DE1922303A1 - Process for the production of colored polymer material - Google Patents

Description

i Process for the production of colored polymer material

i *

The invention relates to methods for producing colored polymer material which is porous or in the form of objects or structures may be porous not as microporous! Films, coatings or sheet materials, which may optionally be strengthened by parsers are, as well as bands, threads or fibers in porous or non-porous form "The invention also relates in particular, but not exclusively, to a process which comprises coagulation of the polymers from a solution and is intended, inter alia, in particular for the production of colored microporous polyurethane sheet materials in flat or other shapes"

Many polymers and especially polyurethanes can be Only difficult to color in such a way that a good intensity and evenness the color and a color fastness can be obtained, and the coloring methods developed so far require a subsequent one Treatment of the polymer article, which affects the manufacturing * Contribution and costs of the colored article increases or the supply of the color pigments to the polymer and their distribution before require fine shaping or costly modifications of: polymers themselves. The known procedures included

Several process steps, since the surface of the polymer 0rst to-be made receptive to the color rnußj this encryption \ ride step However characterized subjected limitations: that the color has to withstand the process conditions, and _it; affects economic viability, especially if relatively ^; small batches of colored polymer are to be produced. In addition, relatively thin, ie "0.4 to 3 mm thick, micro-

9098 / .6 / 12U

especially porous polyurethane sheet materials or foils difficult to color afterwards. Films can be colored relatively easily in the mass, i. E. by prior addition the color or color pigments to the polymer, the manufacture of relatively small quantities of colored polymer material with a large-scale production facility is however unwirtschaftlictu

The invention is based on the finding that a polymer easily absorbs a dye from a liquid that is used for Coagulating the polymer from a solution is used, and that the color so absorbed is held very firmly by the polymer will"

The object of the invention is therefore to create a simple and economical method for coloring of polymer articles that coagulate during manufacture ^ and the polymer is stretched with a liquid carrier and in particular is in solution.

With the method according to the invention, flexible switch-shaped or shell-shaped objects made of polymer material produced in the same way should also be easy to color, with good color fastness being achieved (in particular, these are objects as they are in the at the same time under Claiming the priority of the British patent application Ur ₉ 20737/68 filed patent application (PP36) are described) β:

A further aim of the invention is the manufacture of relatively thick sheet materials, ie over 0.4 mm in thickness, from colored,; enable microporous, elastomeric polyurethanes with good color intensity, color uniformity and color fastness «, _;

According to the invention, this object is achieved in a method for producing colored polymer materials by the fol- following procedural steps solved »:

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(a) Formation of a die with a liquid carrier material 'Stretched polymer-containing mixture, which is preferably - A solution of at least one organic polymer in an organic solvent or in a mixture of organic Contain solvents

(b) Optional shaping of this mixture and '

(c) coagulation of the polymer in colored, and in in

. molded mixtures, self-supporting form having at least one ^: the polymer non-solvent which is preferably at least partially miscible with the liquid carrier or organic solvent and contains a coloring agent which is in solution during at least part of the coagulation process , preferably in the non-solvent; however, the colorant can also be dispersed in the nonsolvent and soluble in the carrier material or solvent? and ^: so at least partially during the coagulation process by the

! liquid carrier material or the solvent for the polymer ι be solved.

When used more than a light solvent for coagulation is, the coloring material is preferably contained in at least the first light solvent. The coagulation can by spraying or otherwise moistening the polymer mixture with the IT non-solvent can be achieved, however, an immersion will be achieved the Pc Iy me mixture in the IT non-solvent preferred

The term "shaping" is understood to mean any process by which your polymer material or the polymer- solution a fora is given, e.g. extruding the polymer solution through one or more slits or holes in a lye bath for the formation of foil or sheet materials, threads Each fiber · Furthermore, a £ esciilossen is a temporary or permanent coating of a carrier with a polymeric solution, for example by brushing on, pouring, knife coating, injection molding, spraying or by lau.chen, v; ctei äie! support flscli or three-dimensional

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BATH

can be so that hollow or shell-like three-dimensional shaped objects are created ©

The term "shaping" also includes the soaking or impregnation of fibrous sheet materials, for example non-woven mushroom; these materials are known for their wide range of applications, especially as leather-like materials, especially those which are processed into suede-like materials by grinding or polishing the surface leave, the surface being roughened, or which can be made by applying one or more microporous polymeric Coverings in leather-like materials with full-leather-like or can be transformed into a grained surface.

_O be the molded articles can be used as filaments, film, be sheet or fiber, it can enartige three-dimensionally formed articles as hollow or scarf ^, for example, as shoe uppers or as components formed therefrom The invention also extends to the production of a wide range of other shaped objects such as upholstery, clothing, for example jackets, pants, coats, hats, gloves, ties or other forms of footwear, for example slippers, boots or sandals, items of luggage, for example suitcases, briefcases, handbags, wallets, purses, jewelry boxes, floor- and wall coverings and other articles to be made from polymer using a coagulation process. The shaped objects can be porous or, if appropriate, also non-porous. If they are not intended to be porous, the porosity resulting from the coagulation can be eliminated by a suitable densification process, for example using heat or pressure or both, or by a combination of these processes. The material for most of the aforementioned purposes is preferably flexible , however, the invention also encompasses inflexible articles colored by the present process.

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The polymer can be any organic plastic or Be a resin material which can be formed into porous or non-porous films or fibers by coagulation from an emulsion, a colloidal dispersion, a gel or a solution »

j The polymer must also be able to withstand the various process steps described below "

however, if the product is to be a sheet-like material intended for use as a leather-like material, an elastomeric polymer is preferably used. Which specific polymer is used depends on the strength and the wear properties that are required for leather-like materials. For shoe upper leather material is ^; a high wear resistance and tensile strength in connection with reasonable elasticity and a suitable initial module! necessary so that the correct wearing comfort on the foot is achieved »

Many thermoplastic polymers can be used, for example polyvinyl chloride and copolymers thereof, Acrylonitrile polymers and copolymers and polyurethanes or mixtures of these compounds »

As is known, elastomeric polyurethanes and mixtures of these compounds with smaller proportions, for example up to 49%, preferably less than 20 ^c / o polyvinyl chloride; and other polymers and copolymers such as nitrile rubber, including solid copolymers of butadiene and acrylic ^! nitrile excellent for use as upper leather materials! for shoes »·

