Götz Dr. Koerner
Friedhelm Nickel
Günter Dr. Schmidt
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Evonik Operations GmbH
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TH Goldschmidt AG
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/647—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing polyether sequences

Definitions

  • the invention relates to a preparation for shrink-proofing wool.
  • GB-A-746 307 describes a method for preventing the shrinkage of the wool, the wool fibers being provided with certain organopolysiloxanes. A certain degree of shrink resistance is achieved in this way, but this effect is not washable.
  • DE-A-2 242 297, DE-A-2 335 751 and DE-A-2 523 270 disclose processes for shrink-proofing keratin fibers by applying organopolysiloxane, an essential feature being that these compounds contain amino groups.
  • the invention is therefore based on the object of finding a preparation for making wool shrink-proof, which contains both in emulsion form and in the form of an organic solution compounds which are suitable for making wool shrink-proof, these properties even after repeated washing of the wool in the customary manner Washing machines should be preserved. It is in particular an object of the invention to find a preparation which can be used optionally in the various stages of wool processing by means of different types of application. The aim is to ensure that the wool can also be treated after the wool has been dyed and that the known treatment methods, such as the pull-out method and the block method, can be used.
  • the active ingredient contained in the preparation must not adversely affect the so-called feel of the wool or the knitted fabrics and fabrics made from the wool.
  • the organopolysiloxane skeleton which is formed from the units a 1 ) and a 2 ), is a slightly to moderately branched siloxane.
  • the units a 1 ) and a 2 ) are preferably statistically distributed in the siloxane molecule.
  • these organopolysiloxanes can have 0.1 to 10 mol% of polyoxyalkylene radicals.
  • wool-affine groups are bound to the organopolysiloxane skeleton. These wool-affine groups are mercaptoalkyl or mercaptoaryl residues, aminoalkyl residues or anionic groups bonded to Si atoms via C atoms. It is sufficient if, in addition to the polyoxyalkylene radicals, only one of the three types of wool-affinity groups shown, e.g. B. 0.03 to 3 mol% of mercaptoalkyl or mercaptoaryl radicals are included.
  • aminoalkyl radicals are present in the molecule in amounts of 0.06 to 6 mol%.
  • 0.1 to 10 mol% of anionic groups bonded to Si atoms via carbon atoms are present.
  • these three different groupings can also exist side by side, e.g. B. mercaptoalkyl radicals together with aminoalkyl radicals or mercaptoalkyl radicals with anionic groups. You can also use all three different groupings be built into the molecule at the same time.
  • R 1 and R 2 groups are methyl groups, of which, however, up to 10 mol% can be replaced by longer-chain alkyl or aryl radicals.
  • alkyl or aryl radicals are the ethyl, propyl, dodecyl or phenyl radical.
  • the polyoxyalkylene radical preferably corresponds to the formula in which or the trimethylsilyl radical and y has a value from 4 to 20.
  • polyoxyalkylene block contains oxypropylene units in addition to oxyethylene units, polyoxyalkylene radicals with at least 40 mol% of polyoxyethylene units are preferred.
  • R 1 and R 2 should consist of 0.1 to 10 mol% of polyoxyalkylene radicals, a range of 0.3 to 5 mol% is particularly preferred.
  • Examples of mercaptoalkyl or mercaptoaryl residues attached to the polysiloxane skeleton are the mercaptomethyl, 2-mercaptoethyl, 3-mercaptopropyl, 3-mercaptoisobutyl or mercaptophenyl residue.
  • the 3-mercaptopropyl radical is particularly preferred.
  • mercaptoalkyl or mercaptoaryl residues are bound to the organopolysiloxane molecule, preferably 0.1 to 1 mol%.
  • Suitable aminoalkyl radicals which are also preferably used, are the 3- (2-aminoethyl) aminopropyl or the 3-aminopropyl radical.
  • suitable aminoalkyl radicals are the 4- (2-aminoethyl) aminobutyl radical or the 3- (2-aminoethyl) aminoisobutyl radical.
  • aminoalkyl radicals form 0.06 to 6 mol% of the radicals R 1 and R 2 .
  • the preferred range is 0.2 to 2 mol%.
  • Anionic groups can also be bound to the organopolysiloxane molecule. These anionic groups are bound to the silicon atom by a divalent hydrocarbon radical.
  • the carbon chain R 3 of the divalent hydrocarbon radical can be interrupted by oxygen, nitrogen or sulfur atoms.
  • the groups are particularly suitable as anionic groups where m is 0 or 1 and X is an -O- radical or the group -OR 4 .
