Classifications

• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
  • H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/22—Roughening, e.g. by etching
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/48—Coating with alloys
  • C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
• • 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
  • D06M15/55—Epoxy resins
• • 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
  • D06M15/63—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing sulfur in the main chain, e.g. polysulfones
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
  • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
  • H05K2203/1152—Replicating the surface structure of a sacrificial layer, e.g. for roughening
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
  • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
  • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating

Definitions

• the present invention relates to a process for modifying keratinous fibres, and in particular, to a process for rendering keratinous textile materials resistant to shrinkage and to a process for imparting durable press characteristics to such materials.
• This process comprises heating the material with a polythiol and an aliphatic polyamine-epichlorohydrin resin, and curing the polythiol on the material.
• the present invention also relates to (1) a composition useful in said process, which composition consists essentially of a polythiol and an aliphatic polyamine-epichlorohydrin resin, and (2) keratinous material bearing thereon a polythiol, in the cured or still curable state, and an aliphatic polyamine-epichlorohydrin resin.
• the present invention relates to a process for modifying keratinous fibres, and in particular, to a process for rendering keratinous textile materials resistant to shrinkage and to a process for imparting durable press characteristics to such materials.
• shrink-resist processes and durable press processes for keratinous textile materials are known, some of which comprise the application'of a resin to the material, which may be in fabric or fibre form.
• Shrink-resistant processes stabilize the dimensions of the material against shrinkage due to felting or relaxation.
• Durable press processes stabilize the desired shape and the surface smoothness of the material against deformation in the presence of aqueous solutions.
• a desirable, though not essential, feature of shrink-resist and durable press processes is that the material so treated should be washable in domestic washing machines, and this sets a severe test for the durable press and shrink-resist treatments.
• Some known treatments result in a uniform but inadequate improvement to the resistance of the material to shrinking whilst others are capable of imparting a very high but irregular resistance. In the latter case, under vigorous mechanical action in a washing machine, felting shrinkage at exposed edges of the garment, such as cufis, can be greater than at less exposed parts.
• polythiols can be used to impart durable press effects and resistance to shrinkage without impairing the handle of the treated material.
• a process for modifying keratinous material which comprises treating the material with a polythiol as aforesaid and an aliphatic polyamineepichlorohydrin resin, and curing the polythiol on the material.
• the aforesaid agents viz. the polyamine-epichlorohydrin resin and the polythiol, may be applied to keratinous fibres by exhaustion from an aqueous medium.
• exhaustion means the method of treating the fibres with an aqueous solution or emulsion of the polythiol or polythiol-resin mixture until a major proportion of the polythiol or the mixture is deposited on the fibres. It is believed that, in addition to promoting the curing of the polythiol, the polyamine-epichlorohydrin resin also promotes exhaustion of the polythiol.
• Aliphatic polyamine-epichlorohydrin resins are known materials. They are cationic, polymeric, and crossable; they are usually water-soluble and are usually made by reaction with epichlorohydrin of a polyalkylenepolyamine such as a poly(ethyleneimine) and particularly an amine containing from 2 to 8 alkylene groups per molecule, sometimes in the presence of a base, followed by acidification.
• a polyalkylenepolyamine such as a poly(ethyleneimine) and particularly an amine containing from 2 to 8 alkylene groups per molecule, sometimes in the presence of a base, followed by acidification.
• the term aliphatic polyamine-epichlorohydrin resin also includes those derived from more complex amines. In particular, there may be used amines made by heating polyalkylenepolyamines with dicyandiamide.
• poly(aminoamides) made from polyalkylenepolyamines and aliphatic dicarboxylic acids or amide-forming derivatives thereof, e.g. their dimethyl ester.
• polyalkylenepolyamines with stoichiometric deficits (calculated on the basis of one epoxide group per amino hydrogen atom) of monoor poly-1,2-epoxides.