; Other polymers that are suitable for the use of leather-like materials are polyacetal resins, vinyl halide polymers (including copolymers with other ethylene-like unsaturated monomers), polyamides, polyester amides, polyesters, polyvinyl butyral, polyalphamethylstyrene, poly vinyl id en * -

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Chloride, polymers of alkyl esters of acrylic and methacrylic acids, chlorosulfonated polyethylene, copolymers of Butadiene and acrylonitrile cellulose esters and ethers, polystyrene and other polymers made from vinyl containing monomers are ο In addition, any polymers can be used which are suitable for the production of wet-spun fibersa

Preferred polymers, however, are elastomeric polyurethanes, which have regenerative properties between which have pure rubber and pure thermoplastic materials ο

In an essay by Schollenberger, Scott and luoore in "Rubber Chemistry and Technology" Volume XXXV, Ifr. 3, 1962, pages 742 to 752 are on page 743 in conjunction with Figo 3, the so-called long "half-lives" of the polyester urethanes, which are made from adipic acid, 1,4-butanediol and diphenylmethane-ρ, ρ ¹ -diisocyanate according to the US Patent No. 2,871,218 and are sold under the trade name ESTAHB 5740. :

Polyurethanes can be made from a large number of precursors that are combined with a large number of voja Polyols, polyamines and polyisocyanates can be reacted o It is known that the special properties: the resulting polyurethanes to a large extent ^ through a suitable choice of the action partner, the action ■ sequence and the reaction conditions the desired uses have it adjusted. i

The preferred polymers are elastopolymeric polyurethane; (Can be used although a polyether or a polyester / polyether mixture 1) thane on the basis of a linear polyester having endstän- \ DIGEM hydroxyl and a diisocyanate! with a small addition of a bifunctional low molecular weight reagent «This addition can be either with

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the other reagents at the start of a one-step polymerization or added in a later process step, in which case it is mainly used as a chain extender works

This type of polyurethane with thermoplastic properties is particularly suitable for the use of shoe uppers. "Particularly suitable are those polyurethanes which are produced from polyesters by reaction with diols and diisocyanates * It is known from US Pat. No. 2,871,218 that many different polyesters, diols and diisocyanates can be used, but that a polyurethane system is particularly suited _f has been implemented in which a polyester of adipic acid with 1,4-iithylenglycol and Buthylenglycol and with 4,4'-Diphenylin.ethandiisocyanat "

In this system, the oil ratios of the polyester and diol vary within quite a wide range, but the combined molar proportion of the polyester and diol will be so chosen that it is practically equal to the molar proportion of the diisocyanate is so that the resulting Polyir.er is practically free of hydroxyl or isocyanate groups which do not react to have.

Such polymers have a better Shore hardness and can be prepared by using a slight excess of diisocyanate and using an iuischpolyester, with a part of the ethylene glycol in the above-mentioned system is replaced by 1, 4-i? ethylene glycol.

Another particularly suitable polyurethane system uses polyesters derived from caprolacions, as they are in the case of- '. for example in British patent specification 859 640, to which reference is expressly made here.

The polymers can be polymerized in the 909846/1 2U

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- α -

Mass are prepared and then in suitable solvents dissolved or prepared directly as a solution in a solution polymerization process

The polymer can contain conventional stabilizers, fillers, processing aids, additives and surface-active agents, contain, for example, water-repellent impregnation or wetting agents.

As already mentioned, the polymer is preferably dissolved in a solvent, but the name! that the polymer is stretched with a liquid carrier, systems are also understood in which the polymer iac is present as an emulsion ¹ , colloid or gel, or in which it can with some justification be described as dissolved. Such colloids or gels can usually be added by adding a nonsolvent into a polymer solution. Examples of such processes are illustrated in British Patents 914,711, 94-6,069 and 984,088. However, other methods can also be used to produce a colloid or gel, for example the addition of an electrolyte, as is described in British patent specification 1 126 060, which reduces the solubility of the polymer in the solvent.

The non-solvent is preferably removed after the solvent, for example by drying, it is only necessary that as long as the solvent still present can still cause an undesired reduction in permeability, only so much non-solvent remains that this phenomenon does not occur; This can be achieved, for example, by using a light solvent whose boiling point is higher than that of the solvent _{or the like}

If the viscosity of the system is sufficient for formation thicker coatings is sufficient, can / can by cooling the mixture or by adding a thickener or on

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BATH ORIGINAL

other usual way to increase · It has been mentioned that one high vapor permeability in certain applications, e.g. when a layer of a polymer solution in a non-solvent for the polymer is desired is miscible with the solvent, bathing can have a certain degree of porosity and a corresponding degree of porosity Steam permeability occur, but the pores formed are not reproducible and evenly distributed and can strongly sohwankeno in their size depending on the most varied of parameters

Equally fine pores can be obtained if finely divided particles of a removable filler material which remains solid in the polymer solution or which is in a finely divided solid state while the polymer coagulates, and that at this point in time or evenly, in the polymer solution can be removed later, for example by leaching ₀

According to a preferred embodiment, the method according to the invention comprises the following steps

i £ a) Preparation of a mixture that is at least a solution of a polymer in at least one solvent containing particles of a removable filler, for example in the form of a solid powder of an inorganic salt, are evenly distributed,

(b) Shaping the mixture, for example into a three-dimensional layer, for example by covering a three-dimensional shape, such as a foot shape or a last, with the mixture and

(o) Coagulating the polymer with a polymer nonsolvent in which a dye is dissolved, wherein the non-dissolving agent preferably at least partially with

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- ίο -

is miscible with the solvent, and either simultaneously or then leaching practically all of the removable PUlIstoffee, so that the polymer in a colored, flexible microporous, self-supporting form remains.

Any material which is practically insoluble in the polymer solvent and which is inert to the solvent and polymer, but which is itself soluble or can be made soluble by means of a liquid which has no adverse effects on the polymer, can be used as a removable filler use. However, preference is given to inorganic salts, such as ammonium sulfate and, in particular, sodium chloride, because of their easy availability and the good possibilities of bringing them into finely divided form. The use of such temporary fillers has the additional advantage that the mixture containing these fillers has a substantially greater viscosity than the polymer solution or the polymer stretched with a liquid carrier, and this property facilitates the formation of three-dimensionally shaped layers and thick layers instead of or together Other pore-forming microscopic particle materials can also be used with the salt particles. Difse particulate materials may be starch (let stand by treating the coagulated layer with an aqueous _f the starch degrading material, for example a known enzyme, remove). Other microscopic solid particles can also be used which are insoluble in the polyurethane solution at least at the stage where the polymer is coagulated, for example urea, and which can be obtained either by treating the coagulated sheet material with water or another suitable solvent for the particles the polyurethane does not dissolve, heseüelee * or otherwise destroyed or removed or dissolved out. Examples of such particles are sodium carbonate, oxalic acid, ammonium carbonate or suitable microscopic hollow bodies or bubbles. On the other hand, the particulate material forming the cavities can also be in the form of dispersed microscopically small droplets in the

- ι ι -

Polyurethane solution insoluble liquid or in the form of dispersed microscopic gas bubbles are present.