  • R 4 is a hydrogen radical or an alkyl radical with 1 to 4 carbon atoms.
  • Examples of such groups are 0.1 to 10 mol% of the groups R T and R 2 are formed by such anionic groups, but preferably 0.3 to 6 mol%.
  • the preparations according to the invention can be produced in two different ways.
  • the reaction can also be carried out in the form of cocondensation in an anhydrous medium.
  • cyclic siloxanes can be used in a known manner (US Pat. No. 2,891,920), optionally from their mixture with organomodified di (tri) alkoxysilanes, such as, for. B. 3-mercaptopropyl-methyl-diethoxysilane, 3-aminopropyl-methyl-diethoxysilane or silanes of the formula the corresponding organomodified ⁇ , ⁇ -polydimethylsiloxane diols are prepared in the presence of anionic or cationic polymerization catalysts.
  • organomodified di (tri) alkoxysilanes such as, for. B. 3-mercaptopropyl-methyl-diethoxysilane, 3-aminopropyl-methyl-diethoxysilane or silanes of the formula the corresponding organomodified ⁇ , ⁇ -polydimethylsiloxane diols are prepared in the presence of anionic or cationic polymerization catalysts.
  • siloxane diols can then be reacted further with trialkoxysilanes modified or modified with polyalkylene glycol ether or with SH or amino groups and also with silanes, for example of the formula via which an anionic group can be introduced into the organopolysiloxane.
  • the synthesis of the organomodified alkoxysilanes is known to the person skilled in the art.
  • organopolysiloxanes in the non-aqueous phase, it is expedient to start from a sulfuric acid ester of an organosilicon alcohol of the formula out.
  • the reaction product also contains terminally reactive SiOH groups which are capable of cocondensation with the alkoxy groups of the silanes modified with polyalkylene glycol ether, optionally also with mercaptoalkyl.
  • cocondensation which is preferably carried out at higher temperature in the presence of tertiary amines, removed the solvents by simple distillation.
  • organopolysiloxanes prepared in this way can also be converted into aqueous preparations according to the invention by incorporating water, possibly in the presence of suitable emulsifiers.
  • a suitable solvent such as methylene chloride
  • the reactants are diluted with methylene chloride to a volume of 500 ml.
  • reaction product After a two-hour stirring phase, the reaction product with 64.8 g (0.071 mol) of a silane of the formula and 7.97 g (0.033 mol HS-) of a slightly condensed partial hydrolyzate of 3-mercaptopropyltriethoxysilane with 15% by weight OH, heated to 60 ° C. and stirred for a further 2 hours.
  • the partially condensed partial hydrolyzate was obtained by the reaction of 3-mercaptopropyltriethoxysilane with 2% hydrochloric acid in methylene chloride.
  • the fine-particle preparation thus prepared contains an organopolysiloxane in which the radicals R 1 and R 2 are 1.29 mol% and 0.322 mol% consist of - (CH 2 ) 3 -SH residues; the remaining residues are methyl residues.
  • the potassium hydroxide solution contained in the emulsion is neutralized by adding 12 g of a 10% acetic acid.
  • a 95 ° C. hot emulsifier solution corresponding to Example 3 is added dropwise with vigorous stirring with 167 g (0.56 mol) of octamethylcyclotetrasiloxane and 15.95 g (0.03 mol) transferred. After the dropwise addition, stirring is continued for 1 h and 6.05 g (0.027 mol) of 3- (aminoethyl) aminopropyltrimethoxysilane are added. Following a further 30 minute stirring phase, the mixture is cooled to 40 ° C. and the emulsion is neutralized by adding 16 g of 10% acetic acid.
  • an emulsifier solution is prepared, which, after heating to 95 ° C. with vigorous stirring, is added via a dropping funnel to 167 g (0.56 mol) of octamethylcyclotetrasiloxane added. After stirring for a further 60 min, 27.98 g (0.03 mol) are added dropwise and stir again for 30 min. The emulsion is then cooled to 40 ° C. and neutralized by adding 12 g of 10% acetic acid.
  • the finely divided aqueous preparation contains an organopolysiloxane, the radicals R 'and R 2 of which are methyl radicals, of which, however, 0.66 mol% are replaced.
  • the required amount of this mixture is dissolved in toluene and diluted to the desired application concentration.
  • the unfinished sample showed a heavily matted surface.
  • the handle of the treated samples was also significantly softer after washing than the handle of the untreated material after washing and corresponded to the handle before washing.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Silicon Polymers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Claims (7)

