DE1619273B - - Google Patents

Description

encounters amides and cured epoxy resins. Has outstanding storage stability, the tech-

For these problems, it has so far been difficult to make genetic progress on what is produced according to the invention

to be found. The problem is justified after the USA.

Patent specification mastered by the fact that the leather target of the invention is accordingly the production of a surface treated with the reaction product of a certain polyamide impregnated with a polymeric material or a complex epoxy. coated flexible, fibrous, porous webs - There is thus the need to first produce a material using an improved elasto-determined polyamide, which is generally meren polymeric material with good adhesion temperatures of 80 to 200 ⁰ C and reaction times on leather or other flexible, fibrous, porous should require from 1 to 4 hours. In addition, the Io sen sheeting material and a relatively large reaction products described there are apparently only permeability or "breathability" for vapor form for the production of coatings and not for im- moisture, the polymer material being ^{suitable as 100% e} impregnation of leather, which is back - Resin mixture on the substrate, in the form of a wäßrizuführ may be that certain properties of the gene emulsion or in a solution in an organic reaction products, such as. B. the elasticity, should not be applied in the 15 see solvent and the optimal dimensions are available. The same subsequently obtained polymeric coating or the obtained parts also apply to the polymeric layer against a water and a 3,220,962 coating described in the USA patent specification. After this patent solvent penetration and scraping is said to be very resistant using the same general eras and tears. The polymeric finishing system 3,130,069 used according to reactants as in US Pat. No. 20 of the invention produces a crosslinked gel which is applied to the leather surface that is intended to be used for treating leather. In contrast, paints, pigments, lubricants, fillers, the aim of the invention is to provide a highly elastic, strong wax, polymer, polish and anti-slip abrasion that is compatible with water and organic agents, as well as the appearance of solvent-resistant coating agents that also improve grained leather can and an excellent impregnating agent for flexible, fibrous, porous outstanding service life with continuously repeated sheeting, such as e.g. B. leather and artificial leather, have bending and finally be suitable, one is to be turned and that is to be produced in a simple and economically synthetic epidermal layer on a leather enthalschaftlichen manner, to form substrate available to tend.

30 It has been found that these and others are first of all a certain polyamide for the purpose of avoiding parts in the manufacture of a product from amino compounds and epoxides in the manufacture of a product from amino compounds and epoxides with one of the problems previously described in the literature . internal structure or coated flexible, from French Patent 1,382,283 it is further known to obtain fibrous, porous sheeting (including leather with a variety of polymeric nonwoven networks, fabrics, etc.), fabrics, including epoxy resins and polyamines, if you impregnate a mixture or, and in the French patent an adduct of (1) script 1 358 084 obtained by prereaction finally the use of a water-insoluble polyether polyprimaryamine epoxy resins for the treatment of leathery materials with a molecular weight of at least 1000 rials proposed. Although the 4 ° described there preferably from 1000 to about 20,000, and in particular polymeric substances can be referred to as flexible, those in the range from 5000 to 15,000, and with one they do not have the elastomeric properties, the terminal primary amino group, the directly everyone has the polymeric material of the invention. Last - end of a polyether part is adjacent, and with res, flexible, fibrous, porous webs - recurring groups, of which at least one material, such as leather or synthetic leather, so to impregnate or cover a larger part of recurring units from oxygenation, that there is tetramethylene in the impregnation and at most a minor part or coatings, the advantages of epoxy systems of recurring units of oxyalkylene or are retained, but without many of the disadvantages, such as thioalkylene with 2 to 6 straight-chain carbon z. B. have a limited elasticity, which consists of atoms, with at least half of the conventional, ie non-elastomeric Epoxysyste- 5 ° termed terminal amino groups are linked to the structure men. For example, as further has -OC ₄ H ₈ NH ₂ , the aforesaid polyether portion being further detailed below, an epoxy resin having less than about 3 weight percent nitrogen atoms results in an equivalence ratio of oxirane to active of secondary amine and less than about 0.3 Hydrogen significantly higher than 20: 1 generally weight percent nitrogen atoms of tertiary amine on hardened end products so hard that this shows as 55, and (2) an epoxy resin with an oxirane hard plastics and not classified as elastomer equivalence (i.e. the number of oxirane groups per According to the invention, however, elastomeric molecule) which is greater than 1, preferably 1.5 to 4, polymeric reaction products of a special type for im- whereby the equivalence ratio of oxirane to active impregnate and cover leather, artificial leather and hydrogen of the primary Amine is 1: 1 to 20: 1, similar sheeting can be used. In this ⁶ ° with or without further inert solvent or in use of the elastomeric reaction products in aqueous emulsion, and which (3) optionally contain a contrast to the reaction product previously used epoxy curing catalyst, and th, including the epoxy resins previously used, one in or cures in situ on the sheet material, is an essential feature of the invention that the equivalence ratio of oxirane to active, also due to the excellent properties of the 65 hydrogen, is obtained by dividing the number of oxirane coatings and impregnations, including equivalents, in the total Epoxy present lent the fact that the polymer of the invention are, through the number of equivalents of an amine material in the form of a permanent emulsion, an adjacent active hydrogen, which in the total