In addition, pore formation can be achieved through dispersion removable / or remaining fibrous fillers are controlled, for example polyvinyl alcohol fibers or Polyamide fibers, or by installing remaining particle fillers such as silica, preferably very small particle sizes of e.g. less than 1 micron.

If a removable filler is used, such as sodium chloride, then the pore size of the resulting, Water vapor permeable material to a certain extent on the particle size of the filler in the paste (mixture) and if a microporous material is to be made, then none of the filler particles must be larger than 100 microns preferably most are substantially smaller, such as less than 50 microns, typically in the range of 1 to 40 microns or 3 to 20 microns.

i The weight ratio is preferably between filling;

substance and material (polymer) in the range 1.5 to 1 to 3 to 1j, preferably 1.7 to 1 to 2 to 1, and the weight ratio of the material for the solvent is in the range from 20:80 to 4-0:60, for example 25:75 to 35:65, preferably about 28 to 72 to 32 to 68. Preferably, the filler is ground so that more than 50 $ of the particles have a diameter of: Range from 4 to 20 microns.

Many solvents for organic polymers are known and any suitable, preferably organic, solvent can be used for the particular polymer used. ^{N, N 1} -DimethyIfor- are suitable for elastomeric polyurethanes. mamid, dimethyl sulfoxide, E-Hethylpyrrolidon, dimethylacetamide and tetrahydrofuran. Dimethylformamide, dimethyl sulfoxide and the other solvents can be diluted in cheaper solvents such as toluene and methyl ethyl ketone,

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BAD ORfGiNAL

which, although not themselves solvents for polyurethanes, do not act as calibrating solvents when mixed with dimethylformamide or mixed with the other solvents mentioned «

As mentioned earlier, the dye can be in the high solvent be soluble for the polymer; preferably the dye is soluble in water or in aqueous solutions which j used as the sole nonsolvent and leachant which coagulates the polymer and is used to leach the removable filler that may be present »

As a nonsolvent for the polymer, however, can also use organic liquids and in this case the dye is beneficial in this particular A non-solvent, for example an alcohol such as methanol, is soluble. '

It has been shown that the following general types of paint, all of which are soluble in alcohol, in particular for use with polyurethanes, especially those made from polyesters by reaction with diols and diisocyanates Polyrethanes are suitable »

Heterocyclic dyes, the thiazine subgroups and, for example, under the trade name methylene blue 2 tl.'S distributed v / earth; Triphenylmethane dyes, for example Disulfine Blue, Brilliant Green YlTS Crystals or iu & lachite green CPSj Anthraquinone colors, e.g. Duranol-Hot IB23CÜJ azo dyes, for example Dispersol-Fast-Red or Carbolan-G-elb 3GS; or azin colors, for example Cocmassie-Elau Gl. The dyes with the trade names mentioned above are from the -! «C.I. Ltd. expelled and are all tis on Cartolan Yellow 5 GS up to a certain degree in Water legible. However, they can be brought into solution very easily, inaerc. you first use it in a small amount of the ITichtlcsunt "sr., either in alcohol, such as lethanol, in cold

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~ 13 -

State or in water by. Heat and then dilute the concentrated color solution with either water or alcohol

The concentration of the dye in the leaching depends on the capacity of the polymer for the dye and the efficiency of the dye from "Usual dye concentrations of 0.1" $ to 25 percent _o $, for example 1FO to $ 5> can be used When using the method according to the invention, however, extremely effective coloring can be achieved even with significantly lower concentrations , 8 mm or more, can be done <>

But even if the penetration of the dye into the material is limited to the surface, the dye will held fast and can only be removed from the dried material with great difficulty with water or alcohol remove in which he had been dissolved.

The method according to the invention is particularly suitable for the production of microporous polyurethanes and for the production of leather-like materials by impregnating felt. Furthermore , the method according to the invention can be used for the production of leather-like materials in the form of sheets, foils or hollow bodies, the mechanical strength of which is not based on a preformed fiber mat material or fiber reinforced and which consist in their entire thickness of elastomeric microporous polymer

In contrast to known reinforced upper leather substitutes, the maximum elongation of which is about $ 20-60, the material produced according to the invention can be stretched over 100 $, for example $ 250, $ 300, even up to $ 500 or $ 700.

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The invention also extends to shaped f-shapes Polymer sheet materials containing elastomeric polymers colored with a dye according to the invention, which is firmly bonded to the polymer without any post-treatment

The colored polymeric sheet preferably has the property that, when peeled from any adherent layer and tested in an unsupported condition, it is in the plane of the layer under a tensile stress which produces a constant elongation of about 10 cm per minute Using a sample 15 cm long and 1.25 cm wide, has a tensile strength of at least 4.5 kg (10 lbs), preferably 9 kg (20 lbs) per 25 mm wide and 1 inch thick - this being the load at which the sample ruptures »The initial modulus is at least 0.9 kg (2 lbs), preferably 1.8 per 25 mm width and 1 mm thickness, this being the load at which an elongation of 5 ° / ° occurs; the tear strength is at least 0.9 kp (2 lbs), preferably 2.25 kp (5 lbs) per mm of thickness, this also being the load at which the specimen tears when using the test methods described in Example 1 of the simultaneous are described under claiming ■ the priority of the British patent application 20737/68 filed German patent application P ...., the ultimate tensile strength for such a sample is at least 2.25 kp (5 lbs), preferably 3.6 (8) to 7, 2 (16),; the initial modulus at least 0.9 kp (2 lbs), preferably 1.8 (4) to 2.7 (6), and the tear strength at least 0.9 kp (2 lbs), preferably 1.8 (4) to 5, 4 (12) "

The method according to the invention is particularly suitable for the production of uniformly colored, three-dimensionally shaped or hollow objects from polymeric sheet material with a typical thickness of 0.5 to 5 mm, which is preferably permeable to water vapor, against liquid penetration Water, however, is preferably resistant, self-supporting, flexible and very dimensionally stable. Such items and

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preferred methods of making them are particularly useful in the footwear, especially shoe industry, such as this is explained in the above-mentioned parallel application «In particular example 17 of this patent application describes how such a product can be manufactured ο With regard to further details of the product, the process to its manufacture and its properties and possible applications, which are related to the present Invention can be implemented, which also relates to uniformly colored products of this type, will be based on them Patent application referenced. Such hollow objects could also be colored in the mass, a subsequent one Inking, however, is a slow, time-consuming process since one does not work with a continuous roller technique can, in addition, a uniform coloring because of the flexibility of shell or shell-shaped products, even if these are filled in or stuffed, it is difficult to achieve.