• the amount of the amine-epichlorohydrin resins used in the present process can be small, often only cata- .lyti'c proportions being used. It is evident therefore, that the success of 'the present process is not attributable merely to any inherent shrinkproofingelfect of the polyamine-epichlorohydrin resin.
• v Amine-epichlorohydrin resins which have been found most satisfactory for use in the present process are obtainable by reaction of a saturated aliphatic dicarboxylic acid of 3 't'o20 carbon atoms (or an amide-forming derivative thereof) and a polyalkylenepolyamine containing 2 to 8 alkylene groups, reaction of the resultant poly- (aminoamide) with epichlorohydrin, and acidification to form a water-soluble cationic resin.
• An example of a commercially-available resin which has proved especially useful is obtained by forming an amide such as is repre sented by the equation followed by treatment with epichlorohydrin and then acidification.
• Examples of aliphatic dicarboxylic acids from which these epichlorohydrinpolyamine resins can be derived are malonic, succinic, adipic, and azelaic acids; examples of their amide-forming derivatives are their dirnethyl esters; there may also be used mixtures of such acids or esters.
• One or more polyamines can be used in the formation of vthese epichlorohydrin-polyamine resins; specific examples, are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, and N,-bis(3- aminopropyDmethylamine.
• Suitable amines preferably contain at least 2 amino groups separated by a hydrocarbon group having the general formula C,,,H where a is at least 2 and -at most 4.
• the term keratinous material as used throughout this spec fication includes all forms of kcratinous fibres or fabricsand garments made therefrom, e.g.
• the treatment will be applied to fabrics or made-up garments though it is quite feasible, and may 'be desirable in some c rcumstances, to treat fibres in the form of tops, for example.
• the material to be treated can consist either wholly of keratinous fibres or of blends of these fibres withsynthetic fibrous and filamentary material, in--.
• the material should contain at least 30% by weight of kcratinous fibres and the most useful effects are obtained with 100% kcratinous fibre material.
• the kcratinous material may be virgin or reclaimed and is preferably sheeps wool. It may, however, also be derived from alpaca, cashmere, mohair, vicuna, guanaco, camel hair, and llama, or blends of these materials with sheeps wool.
• the treatment according to the invention whether to achieve shrink-resist or durable press effects, provides fabrics or garments which will withstand washing in machines without the development of local areas of felt- 4 I f a ing and still retain their orginial dimensions and shape.
• fabrics or garments which will withstand washing in machines without the development of local areas of felt- 4 I f a ing and still retain their orginial dimensions and shape.
• hag d l e tl 1 e t r gt ed material also has good recovery from wrinkling, which is an important attribute in many garments but especially in trousers, where there is a strong tendency to wrinkles in the areas of the knee and back of the knee.
• Thepolythiols usually contain up to isix thiol groups per average molecule and especially good results have been obtained with those containing three or four thiol groups per average molecule.
• a i r The preferred polythiols arethose'having .a molecular weight between 400 and 10,000, particularly those; of formula i -j n, p, and q each represent positive-integers,
• n is an integer of at least 1 and may have different values in each of the p and (q'-1 chains,
• p is at least 2 and at most 6,
• each alkylene group contains a chain of at least 2 and at most 6 carbon atoms between consecutive oxygen atoms
• R represents an aliphatic radical containing at least (but preferably not more than 6)carbon atoms
• X represents an aliphatic radical containing at least one thiol group.
• the oxyalkylene units in individual poly('oxyalkylene) chains may be different. They may be substituted', if desired, by e.g., phenyl or chloromethyl groups.
• esters of the formula u is a positive integer of at most 2
• I p is an integer of at least 3 and' 'at most 6,
• R represents an aliphatic hydrocarbon radical having at least 3 and at most 6 carbon atoms.
• alkylene and m have the meanings previouslyassi'gned
• poly(tetrahydrofuran)s poly(tetrahydrofuran)s, glycerol, l,l,1-trimethylolethane, 1,1,l-trimethylolpropane, hexane-1,2,5 triol, hexane-1,2,
• alkylene oxides include ethylene oxide, propylene oxide, and, less preferable the butylene oxides, cpichlorohydrin, or tetwhydrofurart.