1. Préparation pour rendre la laine irrétrécissable. comprenant
a) 1 à 50% en poids d'organopolysiloxanes constitués par
ai) 90 à 99,8 mol% d'unités de la formule
Figure imgb0061
et
a2) 0,2 à 10 mol% d'unités de la formule
Figure imgb0062
formules dans lesquelles R1 et R2 sont formés d'une part de
0,1 à 10 mol% de radicaux polyoxyalkylène et d'autre part de
0,03 à 3 mol% de radicaux mercaptoalkyle ou mercaptoaryle et/ou
0,06 à 6 mol% de radicaux aminoalkyle et/ou
0,1 à 10 mol% de groupes anioniques rattachés à des atomes de silicium par des atomes de
carbone,
la fraction restante des groupes R1 et R2 étant des groupes méthyle dont, cependant, 10 mol% au maximum peuvent être remplacés par des radicaux alkyle à chaîne plus longue, aryle ou hydrogène, 5 mol% au maximum des atomes d'oxygène rattachés à Si pouvant être remplacés chacun par deux groupes alcoxyle inférieurs ou hydroxyle, et
b) 50 à 99% d'eau, éventuellement d'émulsifiants et/ou de solvants organiques et éventuellement d'additifs usuels.
2. Préparation selon la revendication 1, caractérisée par le fait que les radicaux polyoxyalkylène répondent à la formule
Figure imgb0063
et sont rattachés au polysiloxane directement par un point SiOC ou, par l'intermédiaire d'un radical hydrocarbure divalent, par un pont SiC, Z étant un radical hydrogène, un radical alkyle ou aryle monovalent, un radical acyle ou un radical triméthylsilyle, n valent de 2 à 3 et x valant de 2 à 80.
3. Préparation selon la revendication 2, caractérisée par le fait que les radicaux polyoxyalkylène répondent à la formule
Figure imgb0064
dans laquelle Y est le radical
Figure imgb0065
 ou le radical triméthylsilyle et y vaut de 4 à 20.
4. Préparation selon une ou plusieurs des revendications précédentes, caractérisée par le fait que les radicaux mercaptoalkyle contiennent un radical alkyle à chaîne droite ou ramifiée contenant 1 à 4 atomes de carbone.
5. Préparation selon une ou plusieurs des revendications précédentes, caractérisée par le fait que les radicaux aminoalkyle sont des radicaux 3-(2-aminoéthyl)-aminopropyle ou 3-aminopropyle.
6. Préparation selon une ou plusieurs des revendications précédentes, caractérisée par le fait que les groupes anioniques répondent à la formule:
Figure imgb0066
et qu'ils sont présents sous la forme de l'acide ou totalement partiellement neutralisés, R3 étant un radical hydrocarbure divalent qui peut être interrompu par des atomes d'oxygène, d'azote ou de soufre, X étant le radical -0- ou le groupe -OR4, R4 étant un radical hydrogène ou un radical alkyle contenant 1 à 4 atomes de carbone, et m valant 0 ou 1.
7. Préparation selon une ou plusieurs des revendications précédentes, caractérisée par le fait que R' et R2 sont formés d'une part de
0,3 à 5 mol% de radicaux polyoxyalkylène et d'autre part de
0,1 à 1 mol% de radicaux mercaptoalkyle ou mercaptoaryle et/ou
0,2 à 2 mol% de radicaux aminoalkyle et/ou
0,3 à 6 mol% de groupes anioniques rattachés à des atomes Si par des atomes C
et que la fraction restante des groupes R1 et R2 sont des groupes méthyle, 10 mol% au maximum de ceux-ci pouvant toutefois être remplacés par des radicaux alkyle à chaîne plus longue ou des radicaux aryle.
EP80100297A 1979-03-23 1980-01-22 Produit antifeutrant pour laine Expired EP0016907B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB7910341 1979-03-23
GB7910341 1979-03-23

Publications (3)