Thus, the invention is particularly useful in the manufacture of hollow, molded polymeric articles which are very thin-walled, such as rubber gloves, which have a wall thickness down to 0.05 mm or less and up to 0.2 mm or more.

As far as thick-walled objects are concerned, be careful with the details, such as the various courtesies for the production of hollow molds again to the repeatedly mentioned Referred parallel registration. Above all, there is also the use of preferably hollow and with ventilation ducts provided shoe shapes or last shapes, in particular made of solid or porous sintered plastic films, described, also various possibilities, such as a layer in one, two, three or even more separate, superimposed layers with or without installation of a stiffener and other embellishment er-. and equipment inventory parts, which for a Shoe required, can be constructed; further is there

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described what special plastic and salt concentrations can be used to vary the microporous structure of the polymer leather, the preferred viscosities paste-like materials (for example in of the order of 100,000 to 200,000 centipoise)} further the use of a single layer of a different one Polyurethane and the retention of the sodium chloride in the tie layer until the top layer is a special process has been coagulated to produce a basically three-layer material; also the preferred layer thicknesses for different use cases like 0.8 to 1.5mm for Women's shoes and 1.1 to 2.5 mm for men's shoes, as well as the possible variations in the use of nonsolvents, E.g. that the same gown as the light solvent does not have to be used to leach out the filler for the polymer (which is preferably at least partially miscible with the solvent for the polymer) β

A change in the parameters of polymer concentration and removable filler concentration for a given Polymer concentration, i.e. the ratio of filler to polymer, will of course affect the properties of the final product Object; an increase in the filler to polymer ratio and a decrease in the polymer concentration leads to a more permeable and less solid object, as is a satisfactory one between these tendencies. A compromise can be found is described in German patent applications P 17 53 669.5 and P 17 53 667.5.

If one sees a solid, essentially microporous interior without large pores that are visible to the naked eye wants to produce, for example using a thermoplastic, substantially linear polyurethane, which

made of a polyester by reaction with a diol and a

L'ii s ο cyan at
light I-cerschuß · made in reading in dimethylformamide

and using sodium chloride as a removal

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"Free filler and water from leachant, then lies the polymer concentration is preferably in the range from 25 to 55 GeWo ^, in particular about 30 $>, and the ratio of filler material to polymer is preferably in the range from 1.5 to 1 to 2 to 1 parts by weight

Should be a weaker one, but one that is more permeable and more light-weighted Material with a significant number of larger pores are produced, i.e. a softer and more flexible material, then a filler to polymer ratio of approximately 0.5 to 1 is selected in the same system

The invention can be embodied in various ways and a number of examples are presented for purposes of illustration cited and for comparison a number of examples of subsequently colored materials and in the The proportions, parts and percentages given in the following examples relate to the mass of colored materials refer to the weight, unless otherwise noted.

Examples 1 to 9

The colored material produced was a microporous sheet of polyurethane having a thickness between about 0.5 mm and 0.9 mm «The polyurethane was made in the following manner manufactured:

The starting material was a linear polyester based on adipic acid and a mixture of ethylene glycol and 1,4 - butane diol.

The polyester had the following properties «Average molecular weight about 2000 Hydroxyl value 50-60

Hydroxyl content 1.5 - Λ, 8 &

Acid number 4.2.0

Viscosity at 75 0 500-700 centipoise

Water content <Co, 15? °

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The polyester was carefully dehydrated in vacuo, and ■ about 100 parts were then weighed into a reaction vessel and ^; heated to 15O ⁰ O, 22.0 ^{parts by weight of 50 0} C warm liquid 1,4-butanediol were added with stirring and the stirring was continued for 50 seconds 80 parts of powdered solid 4,4'-diphenylmethane diisocyanate were then added all at once and the mixture was thoroughly stirred "the temperature of the reaction mixture fell initially from .to about 60 C and then quickly rose again and reached after 90 seconds 80 ⁰ Co

The liquid mixture was then poured into a dish heated to 125 ° C. After 3 minutes, the now solid polymer was removed from the dish and placed on a cooled table until it cooled to room temperature? Then it was stored in closed containers for 12 to 24 hours, granulated, cooled and mixed in a drum mixer until the granulate was completely homogeneous _o At this stage, the intrinsic viscosity was about 0.3 to 0.5 deciliters / g (measured in Solution in dimethylformamide, which contained, for example, one percent by volume of dry methanol to prevent the material from polymerizing) "A 25-pound solution of this polyurethane in dimethylformamide was prepared, and three parts of finely divided sodium chloride per part of polyurethane was evenly distributed by grinding into the solution"

The sodium chloride was v / in a pin and disk mill with air flow separation of the different sized particles ground, whereby fine particles were separated out and oversized ropes were returned to the tach grinding, that Sodium chloride powder had prior to being dispersed in the polymer solution typically has an average particle size of about 10 to 20 microns, usually about 13 to 17 microns for a mean deviation of the order of + 10 microns- · -_ .. This measurement was carried out by sedimentation using a photo extinction sedimentometer (Evans Electro Selenium Ltd ,, Model 41 taking into account the usage

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instruction according to H ₀ Eo Rose in "Engineering" from March 31st and April 1st 1950 and "ITature" 1952, Volume 169, page 287).