• n and u have the meanings previously assigned, and t is an integer of at least 2 and at most 3.
• Polythiol esters most preferred for the purposes of the present invention are those obtained from glycerol, propylene oxide, and thioglycollic acid, i.e. of formula where m has the meaning previously assigned, having a molecular weight within the range 1000 to 6000. Such esters are commercially available.
• the second class of thiol-terminated poly(alkylene oxides) includes those ethers of formula in which R; denotes OH, (Oalkylene) OH,
• v is an integer of at least 1 and may have different values in each of the p chains.
• the oxyalkylene units in the individual poly(oxyalkylene) chains may likewise be different, but are preferably the same, and may be substituted if desired by e.g., phenyl or chloromethyl groups.
• ethers Preferred among such ethers are those which are also of formula 1 (oalk 1ene) 0CH,CH0H,sH
• alkylene, R m, R p, and q have the meanings previously assigned, and further preferred are those of the formula in which R t, m, and p have the meanings previously assigned.
• the ethers of formula II in which R denotes OH may be prepared in a known manner by reaction of an alkylene oxide with a polyhydric alcohol, etherification of the hydroxyl groups of the product with epichlorohydrin, and treatment with sodium hydrosulphide to replace the chlorine by a sulphydryl group (see US. Pat. 3,258,495, and United Kingdom Specifications 1,076,725 and 1,144,- 761). In many cases the average number of thiol groups per molecule is not an integer but, for example, may be 2.6.
• chlorohydrin ether obtained by reaction with epichlorohydrin may also react with epichlorohydrin, so forming an ether which contains two replaceable chlorine atoms per hydroxyl group originally present in the polyhydric alcohol.
• Ethers of formula R.j o onmmo cmt znernsn l L 0 ounmon l m in which R 1, m, v, and p have the meanings previously assigned, may likewise be used.
• ethers having a molecular weight within the range 700 to 6,000.
• ether-esters of formula II in which R, denotes O.CO.C,,H ,,SH or --(Oalkylene) 0.CO.C H SH are obtainable by esterification of the corresponding alcohol with a mercaptocarboxylic acid HOOCC H- SH.
• the epichlorohydrin-polyamine resins usually dissolve in water present in the treatment bath. Many of the polythiols are insoluble in water but can, as has already been indicated, he applied as aqueous dispersions or emulsions in which the epichlorohydrin-polyamine resin may for convenience be included.
• the polythiols may also be applied to fabrics and garments from organic solvents, for example lower alkanols such as ethyl alcohol, lower ketones such as ethyl methyl ketone, benzene, halogenated hydrocarbon solvents, especially chlorinated and/or fluorinated hydrocarbons containing not more than three carbon atoms such as the dry cleaning solvents carbon tetrachloride, trichloroethylene, and perchloroethylene.
• organic solvents for example lower alkanols such as ethyl alcohol, lower ketones such as ethyl methyl ketone, benzene, halogenated hydrocarbon solvents, especially chlorinated and/or fluorinated hydrocarbons containing not more than three carbon atoms such as the dry cleaning solvents carbon tetrachloride, trichloroethylene, and perchloroethylene.
• the amount of polythiol used depends upon the effect desired. For most purposes from 0.5 to 15%, based on the weight of textile material is preferred; stabilization of knitted fabrics usually requires from 1 to 10% polythiol. A high level of shrink-resistance, crease-setting, and substantial resistance to wrinkling can be achieved on woven fabrics with rather smaller quantities, especially from 1 to 5%.
• the amount of the aliphatic polyamine-epichlorohydrin resin which can be used depends to an important extent upon the nature of the polythiol present. In general from 0.1 to 1.0% of polyamine-epichlorohydrin resin based upon the weight of material is sufiicient but the amount must be carefully selected to give the best result.
• the desired effects are not fully obtainable until substantially all the polythiol on the material has been cured.