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EP0016907A2 EP0016907A2 (fr) 1980-10-15
EP0016907A3 EP0016907A3 (en) 1981-03-18
EP0016907B1 true EP0016907B1 (fr) 1982-02-17

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EP80100297A Expired EP0016907B1 (fr) 1979-03-23 1980-01-22 Produit antifeutrant pour laine

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US (1) US4283191A (fr)
EP (1) EP0016907B1 (fr)
JP (1) JPS584114B2 (fr)
AU (1) AU529018B2 (fr)
DE (1) DE3060191D1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3034380A1 (de) * 1980-09-12 1982-03-25 Th. Goldschmidt Ag, 4300 Essen Zubereitung zum schrumpffestmachen von wolle
JPS57171768A (en) * 1981-04-15 1982-10-22 Shinetsu Chem Ind Co Fiber treating agent
DE3417912C1 (de) * 1984-05-15 1985-07-25 Goldschmidt Ag Th Betaingruppen enthaltende Siloxane,deren Herstellung und Verwendung in kosmetischen Zubereitungen
DE3735086C1 (de) * 1987-10-16 1989-02-02 Goldschmidt Ag Th Organopolysiloxane mit Buntesalzgruppen
US5269950A (en) * 1989-06-05 1993-12-14 Sanyo Chemical Industries, Ltd. Textile treating compositions
US5336419A (en) * 1990-06-06 1994-08-09 The Procter & Gamble Company Silicone gel for ease of ironing and better looking garments after ironing
DE4100703A1 (de) * 1991-01-11 1992-07-16 Chu Tjoei Ho Textilausruestungsmittel
EP0791096A1 (fr) * 1994-11-10 1997-08-27 The Procter & Gamble Company Composition attenuant les faux plis
US5532023A (en) * 1994-11-10 1996-07-02 The Procter & Gamble Company Wrinkle reducing composition
US20070190872A1 (en) * 2006-02-16 2007-08-16 Weber Robert F Fire retardant silicone textile coating
CN103958530A (zh) * 2011-11-04 2014-07-30 道康宁公司 亲水性有机硅烷

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB594901A (en) 1945-04-11 1947-11-21 Wolsey Ltd Improvements relating to the treatment of materials consisting wholly or partly of wool
GB613267A (en) 1946-06-14 1948-11-24 Wolsey Ltd Improvements relating to the shrinkproofing of materials consisting wholly or partlyof wool
GB629329A (en) 1947-05-05 1949-09-16 Wolsey Ltd Improvements relating to the shrinkproofing of materials consisting wholly or partlyof wool
US2728692A (en) 1953-04-20 1955-12-27 Dow Corning Method of preventing shrinkage of wool
US2891290A (en) * 1957-07-16 1959-06-23 Gen Bronze Corp Window scupper arrangement
NL279187A (fr) * 1961-06-01
CH106968D (fr) * 1965-01-21 1900-01-01
DE1594953A1 (de) * 1966-05-28 1969-07-03 Rotta Chem Fab Theodor Verfahren zur Ausruestung von Fasergut mit Polysiloxanen
GB1431321A (en) * 1973-01-30 1976-04-07 Ici Ltd Surface treating compositions
CH615968D (fr) * 1967-04-26 1900-01-01
GB1396509A (en) * 1971-08-28 1975-06-04 Dow Corning Ltd Treatment of keratinous fibres
US3876459A (en) * 1973-06-29 1975-04-08 Dow Corning Treatment of fibres
GB1502265A (en) * 1974-05-28 1978-03-01 Dow Corning Ltd Treatment of fibres
AU1823676A (en) * 1975-10-13 1978-04-06 Commw Scient Ind Res Org Treatment of wool with polyorganosiloxanes
GB1548224A (en) * 1976-02-12 1979-07-04 Goldschmidt Ag Th Organosilicon compounds and textile fibre dressings which contain these compounds
GB1572397A (en) * 1976-06-11 1980-07-30 Dow Corning Ltd Fibre treatment composition and process

Also Published As

Publication number Publication date
DE3060191D1 (en) 1982-03-25
AU529018B2 (en) 1983-05-19
AU5673280A (en) 1980-09-25
JPS55128076A (en) 1980-10-03
EP0016907A2 (fr) 1980-10-15
US4283191A (en) 1981-08-11
JPS584114B2 (ja) 1983-01-25
EP0016907A3 (en) 1981-03-18

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