weight of the amine are present. The at least 14.06 kg / cm ² tensile strength, when combined with the composition, can also include various dissolved or a stoichiometric amount of diglycidyl ethers of the dispersed polymers (e.g. polyacrylates or 2,2-bis (parahydroxyphenyl) propane (oxirane equiva- Polyurethanes), paints, pigments, fillers, waxes, lent weight from 190 to 200) in the presence of 2%. Lubricants, natural or synthetic fibers (eg., 5 based on the total weight of the solids, leather fibers), lubricants and other for leather-thiobis (di-sec.amylphenol) for 4 hours at 12O ⁰ C finishes valuable substances. A film made from this material will then, in terms of its properties, have a significant impact on the quality of the manufacturing strength and tensile strength of the final sheeting made in ASTM Poly-10 D-412-62T set process using ether polyprimaryamine in the lower molecular weight of Form C for sample preparation and a weight range, it is generally a desirable expansion rate of 10 inches per minute, an equivalence ratio of oxirane tested to active at a test ^{temperature of 23 0} C. Apply polyhydrogen from 1: 1 to 2: 1 in order to obtain an ether polyprimäramine with a molecular weight material that after curing a 15 over 3500 must cured products with at least extensibility of at least 50% in film form having ig ^e r tensile strength and at least 35.15 kg / 400%. If there s Polyätherpolyprimäramin a cm ² tensile strength using the above molecular weight in the higher ranges, z. B. Test procedure result. This polyether polyprimär of 10,000 can advantageously be an equivalent amine can be used by reacting a tetrahydrofuran ratio of oxirane to active hydrogen of 20 and up to about 40 mol percent of another cationic 1: 1 to 20: 1. If the epoxy see polymerizable cyclic ether or cyclic resin has a high aromatic content, such as. B. see thioethers in the presence of trifluoromethane. C of the diglycidyl ether of bisphenol A, it is advantageous sulfonic acid anhydride at temperatures from about -40 a slightly lower equivalence ratio of oxirane to + 8O ⁰ C in a polymerization system that is free to active hydrogen, as in the case of the essential substances from 25 is that monoalkylate a chain end borrowed aliphatic epoxy resins, such as. B. the Di- can be produced. Use suitable cationic glycidyl ethers of 1,4-butanediol. If polymerizable cyclic ethers (including the cyclic equivalence ratio of oxirane to active shear thioether) are oxacycloheptane, 3,3-bis- (chlorine-hydrogen of 1: 1, the amine-methyl) -oxacyclobutane, phenylglycidyl ether, propylene oxirane Reaction through the incorporation of a catalyst, ethylene sulfide, epichlorohydrin, 2-methyl tetrasator of the neutral salt type (e.g. lithium bromide) hydrofuran; all of the foregoing compounds are accelerated into the finish composition. have 2 to 6 ring carbon atoms per molecule. Without such a catalyst the full can, the Polyätherpolyprimäramine may require about 2 weeks, by reac-curing reaction at 21 ⁰ C, "tion of tetrahydrofuran or together but with the web material, during the ausgedehn- 35 up to 60 mole percent of a suitable cationic th curing without being subjected to serious complications normal polymerizable cyclic ether as a mixed mono-processing curing can mers in the presence of Trifluormethansulfonsäureauch by an increased temperature accelerates anhydride at temperatures from about -. 