• the curing reaction is greatly accelerated by the use of the epichlorohydrin-polyamine resin and generally it is preferred to add it to the material to be treated at the same time as the polythiol is applied although it may be added before or afterwards if desired.
• Curing of the polythiol is also assisted by using elevated temperatures and if especially rapid results are required then temperatures in the range 30 to 180 C. may be used. High humidities also tend to accelerate the curing: autoclaving of the treated material may therefore be desirable.
• Curing is preferably carried out under neutral or slight- 1y alkaline conditions (e.g. in the presence of sodium pyro phosphate or sodium bicarbonate), say, at a pH in the range 7 to 9, and may also be accelerated by means of a freeradical catalyst, e.g. hydrogen peroxide.
• a freeradical catalyst e.g. hydrogen peroxide.
• the polythiol and the epichlorohydrin-polyamine can be applied to the keratinous material in conventional ways. For example, where wool tops or where fabric is to be treated, they may be padded on or the material may be immersed in a bath containing the agents. If garments or garment pieces are to be treated then it is convenient to spray them with the agents, and more convenient still to tumble them with the agents in an organic solvent. For the latter method a dry-cleaning machine using a drycleaning solvent is a particularly useful apparatus.
• the polythiol and the epichlorohydrin-polyamine resin can, as already indicated, he applied to the fabric by exhaustion, and such a treatment can be applied before, simultaneously with, or after dyeing. Exhaustion can be carried out at a pH in the range 2-10, especially 4-8, and at any temperature from room temperature (say, C.) to 100 C., and will normally be complete after l-2 hours. The process is especially advantageous in that exhaustion may be carried out at temperatures up to 50 C. with substantially complete exhaustion of the agents.
• a shrink-resist treatment is usually convenient to apply the reactants to the fabric although, as previously stated, they may be applied to fibres in the form of tops or card sliver.
• Setting including flat-setting of the fabric, whether carried out before or after treatment with the polythiol and the epichlorohydrin-polyamine resin, may be effected using any of the known methods, for example by means of setting agents, such as reducing agents, bases, water, and superheated steam.
• Monoethanolamine sesquisulphite is the most frequently used and may be used in association with a swelling agent, e.g. urea.
• the material is impregnated with a swelling agent and an alkanolamine carbonate, e.g. urea and diethanolamine carbonate, dried, and semi-decated.
• the fabric may be set in the presence of the agents, thus effecting setting and shrinkproofing treatments simultaneously.
• a durable press treatment there are a number of ways this may be achieved.
• One method is to treat the material with the agents, make the material up into garments or garment pieces and insert therein pleats or creases, using reducing agents, bases, or superheated steam as setting agents.
• the agents may likewise be applied to the fibres at any stage during the manufacture of the fabric, eg. in the form of tops or yarns.
• substances which block the thiol groups of the wool e.g. formaldehyde or higher aldehydes, may be applied to the creased or pleated garments after curing the poly thiol.
• Another method of applying the polythiol to obtain a durable press effect comprises treating the made-up garment or garment piece, which is already in the desired configuration, e.g. has creases or pleats imparted thereto, with the polythiol dissolved in an organic solvent.
• this method it is essential that the polythiol is applied in an organic solvent because treatment with aqueous systems would remove the creases or pleats already set in the fabric.
• An alternative method which is primarily concerned with the production of durable press pleats or creases only, comprises impregnating the fabric with the agents in the area where a fold, such a crease or pleat, is to be inserted, imparting the desired configuration, and maintaining it in this position whilst heat and pressure are applied.
• a method for flat-setting and shrinkproofing keratinous fabrics comprises treating the fabric with a setting agent and setting it in a flat configuration by heating the fabric while wet, impregnating it with an aqueous emulsion or dispersion of the agents, drying the fabric and curing the polythiol. Finally the fabric is made into garments, and creases or pleats set therein, if desired, by steaming in the presence of a setting agent such as monoethanolamine sesquisulphite.
• a setting agent such as monoethanolamine sesquisulphite.