This device consists of a chamber in which the solid, the particle size of which is to be determined, can be dispersed in a liquid by ultrasound, the settling speed then being measured optically the measurement of this change allows the calculation of the mean particle size _a These sedimentometer investigations give an indication of the general order of magnitude of the particle size for the majority of the particles

Shadow photographs of typical samples of the ground salt have shown that the salt particles are random, rough, irregular shapes, including relatively long shapes as well as compact cubes or block shapes ο

The dispersions typically contain a few particles, the maximum dimensions of which are up to 70 microns, practically all the particles were smaller than 40 to 50 microns, and most of them were in their max 30 Uikron ur.c. had dimensions ir. A range down to 1 Uikron, -.vc with some so.car even smaller «The salt used had a low * moisture content, in particular not ::. El: r than 1 ^c / o, preferably below 0.5 / ", in particular just i: r. -.- range of 0.2 - C. 4 ->, so that it did not tend to form lumps. from commitments precipitated... K f - 1 '' and öilicat of very small P & rtikelgrcße as it is sold by Joseph Crosfield & Sons Ιτα ". The Lischen and Ilahlen was preferably j at relative humidities of less than 70?, And in particular ^ 5C, ausge'fiüirt at 25 ⁰ C.

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BATH ORIGINAL

The paste-like mixture had a viscosity of 80,000 to 90,000 centipoise ^{at 25 ° C.} It was applied as a wet layer about 1.4 mm thick on the smoother surface of a commercially available sintered porous polyethylene film (trade name VYON). This sheet material was created by spreading a uniform layer of high-density Ziegler polyethylene powder on a smooth metal surface and then heating the layer on the metal surface, the powder melting at its contact points and creating a solid, self-supporting but flexible sheet. The surface of the foil which was in contact with the metal surface is smoother than the other surface and was preferably used as the surface which was coated with the polymer solution. A preferred shape of this sintered foil material is 0.067 "+ __ 0.004" thick and has an air permeability of 18 + 4 cubic feet / square foot per minute at a pressure of 20 cm of water and weighed 144 g / square foot. Another suitable grade had an air permeability of 60 + 4 cubic feet per square foot per minute at 25 mm water column.

The former material had an average pore size of 50 microns as measured on the British Standard Hr, 175211963 using n-propyl alcohol.

The layer on the base was then immersed in a dye bath for 2 hours to remove virtually all of the dimethylformamide and sodium chloride immersed. Then it was dried and removed from the base.

The color bath used in Examples 1 to 8 according to the following Table 1 was prepared as follows », 15 g of the dye was dissolved in 15 cm of methanol or dispersed and this solution was diluted with 4000 g of water.

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ZJr. dye

ID Χ3 ID

Ι)! eke of the dried Scliicht

- 2.1 -

Table 1

Concentration pH- ¥ ert the penetration of the dye-dye depth in bathe bathe the class

Appearance

1i "ethylene

■ "Blue 2 BUS

2. '. Disulfine

'·'. blue

3. Brilliant green ΏΙ3
crystal

ο malachite

green

ο Duran ο1-Eo t

TB 2300

β dispersol

Almost fiot

7 “Coomassie blue GIi

8. Garbalon-Yellow 3 GS

Malachite ~

0.76 0.91

0.80 0.90 0.88

0.91 0.86

0.55 0.90 0.375 ^

7.4 8.2

3.9 2.9 7.9 8.1 8.2

not measurable

0.01 mm

Parch density greater on the surface

Penetration through the entire thickness, but much closer than on the surface

0.8mm $ 100 material saturated with color

0.9mm $ 100 material saturated with color

0.6

Penetration not quite completely

gradually imperfect disappearing penetration

Most of the color on the surface cannot be measured

0.55mm $ 100 full penetration

not measurable color intensive, but on the surface does not limit color to water resistance

In Example 9, an after-treatment of an undyed material was carried out which was identical to that described above, but had been coagulated for 2 hours in water instead of in a dye bath. The material was then dried and ^{immersed in a dye bath at 20 °} C. for 2 hours, removed, rinsed off and dried and then removed from the sintered foil base. Methylene blue 2 BNS is regarded as an azine dye, which has the chemical formula shown in FIG. 1, malachite green GPS is regarded as a triphenylmethane dye with the formula shown in FIG. 2 »

The acidic dyes give the highest penetration in these examples and are more effective in this regard than the basic dyes of Examples 1, 2, 7 and 8 or the disperse dyes of Examples 5 and 6, in Example 5 a fine dispersion was used, although some dye may have dissolved, and the invention is therefore as mentioned, not limited to the use of dyes which are completely dissolved in the calibration solvent »

Even if the material is incomplete from the dye is penetrated, it can be of considerable advantage to provide a colored base for a pigmented lacquer that then may have a lower pigment content, which accordingly Materials colored according to the invention can be given any desired surface-modifying finish, for example a lacquer finish or spray finish with dimethylformamide, which deepens the surface color.

This latter technique is a particularly suitable one Surface treatment represents and completes the treatment the surface with fine droplets of a solvent and Heating in such a way that the microporous structure on the surface partially collapses and a thin, molten polyurethane skin forms thereon. This is how i-aterialien treated often have a number of depressions at small intervals that are partially melted on this surface

809846/1214

BATH ORIGINAL

Polyurethane material (e.g. 2 to 15 microns thick) are filled. In another suitable surface treatment, a thin top layer is applied to the surface of the microporous material, for example an aqueous solution of a suitable polymer (such as an alkyl acrylate polymer or mixed polymer, such as a mixed polymer of butyl acrylate with about 15 $ acrylonitrile 1 and about 1-2 Itaconic acid, which, when heated, can be crosslinked by adding a urea-formaldehyde condensation product to the emulsion, as is known) ) Be layer, so that the appearance of the material is improved without its water vapor permeability is reduced inadmissibly. The surface coating can form a continuous layer, which gives your material a shiny, lacquer-like appearance.Thus, a solution of a polyvinyl butyral dissolved in a common organic solvent, which is mixed with a melamine-formaldehyde resin dissolved in the solvent, can be used to evaporate the solvent and cure the mixture of these two resins ^: (crosslink).

Examples 10 to 27

In the procedures of Examples 1 to 8, the parabid bath was used not only to coagulate the polymer but also to coagulate it also for the removal of practically all dimethylformamide and sodium chloride used. In a continuous process, this undesirably requires two hours of immersion large amounts of dye liquid. In the examples described below, a previous dye bath is therefore used used, in which practically only the coagulation is effected for, for example, one hour, which is followed by a two hour leaching in dye-free water. Although this technology leads to a lower input

9Q9846 / 12U

penetration and color strength in some of the dye used e _f however, the dye bath to halve the volume, and still with certain other dyes ■ drawn off results achieved. With certain dyes , even better results are achieved with the dye bath technique than with dyeing in the mass or subsequent dyeing, the disadvantages of which have already been mentioned _e

The same polymer formulation was used in all of these examples. The polymer used was a polyurethane, that in solution in dimethylformamide from a polyester by reaction with a diol and a diisocyanate in an inert Atmosphere had been established.