40 to + 8O ⁰ C, though usually a prolonged heating produced in a polymerization If a stoichiometric excess of epoxy-alkylating can be used to use such a polyether with a resin, it is generally necessary to have high levels of cationic activity ät to apply a catalyst to the ends of the polyether chain. The molecular weight (epoxy resin as such in its solidified thermally dicationically active polyether to convert to recured form. Such catalysts 45 reversed with the concentration of the trifluorine are well known in the art for the curing of epoxy resin, methanesulfonic anhydride, and a molecular one. A particularly suitable one Catalyst class weight from 1:20 to 1: 400 of trifluoromethane is the class of the tertiary amines, for example 2,4,6-tri- (disulfonic anhydride to the cyclic ether monomethylammomethyl) phenol, tributylamine or N-mers generally desirable to polyether having thylpiperidin. polyalkylenepolyamines polycarboxylic 50 to produce about 50 ° / ₀ ig ^em turnover a molecular weight of 1,000 to about 20,000 with ren and anhydrides, polythiols and their salts can. The can be polykatioebenfalls used as catalysts. A nicely active polyether is a highly alkylating agent, excellent catalyst, which generally i In which and can react with ammonia to apply pri range of 1 to 10 percent by weight, based on the amine radicals at the cationically active sites, total weight of the resin, is to be added. Stoichiometric to excess men-2,4,6-tri- (dimethylaminomethyl) -phenol. Ammonia are preferred in this reaction. The polyether polyprimaryamines, which are used according to the invention and a temperature of about -100 to about + 60 ° C, are exceptionally suitable, although the lower high levels of primary amine are used Terminal temperatures (below about 25 ^° C.) to moderate the function and are essentially free of terminal reaction rate, generally preferred for hydroxyl groups. In fact, you can get higher. Solvents inert to primary amine terminal alkylation, such as methylene chloride, trichloromethane, and their ability to react with a standardized epoxy formulation, cyclohexane, can be used. Depending on a cured product with good values of the concentration ratio of ammonia for tensile strength and elongation strength to 65 to the polycationically active polyether, the reaction can be characterized. In particular, polyamine product secondary or tertiary aminodiese Polyätherpolyprimäramine cured product groups, which are arranged within the substantially linear with at least 50% elongation strength and polyether part, while the