• Milling effects can be imparted, especially to knitted woollen goods, by tumbling them in a dry-cleaning solvent containing the reagents and a controlled amount of water.
• the exhaustion treatment can be combined with dyeing with any anionic dye which will exhaust onto the wool.
• Commercially available acid levelling dyes can be used, for example Supracid Yellow R (Francolor, Erio Fast Floxine KL, Erio Fast Blue ZGL, and Solophenyl Turquoise Blue GL (Ciba-Geigy), Lissamine Fast Red B and Solway Blue PFN (ICI), and A20 Rubinole 3 GP (Sandoz).
• Suitable premetallized dyes include Cibalan Orange G and Irgalan Brown GRL (Ciba-Geigy), Carbolan Green G 125 (ICI), Lanasyn Yellow 2RL (Sandoz) and Neolan Red BRE (Ciba- Geigy).
• Suitable reactive dyes which include Lanasol Yellow 4G, Lanasol Red 6G, and Lanasol Blue 3G (Ciba- Geigy) and Procilan Red GS (ICI) can also be used.
• Acid milling dyes for example, Polar Brilliant Red 3BN (Ciba-Geigy) can also be used.
• the polythiols used were prepared as follows.
• POLY'I'HIOL A A mixture of 800 g. (0.2 g.-mol.) of a triol of average molecular weight 4,000 made from glycerol and propylene oxide, 55.2 g. (0.6 g.-mol.) of thioglycollic acid, 5 g. of toluene-p-sulphonic acid and 350 ml. of toluene was heated to reflux with stirring in an atmosphere of nitrogen. Water (10.8 ml., 0.6 g.-mol.) formed during the reaction was removed as its azeotrope with toluene. The mixture was cooled and washed with water, and the organic layer was separated. On removal under vacuum of the solvent from the organic layer there remained 793 g. (94% of the theoretical yield) of the desired tris(thioglycollate) (Polythiol A), having a thiol content of 0.59 equiv./kg.
• 'POLYTHIOL B This is a poly(2-hydroxy-3-mercaptopropyl) ether prepared from a glycerol-propylene oxide adduct having an average molecular weight of 4,800, epichlorohydrin, and
• the polyamine resins were:
• Polyamine resin I Polyamine resin II Three moles of diethylene triamine are first heated with 1 mole dicyandiamide and then with 2 moles of dimethyl adipate. This reaction product is then heated with 4.5 moles of epichlorohydrin, and the resin is finally diluted with water to give a 20% solution of Polyamine resin II.
• Polyamine resin III An epoxide (68.5 g.), having an epoxide equivalent weight of 685 and which has been made by reaction of 2,2-bis(4-hydroxyphenyl)propane first with epichlorohydrin and then with a mixture of l-aminoeicosane and l-aminodocosane, is dissolved in 37 g. of isopropanol and heated to 88. Then a poly(aminoamide) (24.7 g.) prepared from polymerized linoleic acid and diethylenetriamine (0.1 amino group equivalent), dissolved in 15 g. of isopropanol, is added dropwise to the epoxide solution.
• a poly(aminoamide) (24.7 g.) prepared from polymerized linoleic acid and diethylenetriamine (0.1 amino group equivalent), dissolved in 15 g. of isopropanol
• the emulsions containing the polythiol were prepared by dissolving 0.5 part of sodium carboxymethylcellulose in 44.5 parts of water at 70 to 80", allowing the solution to cool, adding 50 parts of the polythiol and 5 parts of Wetting Agent I, and stirring with'a high speed mixer for 5 minutes.
• the samples were then dried flat in an oven at 70 and were conditioned for 16 hours at a temperature of 20 and a relative humidity of
• the dimensions of the fabric were measured before and after washing and the linear shrinkage in length and width was calculated.
• the area shrinkage was calculated from the changes in linear dimensions.
• EXAMPLE 2 The fabric employed was a wool flannel weighing ap proximately 170 g. per square metre. Samples were padded to 140% pickup with the following formulations (Polythiol A was added as an aqueous emulsion), both of which also contained suflicient sodium bicarbonate to bring their pH up to 7.8.