The reaction was carried out in pure N, N ¹ -dimethylformamide (360 kg) using 130 kg of anhydrous adipic acid-ethylene glycol-butane-1K-diol mixed polyester with a molecular weight of about 2000 and a hydroxyl number of 52.8, I (as marketed by Bayer under the trade name DESMOPHEN _; 2001) and using 28.38 kg of water; Free Butan-1: 4-Diol <> Then 108.8 kg of pure 4,4′-diphenyl- * · methane diisocyanate were added and the mixture was cooled so that it remained at a temperature below 50 ^° C. As the reaction was practically complete, 4-Diöl was butan-1! added, which reacts with the remaining free isocyanate groups, and the temperature was maintained at about 50 ⁰ C until the viscosity at 24 ⁰ C about 2300 poise fraudulent This additional amount of diol was Finally 3.4 kg _e, 5 kg of a mixture of ethanol and IC-IT-dimethylformamide in the ratio 1:!.! added 1, ".velohes free with residual traces _isocyanates: which are still present, react at this stage. the viscosity of the material at 24 ^° C. was 2700 poise.

The viscosity of the final solution was at 24 ⁰ C the next day 2,100 poise that solids made $ 31.5, which Eigenviscosität was 1.075, and the Huggin'sche ICeigungs-

909846 / 12U

BAD ORKSiNAt

constant K of the viscosity number curve was 0.37 »

A sample of this solution was then diluted so that the content of polymeric solids was 15 $ and poured into a flat glass container , so that finally a solution- \-free, transparent film of 0.2 mm thickness would arise

The tensile strength was 789 kgf / cm as measured by the <British form ilo. 3144/1968. The tear strength was 161 kp. ^:

Figo 3 shows the stress / strain curve for this polymer: film using a jacket-shaped sample such as for determining the tear strength "This curve was obtained by I combining the load-time diagram, which was obtained with a [Instron tensile tester at which ι the specimen was stretched at a constant rate of $ 50 per minute, with an elongation-time diagram which had been measured by hand using reference marks which were recorded on the specimen to determine the actual elongation. Both series of measurements were carried out at room temperature »

From Figo 3 it can be seen that the initial modulus at 25 $ elongation is 64 kp / cm "

4 shows the result of a corresponding material test at $ 60 elongation per minute using a specimen measuring 5 cm 1.2 cm 0.4

- A stabilized polymer paste, which dis-. pergierte contains microscopic particles salt was prepared '■ the Polymerlöaung described above by mixing 10 kg 2.64 kg IT, IV-dimethylformamide, 9.48 kg of finely divided sodium chloride of the same particle size as in Examples 1 to 8, 118.5 g S! EABOXOL, an arbodiimide stabilizer against

909846/1214

Hydrolysis of the polyurethane (as 40 $ solution in IT, N'-dimethyl | formamide) undCTASOEB UV 24, namely 2,2 ^{l-dihydroxy-4-methoxy} benzophenone j, a stabilizer against decomposition of the Polyrethans' by ultraviolet radiation, and IRGrAiTOX 1010, namely Te. tr akia-; (Methylene 3- (3 ', 5 ¹ , ditertiärytutyl ^' - hydroxyphenyl propionate) -. Methane, an antioxidant for the polyurethane. Ι

The last two components were used as a mixture in the
Ratio 4 * 1 in solution in dimethylformamide with a concentration of 50 $ added. 153g of this mixture
used. ; "

The paste was made in a water cooled three roll mill
mixed under high shear stress until a uniform dispersion of the salt in the polymer solution was achieved »The
Paste was then carefully deaerated in vacuo and stored in sealed containers.

Examples 10, 12, 14, 16, 18, 20, 22, 24 and 26

These examples apply to all materials that appear in the '. Mass have been colored. In each example, the dye was used in an amount of $ 0.5 of the polyurethane of the above! written paste was added, which was stirred until
the dye was evenly mixed with it "" The mixture _; was then milled in the three-roll mill until the urodium chloride was evenly dispersed and the mixture was at
! Degassed at room temperature in a vacuum for one hour. The paste |

^; was then on the above-described: sintered film with

the lower permeability using a squeegee
: up a gap of 1.5 mm wide and vice versa one hour
ι long immersed in water of 35 ⁰ C, so that the polymer becomes a; ^: self-supporting form coagulated. Then it was two hours '> -: immersed in 60 ⁰ C water, so that virtually ■'
· ■ entire dimethylformamide and sodium chloride was removed, [and finally it was getrocknetο at 9O ⁰ C

9QS848 / 12U

- • 27 -

Examples 11, 13, 15, 17, 19, 21, 23, 25, and 27

T, ~ ■ ι ■ ι ι ι ii ι

In these examples, the coagulation according to the invention took place in a dye bath. In each example, the paste described above was applied to the described sintered film of lower permeability using a hook gap of 1.5 mm width and vice versa in a 35 C warm dye bath for one hour immersed, which consisted of a 0.5 $ solution of the dye in a mixture containing 25 $ methanol and 75 $ water in order to coagulate the polymer and at the same time to color it, then the; Layer formed for two hours in a water bath at 60 ⁰ C to remove practically all Dimethy! formamide and sodium chloa? rids dipped and finally dried at 90 °.

In Table 2 are the dyes used and the ■ Results of the coloring of the materials for Examples 10 to 27 are listed.

A cross indicates that the example in question is the best of the three comparative tests with the example in question Dye is

To test for water resistance, the samples were boiled in water for 3 hours, washed with cold water and dried at 90 ° C and the color changes recorded against the British ITorm gray scale.

To test the light resistance test, the sample ZO was subjected to hours of intermittent ultraviolet radiation, in front of the sample a Ulxraviolettlampe -T.il "turned at a speed of four rotations per IJiiiute and the sample of the radiation was exposed at each during one half. Rotation. The Color change was again recorded according to the British ÜTorn-3 rough scale.

9098A6 / 12U

The wet abrasion resistance was determined using the SAIRA test tested in which a boiled in water and treated with water

; saturated wool felt cushion is used. It is then attached to a rotatable, resilient shaft that carries a load of 500 ρ is pressed onto the surface to be tested and a total of 1024 on the surface at 150 revolutions per minute Rotations. Again, the change in color is determined using the British standard gray scale.