terminal primary amino radical further alkylated by another cationically active polyether molecule can be. The presence of nitrogen atoms in the form of tertiary amine in the polymer chain may have some branched chains with repeating units similar to those in the main polymer chain generate, but the molecule can still be viewed as essentially linear. For the production of a polyether diprimaryamine will be a large excess of ammonia, generally at least one five-fold excess, preferred.

An exceptionally large leeway is available in the choice of conditions to be used when carrying out the reaction of the polyether polyprimaryamines with epoxy resins are given. In such Vulcanization reactions are to be seen as the main variables:

1. The choice of the special epoxy resin,

2. the manner in which the polyether polyprimaryamine is added to the epoxy resin,

3. the use of catalysts or co-vulcanizing agents with these reactants and

4. the proportions of the reactants.

Any of a wide variety of epoxy resins can be used in such vulcanization reactions will. In addition to polyepoxides, these can be monoepoxides. When a mixture of epoxy resins is used, it is important that the oxirane equivalent be greater than 1, preferably at least 1.5. The use of an aliphatic epoxy resin is generally used to produce a final vulcanization product which has superior tensile strength having. The use of epoxy resins with a high content of aromatic or fused ring structures generally gives a final vulcanization product, the superior one Has resilience, but has a slightly lower tensile strength. The polyepoxy resins, which are particularly suitable for the manufacture of the vulcanization products according to the invention are well known and need not be described in detail. Monoepoxy resins that may be used to advantage, particularly when lower viscosity mixtures are desired butylglycidylether, phenylglycidylether, AHylglycidylether and the glycidylether of m-pentadecenylphenol being. A particularly preferred class of polyepoxy resins is derived from the reaction of Epichlorohydrin with bisphenol A. This class can be represented by the formula:

CH, - CH - CH, - O- < > —C

M CH ₂ CH-CH ₂ -O

OH

- Crio - OJHL -

In this formula, η can have a value between 0 and about 10. The structure of this class of diepoxy resins can be described either by specifying its melting point or, as is customary, by its oxirane equivalent weight. When η is O, the resin has an oxirane equivalent weight of 170, and when η is 10, the resin has an oxirane equivalent weight of 1590. The polyepoxy resin used for the purposes of the invention is im generally represents a mixture of compounds and will generally have an oxirane equivalent weight in the range of 170 to 1,600. However, epoxy resins of lower or higher equivalent weight can sometimes advantageously be used.

Two methods are generally used for reacting the resins in the process of the invention. The first method consists simply of mixing the polyether polyprimaryamine with the epoxy resin, either with or without a solvent, and converting it directly to a vulcanized rubbery state after application to the sheeting. This process is commonly referred to as a "Α-step" process. An alternative method of producing this vulcanization product consists in a pre-reaction of the polyether polyprimaryamine with the epoxy resin to form an adduct which is still soluble and workable. This process is usually referred to as a "B-Step" process. Adducts of this type can easily / are ₀ solution of the mixed resins in toluene or other suitable solvent at the reflux temperature in about 2 to 8 hours prepared by reaction of these Polyätherpolyprimäramine with an epoxy resin in a 50 °. In the B-stage reaction it is usually desirable to use an equivalent ratio for oxirane to active hydrogen of at least 1.5: 1, preferably at least 2.5: 1. The viscosity and the period of existence of the adduct solution are very dependent on the molecular weight of the polyether polyprimaryamine used as the starting material and the equivalence ratio of oxirane to the active hydrogen adjacent to the amine. at

a lower equivalence ratio of oxirane to active hydrogen, e.g. B. from 1.5: 1 to 4: 1, increases the viscosity increases considerably in the course of the reaction. An initial viscosity of 1500 cP at room

209 535/543

9 10

temperature is for a 50 ° / ^e oig .Toluollösung in which a When the poly- used as starting compound

Polyätherdiprimäramin with a molecular weight ether polyprimäramin a molecular weight of about

of 10,000 is used at the start of the reaction, has 1,000, has an equivalence ratio of oxirane to

typical. After 4 hours at reflux, the vis-active hydrogen normally increases from 1 to

viscosity to about 5000 cP when the equivalent 5 hardening a product with a tensile strength of

ratio of oxirane to active hydrogen 3: 1 results in at least 50%.

and the diglycidyl ether of the 2,2-bis- (para-hydroxy- If the poly-

phenyl) propane has been used as an epoxy resin. ether polyprimäramin a molecular weight of about

If a 7: 1 equivalence ratio for the same has 3500, an equivalence ratio of oxirane has to

Resin mixture is applied, the active hydrogen viscosity increases from 1: 1 to 5: 1 normally

to only about 220OcP. Usually after hardening this has a rubbery product (Shore-A _s -

Adduct resin has a long and useful life, hardness below 95). When the polyether poly

especially if it has a molecular weight of about 5000 in the form of a 50% solution in primary amine,

an inert solvent such as toluene is used so has an equivalent weight of oxirane to active

will. Such an adduct resin is subject to a low hydrogen of 1: 1 to 8: 1, and if the poly-