• Weight Agent III is an adduct of p-octylphenol with 8 mol. of ethylene oxide.
• the samples After being dried at for 15 minutes, the samples were heated for 5 minutes at or steamed for 2% minutes with a steam iron to complete the curing.
• the washing liquor was an aqueous solution of soap flakes (2 g. per litre) and anhydrous sodium carbonate (0.8 g. per litre), and the liquor/sample ratio was about 30:1.
• the samples were rinsed in cold water, spun in the machine, and then dried for 30 nun' utes in a Parnall tumble drier on full heat.
• the samples were washed in. a Bendix MRE rotating drum washing machine for onehour in phosphate buffer of pH 7 at 40 using a liquorzgoods ratio of 22:1. .After washing the samples, they werecen: trifuged for 30 seconds. Some of the samples were washed for a total of 10 hours to detect any break-down in the effect of the agents on prolonged washing.
• EXAMPLE 6 This Example illustrates impregnation with two baths. "'Wool-flannel'waspaddedto' 300% 'uptake with a perchloroethylene solution 'ofiPoly'thiol A so as to leave 3% of- Polythiol A on' the weight of wool.
• the treated fabric dried 'in an oven at at its original dimensions. Portions of the flannel were then padded to uptake with a 18%" aqueous solution or Polyamine I containihgjlo 'g. per litre of sodium bicarbonate.
• the cloth was dried at 70 C. in. an oven at its original dimensions, and. washed by the procedure described in Example 3.
• the shrinkage in area was 4.5%; untreated wooltlannel shrank by 19.5%, while samples treated only with the polythiol shrank by 16%.
• a double jersey Ponfe di Roma fabric knitted from 32's worsted'.yarn 'to .cover factor-of 1.35 with a run-in ratio of 111.3
• polythiol being added as an aqueous emulsion.
• the treated fabric was then soaked for 60 minutes in an aqueous solution containing 3% of sodium carbonate (calculated on the weight of fabric), spun in a centrifuge, and dried. A level-dyed fabric having excellent shrinkresist properties was obtained.
• EXAMPLE 10 EXAMPLE 11 Example 9 was repeated except that in place of Polythiol A there was used the same amount of Polythiol B. This polythiol performed in the same way as did Polythiol A, and the resulting fabric exhibited a 1% area felting shrinkage after washing for 1 hour in a Cubex.”
• EXAMPLE 12 Samples of a scoured single jersey fabric knitted from 2/24s worsted yarn to cover factor of 1:1 were treated by exhaustion with the compositions specified in the following table (Polythiol A being added as an aqueous emulsion) at a temperature of 22 and at a liquorzgoods ratio of 50:1. The amounts of the polythiol and polyamine resin are expressed in terms of the weight of the fabric. After treatment was complete the samples were spun dry, soaked for 20-30 minutes in a solution containing 10% sodium carbonate on the weight of fabric at a liquor:goods ratio of 50:1, and oven-dried. The samples were then washed for 1 hour in a 15 litre Cubex at 40. The following results were obtained:
• Example 13 The scoured single jersey fabric of Example 12 was treated by exhaustion with an aqueous emulsion containing 5% by weight, calculated on the weight of the fabric, of Polythiol A, and 5% by weight, calculated on the weight of the polythiol, of Polyamine I. Exhaustion was carried out at 50 and was found to be complete after 15 minutes. The fabric was rinsed, and then treated with hydrogen peroxide and/or sodium pyrophosphate as shown in the following table at a temperature of 50 for 30 minutes to effect curing. The samples were then rinsed and dried.