Table 2 shows the results using the following symbols: NC means no change, G5 only a very small change and therefore a good result, Gr1 a substantial change and thus a poor result, L means a change to a lighter color and D one . Change to a darker color ₀

909846/1214

10
11th ρH-TiTert des
i dye
bath - 29 - 2 I. S5L
G4L G5L
G4L G5L 12th
13th 8.2 Tabel dyes
urgency Wet abrasion
Uniform light resistance
migkeit keit _Qber , ^,
side bejbe G3L
Έ0 G5L
G5L G4L 14th
15th 7.45 Resistance
ability ge
for water
at 10O ⁰ C $ 100 Well
good ⁺ G5L
m G4L G4L
G4L 16
17th 8.0 IC
G2L $ 100
$ 40 Well
Well G4D
G5D G5L
G5L AT THE
I. Dye example 18th
19th 7.4 G3L
G3L $ 100
$ 100 Well
good ⁺ G3L
G4L G5L G4L fU> Irgacet
Black EL 20th
21 8.1 G3L
G2L $ 100
$ 15 Well
excellent G1L
G1L G5L
G5L G4L Spirit
ITigrο sine SS 22nd
23 7.8 G3L
G2L $ 100
$ 60 Well
Well G1L
G1L G3L
G4L G4L "Cibalan Black
cd * ⁰¹ 24
25th 3.75 G3D
G3L $ 100
$ 60 good ⁺
satisfactory G5L
G5L G5L
G3L G4L
G3L οIrgacet Brown
CD ₂ tbsp
OD 26th
27 7.2 G4L
G2L $ 100
$ 70 Well
Well* G4L
G5I G4L ⁰⁵ Duranol Blue
22 Green B300 7.9 G3L
NC $ 100
$ 100 satisfactory ⁴ "
satisfactory 1922303 toDispersol Fast G3D
G3L $ 100
$ 50 Well
excellent lalachite
Green CiPS G3L
G3L Methylene Blue
2 BETS oarbolane
Brilliant blue

The colors used in Examples 12 to 17 and 22 to 27 according to Table 2 are all soluble in a 25% aqueous methanol solution. The Irgacet Black EL used in Examples 10 and 11 when Ilian löslieh but forms after half an hour a gel _n DURANOL cyan ι B300 is only with difficulty soluble Dispersol Fast Hed R300 is not soluble, although for two to three hours stable dispersion can be produced.

In Examples 11, 15 and 17 is practical, no · Color of the coagulated dyed polymer during Auslaugschrittes in ffasser removed in these examples are all Honoazo-2: 1 metal complex dyes used ^": Oibalan Black BGL probably in Fig. 5 Formula shown. Irgacet dyes are similar and are made in accordance with US Pat. No. 2,551,056 to Geigy AG.

It is of interest to note that the dye bath in these examples is neutral to slightly basic. ITach \ the aforementioned U.S. Patent can be a further Bereichj of colors using dyes of this type by the general formula Ohromierverbindungen

[χ- AN = U- b3 - (SO ₂ - CH ₃ ) _n

manufacture, where

A a benzene ring,

B a phenol, naphthol or eno1 coupling group radical,

which couples to the hydroxyl group in the ortho position,

X is a metallizable group in the ortho position to the azo group with the condition that all other components at A and B

are non-ionogent, and. ,

η denotes the number 1 or 2 and the methyl sulfone group

is aromatically bound

If a two-stage coagulation and leaching for ■; Implementation of the invention is applied and if a color

909846 / 12U

substance is only used in the first stage, it is appropriate to use monoazo-2ι1-metal complex dyes of the vorbesohriebenen type to use.

In Examples 13, 15, $ 21 and 27 is only a little coloring of the coagulated colored polymer at the Auslauge- or second step of immersing in the non-solvent lost Spirit Nigosine SS (Example 13) is an aniline dye Geigy AG DURANOL Blue Green B300 ( Example 18) is considered to be an anthrachionic dye having a formula of the type shown in Fig. 6. Dispersol Fast Red E300 (Example 19) is considered to be an azo dye. Oarbolan Blilliant Blue (Example 27) is considered to be an acidic azo dye with the formula of Fig. 7, in which H represents a long chain alkyl group.

In all of these examples the dye bath is neutral or slightly basic.

In Examples 23 and 25, much of the color comes out of the coagulated colored polymer during the second treatment stage lost · However, in Examples 23 and 25, the coloration after the first stage was intense, so that the loss of color in the second stage can be accepted, malaohite green was in Examples 23 and 4, methylene blue used in Examples 25 and 1. Preferably, the methods of Examples 1 and 4 can also be used for these two Colors are used

As already mentioned, the Irgacet and Spirit Rigosin £ e colors are manufactured by Geigy according to Table 2. Cibalan ! -lack BGL is made by Ciba-Clayton and the others in Table 2 listed colors of I.C.I. Limited manufactured.

In the two-stage technique, one light solvent is preferably used in the first stage, in which the

9 0 9846 / 12U

BATH

ι Color is just soluble, and in the second stage becomes a

Non-solvent used in which the paint is less soluble, is preferably practically insoluble. If the dye, however

: jji also insoluble to the nonsolvent of the first stage so that it is only present in a dispersion, then dennojjh sufficient coloration will occur provided that the color is soluble in the solvent in which the polymer is used

'is solved (see example 21). Why this occurs is not entirely clear; presumably the solvent dissolves when it sioh with the nonsolvent during the coagulation process mixed, the dye in the vicinity of the coagulating polymer and thereby causes the coloring

The pH of the dye bath does not seem to have any controlling influence on the dyeing process, but it does alkaline dyes according to Examples 11, 15, 17 and 13 »19, 21 and 27 appear to be leaching in the second stage better to resist o

The temperature of the coloring bath appears in the range of 20 to 4O ⁰ C also exert no substantial influence on the coloring process, at least in the case of Irgacet colors, although the penetration of Irgacet Brown 2RL at 4-0 ⁰ C substantially less than at 30 or 2O ⁰ C was «

The concentration of the dye bath also appears in the range from 0.25 to 0.75? ° to have no particular influence on the coloring process, at least as far as the Irgacet colors and a concentration of 0.57 ° seems to be a favorable concentration, although with the colors Irgacet brown and Irgacet black differ in terms of penetration * Trends have been observed. The optimal concentration for each dye is easy to determine.