Greater than about 50% increase in viscosity in the case of ether polyprimäramin a molecular weight of about

Room temperature in a period of about 6 months. 10,000 has an equivalence ratio of oxirane to

The viscosity of the solution of the adduct resin to the active hydrogen is from 1: 1 to 12: 1 in general

Time at which it is applied, preferably resulting in a rubbery cured product,

less than about 20,000. 20 If that used as the starting compound

These adduct or "B-stage" resins find in polyether polyprimaryamine a molecular weight of

different leather coverings or finishes together has about 20,000, is generally an equivalent

Settlements use and are ultimately converted into a ratio of oxirane to active hydrogen of 3: 1

hardened or »C-stage« state converted. up to 20: 1 desirable to get a rubbery hardened one

The B-step process is often a preferred 25 product to produce. At ratios of oxirane to

Method for making rubbery hardened active hydrogen that is significantly higher than 20: 1

Coatings, because the adduct are normally still in, are generally the final cured products

common inert solvents and is hard enough to be used as hard plastics (Shore-A ₂ -hardness-

finally to be classified by adding a catalyst with or worth at least 95), and they

can be cured without the application of heat. 30 are primarily applicable to leather, which is a

Regardless of whether "A" or "B-stage" resins are not subjected to bending. It was found that

are used, there is a large margin for a given molecular weight of the polyether

the selection of the chosen conditions for the polyprimaryamine values for the equivalence ratio

Hardening reaction. It is possible, as catalysts, from oxirane to active hydrogen, which is substantially about

in order to accelerate the hardening, tertiary amines to the upper preferred value are a hardened one

use, such as a Lewis acid complex (e.g. boron product with values for the tensile strength

trifluoride diethyl etherate) or a large number of organobes, which are generally too low to be suitable for the

metallic compounds (e.g. dibutyltin laurate). Treatment of leather that is in use

A particularly suitable method of vulcanization when subjected to considerable bending is, too

is in the application of about 0.5 to 10 weight 40 suitable. Leather, especially leather

share 2,4,6-tri- (N, N-dimethylaminomethyl) -phenol dung is intended as shoe upper leather, normal-

as a curing catalyst, based on 100 parts of the multiple finishing operations by the

Resin. When this catalyst is used, several coatings are deposited on the substrate

the curing conditions normally are subjected to vary.

of approximately 1 day at 25 ° C to 2 minutes at 45 often five separate Appreturüberzüge to 150 ⁰ C the leather can be applied using from about 3 weight to the desired share of the catalyst per 100 parts of the adduct. Of the effects. Although it is possible and often desirable to use a catalyst immediately before its application, the compositions used according to the invention as the sole binder for mixed into the resin formulation on the leather surface. Using the physical properties of the hardened coating of any of these coatings, it is particularly desirable to vary with the molecular weight of the compositions as the base of the starting polyether polyamine and also with the coating or impregnation coating for the leather to applied equivalence ratio of oxirane. In general it is desirable to use leather or active hydrogen. In some cases it may be advantageous to impregnate other porous basic substances either with an emulsion co-vulcanization or a solution to be added to the reaction mixture, e.g. B. an additional polyprimär- 5 to about 40 weight percent of the combined polyamine or an organic polyanhydride. So merisats can contain, with other additives or without meta-phenylenediamine or diethylenetriamine together with other additives that are suitable in the leather impregnation gemen with the polyether diprimaryamines, the viscosity being adjusted so that the proportion of epoxy resin used 60 optimal Results are achieved. The compositions used after finding an equivalence ratio are increased in amounts of oxirane to active hydrogen of about 1: 1 in amounts of about 1 to about 10 g of the total resin on a Α-stage formulation and at least 1.5: 1, 929 cm ² leather applied. As previously indicated, preferably at least 2.5: 1, 'in a B-staging, can include other ingredients in the co-formulation. Various other fillings for the impregnation or finishing substances and additives, which are expediently incorporated into. The combined polymers and curing used by epoxy resins, the cured products of which adhere to leather, can also be added. Very good (this is an essential property for