• the scoured single jersey fabric of Example 12 was treated by exhaustion as described in Example 13. Instead of the peroxide/pyrophosphate curing treatment the fabric was treated with a mordant composition comprising sodium dichromate (1.5% by weight based on the weight of the polythiol and the resin) and formic acid (3.0% based on the weight of the polythiol and the resin) at the boil at a liquor: goods ratio of 50:1 for a period of 45 minutes. Sodium metabisulphite (1% by weight) was added to the bath and boiling was continued for a further 15 minutes. The bath liquor was drained away and the fabric was treated with the following dye composition, the percentages being the weights calculated on the weight of the fabric:
• Weight Agent III is an amphoteric polyglycol ether derivative.
• the bath was maintained at 50 for 30 minutes and then maintained at the boil for minutes.
• a yellow-dyed fabric was produced which exhibited a 5% area felting shrinkage after washing for 1 hour in a 15 liter Cubex.”
• Process for modifying keratinous material which comprises treating the material with (i) about 0.5 to 15% its weight of a polythiol having at least two thiol groups per molecule and containing (a) a radical of a polyhydric alcohol,
• R represents an aliphatic radical containing at least 2 carbon atoms
• X represents an aliphatic radical-containing-at least one t h iol group.
• r is a positive integer of from 1 to 24.
• u is a positive integer of at most 2, r'.;" H
• p is an integer of at least 3 and at most 6, I Y
• R represents an aliphatic hydrocarbon radical having at least 3 and at most 6 carbon atoms.
• u is a positive integer of at least 3 and at most 6-,
• t is an integer of at least 2 and at most 3;
• R, alkylene, m, p, and q have the meanings assigned in claim 4, H leis a positive integer of at least 3 and at most 6, and v is an integer of at least l and may have different values in each of the p'chains.
• polythiol is also of the formula [Rig- 10C HMmO'CHaCHCHzSH] in which m isan integer of at least 1 and may have different values in each of the p and ((1-41) chains,
• t is ;a positive integer of at least 3 and at most 6.
• polythiol is also of the formula CHE-(O CrHQmOCHAIEHCHzSH v I r 0H K-(OQtEMOCHzCHCHzSH H 'orr; -(o o,H'. ...ocH,( :HoHrsH Q A 0H v where m is an integer of atleast 1 and may have different values in each of the p and (ql) chains and has a moleg ular weight in the range 700 to 6,000.
• the aliphatic polyamine-epichlorohydrin resin is one made by reaction of a polyalkylenepolyamine containing from 2 to 8 alkylene'groups "with epichlorohydrin, followed by acidificati o n.
• the aliphatic polyarnine-epichlorohydrinresin is one made by heating a-polyalkylenepolyamine containing from 2 to 8 alkylene groups with dicyandiamide, ammonia being liberated, followed by reaction with epichlorohydrin and by acidificat-ion.
• the aliphatic polyamineepichlorohydrin resin is one made by heating 1 7 a polyalkylenepolyamine containing from '2 to 8 alkylene groups with an aliphatic dicarboxylic acid or an amideforming derivative thereof, followed by reaction with epichlorohydrin and acidification.
• the aliphatic polyamine-epichlorohydrin resin is one made by reaction of a polyalkylenepolyamine containing from 2 to 8 alkylene groups with a stoichiometric deficit of a monoor poly-1,2-epoxide, followed by reaction with epichlorohydrin and by acidification.

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• 1970
  • 1970-12-14 GB GB5935670A patent/GB1379203A/en not_active Expired
• 1971
  • 1971-12-13 CH CH1814471A patent/CH555931A/xx unknown
  • 1971-12-13 AU AU36825/71A patent/AU465757B2/en not_active Expired
  • 1971-12-13 CH CH1814471D patent/CH1814471A4/xx unknown
  • 1971-12-13 US US00207554A patent/US3813220A/en not_active Expired - Lifetime
  • 1971-12-14 FR FR7144875A patent/FR2118080B1/fr not_active Expired
  • 1971-12-14 DE DE19712162066 patent/DE2162066A1/de active Pending
  • 1971-12-14 DE DE19712162056 patent/DE2162056A1/de active Pending
  • 1971-12-16 FR FR7145214A patent/FR2118115B3/fr not_active Expired

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