The method according to the invention has compared to the method in which the mass is colored as a whole, also the advantage that a large amount of a standard paste

909846/1214

is produced and the coloring only according to the requirements can be done by changing the dye bath without preparing a new batch of pigmented polymer would have to

Example 28

This is an example in which what is described in patent application P. Method is used * In this example, a pair of one-piece uppers is molded with an Inner sole produced, the upper part being colored during its formation by the method according to the invention is ο The upper part is sewn, welded or glued attached to a leather, plastic or rubber sole and receives a surface treatment according to Example 1

For example, a polymer made from a mixture of 25 $ polyvinyl chloride and 75 $ polyurethane was used, which in dimethylformamide was dissolved. The resin concentration was $ 28. The solution contained two parts of fine sodium chloride particles for one part of resin dispersed by grinding. That Salt had the same particle size as in Example 1,

The polyurethane was the same as that in the examples 10 to 27 and the solution contained the same stabilizers, however, the amounts were $ 1.5 carbodiimide stabilizer, 2, JDJi UV stabilizer and $ 0.5 antioxidant as in example $ 10 the percentages are on the plastic part related * ■

Sine cave form from the mentioned sintered foil in Shape of a shoe last, which is provided with ventilation channels was as in Example 1 of the aforementioned German patent application P, -. ,, was immersed in the paste and after one minute in the example 9 of this patent application

909846/1214 _{OR1S1NAL 1NS} pecth>

Message I'd rather take it out in a flat way. Then a stream j of ^{air heated to 40 to 100 G} 0 was blown over the paste

the surface had rested to solidify "Wachdem the paste two Mijnuten, the shape wujde with the end on their 'coating 18 hours / a dye of 20 ⁰ C was dipped and then rinsed with water, stripped from the mold and gej dried, the result was an evenly brown colored one _; Shoe upper part o The dye bath was prepared by adding water to a 50% solution of IRGACEI BROW 6BL dye powder (manufactured according to UB patent specification 2,551,056) in methanol, so that a 0.5% dye solution was formed.

One of the uppers was made without the surface treatment leave and cut according to Example 9 of the above-mentioned German patent application, so that the physical Properties could be measured.

The material ranged in thickness from 1.01 to

1.73 mm and the colored layer on the outside was 0.08 j

to 0.12 mm thick "The material weight was 4-90 g per square '> ■

meter. |

Two measurements were carried out to determine the tensile strength, the initial modulus and the extensibility until tearing » A sample 1.18 mm thick gave values of 3.7 kg / cm,: 2.1 kg / one or 120 ^ j the other sample with a thickness of 1.57 mm Values of 7.4 kg / cm, 2.3 kg / cm and $ 173, respectively. In a single measuring ; The maximum pore size was 5.5 μm, the average pore size 2.3 μm and the hydrostatic compressive strength determined to be 280 Sorr.

The tear strength was measured from outside the cap by turning a sample 1.18 mm thick at 2 kg and along the side or top using a sample 0.98 mm thick at 1.7 kg. The material also had a water vapor permeability of 2750 g / m 2 in 24 hours. These _: measurements were made according to Example 9 and Example 1 of the above

909846/1214

ORIGINAL INSPECTED

mentioned the German patent application filed at the same time.

The material also had a resistance to water penetration using a Bally penetrometer of 15 cycles. This method is described in British Standard Sheet No 3144/1968 · · In this method, a trough-shaped container from the material under investigation mm to about 75 length is formed, the ends 50 times are compressed mm per minute to approximately 3 minutes. The outer surface of the material is used as the outer surface of the trough-shaped container, immersed in a bath of distilled water and bent therein. The penetration of water through the material is measured electrically by a suitable electrode arrangement.

9098A6 / 12U

Claims (1)

Claims 1. Process for the production of colored polymer material, characterized in that a starting mixture of a mixture stretched with a liquid carrier material Polymer is produced, and that the polymer in colored form with a polymer non-solvent, the containing a coloring agent which is in solution during at least part of the coagulation is coagulated. 2, method of making colored polymer materials, characterized in that a mixture of a solution of an organic polymer in a solvent and that the polymer is formed into a self-supporting, molded shape having a non-absorbent end for the polymer Agent is coagulated, the polymer non-dissolving agent initially containing a coloring agent which is at least is in solution during part of the coagulation. 3 · Process for the production of colored polymer material, characterized in that a pasty Mixture of a polymer extended with a liquid carrier material is produced that the polymer is made of a self-supporting, three-dimensional or shell-like form is coagulated with a non-solvent for the polymer, wherein the polymer nonsolvent contains at least one dye initially which is present during at least a portion of the coagulation is in solution 4. The method according to claim 1, 2 or 3, characterized in that microscopic Particles of a removable filler are evenly distributed, which then practically completely is removed from the colored coagulated polymer * 909846/121 U - 57 - 5 · Method according to claim 1, 2, 3 or 4 »thereby characterized in that the coloring agent contains a dye which is in the solvent for the polymer Is at least partially soluble. 6. The method according to any one of claims 1 to 5, characterized in that the coloring agent contains a dye which is initially in the nonsolvent '. agent for the polymer is in solution «, j 7. The method according to any one of claims 1 to 6, d a -; characterized in that the coloring agent is a heterocyclic substance containing ihiazine groups, a triphenylmethane dye, an anthraquinone dye, an azo dye, an azine dye, or a monoazo 2: 1 metal complex dye contains «, ₍ 8 β method according to claim 7, characterized thereby indicates that the monoazo-2 »1 metal complex dye is a metal complex of a monoazo dye of the following - _L Formula is: j A - Έ = N - bJ - (SO ₂ - Where A is a benzene ring, B is a phenol, faphthol or enol coupling component radical, that couples to the hydroxyl group in the ortholage, X is a metallizable group in the ortholage to Are Jlzo group, the dye has no other ionogenic group, η is the number 1 or 2 and each methyl sulfone group is aromatic is bound » 9 »Process according to one of claims 1 to 8, characterized in that the organic polymer contains a polyurethane material which is formed from polyester material by reaction with diol and diisocyanate, and that the concentration of the dye in the high solvent is in the range between O ₉ I fo up to 25 Ί » . 909846 / 12U Porvair Ltd. "8055-69 / Dr.v.B / * -38- 10. The method according to claim 9 *, characterized in that the concentration of the dye is in the range between 0.375 % and 1 % . 11. A method for producing a colored object, characterized in that it is carried out according to one of the description examples 1 to 8, 11, 13, 15, 19, 21, 23, 25, 27 or 28. 12. The method according to one of the preceding claims, characterized by the application to shoe uppers made of a 0.5 to 5 mm thick, water vapor permeable, self-supporting, flexible and essentially dimensionally stable sheet material. 13. The method according to claim 12, characterized by the application to the production of a Shoe item. 909846 / 12U