11 12

an impregnation or a coating) and imparting In general, selected polymeric the leather, if it is preferred to this as final or finishing ingredients and the catalysts that Coatings have been applied that require an exceptional curing period between lent resistance to abrasion, abrasion and 6 hours and about 14 days at room temperature Wear and give the leather a ver 5 varied to the fully hardened rubbery improved "flexibility". When the co-product surrender. Elevated temperatures: up to Settlements for the treatment according to the invention as 93 ° C can also be applied to the Waterproofing coatings can be used to accelerate hardening, which in some cases occurs in finally finishing or finishing coats is achieved either 10 minutes. Sheeting that comes with the before or after the hardening of the finish compositions during the impregnation by the method of tion applied resin are applied. Has been treated for the invention, polishing and For example, natural leather can be impregnated over-plating at any time, train through a solution containing 20 percent by weight of a polyether polyprimaryamine after the surface appears tack-free be thrown with an equivalent.

weight of 10,000 and an epoxy resin with a 15 In contrast to leather materials with reactive equivalent weight of about 200 and the equivalent polyurethane substances, the free isocyanate groups ratio of oxirane to active hydrogen of containing treated are the hardened ones contains about 3: 1. An acrylic product from the compositions according to Emulsion can then be directly applied to the impregnation process of the invention due to its insensitivity th leather are deposited before the im- 20 compared to the moisture content of the leather and the impregnation solvent has been removed; d. i.e., humidity of the environment in which curing will occur the impregnation coating has dried. is performed, excellent. Another significant one

The above considerations also apply to the advantage is the ability of these polymers to produce synthetic epidermal layers or a predetermined stable rubber-like state, except for coatings for torn leather, ie for leather with which no further crosslinking takes place, to harden, which the natural Epidermal layer has been removed. It is also used for polyurethane treatment or for fabric or synthetic fibrous substrates. average hardness to speed and extent. Such synthetic epidermal layers can adjust to hardening based on the water sensitive coating weight which is 10 g of the total resinousness of the agents. Furthermore, the area tends to be 929 cm ² and even more, depending on the sensitive polyurethanes to an extensive extent on the surface properties of the article (e.g. age to further hardening, which occasionally causes the roughness) and on the desired appearance of the brittle film produced that is responsible for breaking or epidermal layer (e.g. smoothness). Because of the tearing off during the measures for the durable adhesion of the hardened polymer making the shoe or during the wearing of the composition on leather, natural leather is prone to finished shoe. Another desirable synthetic property or synthetic property containing leather fibers is preferred in the compositions of polyether substrates. polyamine epoxy resins for post-treatment treatment

The incorporation of leather fibers (e.g. leather invention is their good storage stability than dust) in such epidemic coatings there is a particularly stable emulsion, an advantage that comes with the sensitive This is preferred because it does not allow the polyurethane to be permeable. It was found, vaporous moisture and the ability such that the treatment method according to the invention the Layers, before the application of the usual leather, leather and leather fiber-containing base sub-finishes to have a soft polish is improved. punch an exceptional degree of chafing if desired can, before the strength of the invention confers when the compositions as applied coatings are fully cured, 45 primer or impregnation coating has been applied Fiber flakes on the uncured, tacky surface are believed to have this property brought on, creating a unique suede on the rubbery characteristic of the hardened film like finish is produced. and its superior adhesion to leather or

The compositions for treatment according to attributable to collagen-derived fibers of the invention can be done by any of the known measures. This rub resistance seems to be much greater took for the treatment of leather or other than being those who erode with acrylic resins a fiber derived from collagen is contained. Another valuable property of the Tending basic substances are applied, such as by cured products applied according to the invention Overcoating, peeling, knife application, whale is their relatively high permeability for zen application, roller brush application, flow coating, 55 vaporous moisture, a very important self-continuous coating or spray method. Synthetic shaft of finishes for shoe uppers, the essential epidermal coatings can also be borrowed by knife for comfort of the foot while wearing order or press order can be produced. contributes. The hardened products, if they are used as synthetic

As has been shown above, the poly _, table epidermis layer can be applied to a low-quality leather amine and epoxy resin immediately before the substrate, e.g. B. on cracked leather, applied to the porous base substance with a product mixed with a good physical own suitable catalyst and applied directly to the shafts (e.g. with permeability for moist steam, underlay. Alternatively, a Resistance to bending, etc.) and good appearance,
preformed adduct made from the epoxy resin and one of the disadvantages of using appre-

the polyether polyamine has been manufactured as 65 doors and covers made of polyurethane for leather and Solution or emulsion prepared and another suitable porous base substance is the extraordinarily catalyst immediately before the application of the borrowed difficulty and often the impossibility Adducts are added to the basic substance. subsequently apply coatings, if that was done beforehand

13 14

applied polyurethane an advanced addition t> ie 1 2
state of hardening. This seems to be the case

The fact that the currently common 1.63 kg of a catalyst made from freshly distilled leather finishes is not ¹ sufficient adhesion Trifluoromethanesulfonic anhydride is 79.9 kg strength on the cured polyurethane surface 5 tetrahydrofuran in a 110-1 kettle, the develop with glass. In contrast, the combined lined, under 0.7 kg / cm ² nitrogen pressure, adhere to polymers that were added according to the method of the invention. The mixture will be applied for 30 minutes and its cured products will stir well. During this time the temperature drops from 15 to well on the cured polyurethane surfaces. Be 46 ° C increased. At this point in time, the composites, if slightly increased temperatures are applied quickly to hardening in the boiler through a pipe made of polythene, the polymers can be converted into a solution of 3.27 kg of ammonia in the process of the invention for treating 42 in the case of ethylene 13 kg of toluene, which is stirred and kept at 12 ° C leather or other similar microporous structures, is fed into a 220-1 reactor made of corrosion-resistant steel, which is a hardened or partially hardened polyurethane steel. After 30 minutes, the over-resin will be used on its surface or as an internal component containing 15 amounts of ammonia, tetrahydrofuran and toluene, thereby removing the finish from the product. Toluene is added, made possible by sheeting, which on the other hand results in a 30% solution that is treated with a highly difficult, if not impossible, to appre-basic anion exchange resin to animals, and which also makes the production all traces Removing catalyst residues from epidermis coatings on leather fibers containing 20 The product substrates' consisting of polyether diprimaryamine is made possible. is dried and characterized. The equivalent weight of the amine is 4050, the associated viscosity

. sity in benzene at 25 ° C is 0.39 and the viscosity of

JJ e 1 s ρ ι e 1 1 _mass ^ _{) ulk viscosity} ) _{at 65} ° _{c 48 700 c} p.

25 A solution of 100 g of this poly (tetramethylene

2100 ml of tetrahydrofuran is distilled over LiAlH ₄ in an oxyd) -diprimäramins and 48 g of the diglycidyl ether 3-liter flask, which is equipped with a stirrer and dry-from bisphenol A (384 molecular weight) in 150 g of supply tube. The temperature is lowered to toluene, which has an equivalence ratio of oxirane to -70 ° C., and 210 ml (CF ₃ SOa) ₂ O active hydrogen of 5: 1 is added. Reactants are quickly set to 30 and held at 22 ° C for 24 hours with a partially reacted B-stage adduct being warmed to -10 ° C and held at temperature for 7.5 minutes. The resulting solution will hold. This solution is then reduced to 30% polymer solids and is cooled to -23 ° C. The polymer content is diluted by adding toluene, and merization is carried out by pouring the reaction components into a mixture of 1485 ml of liquid phenol. 4.8 g of 2,4,6-tri- (dimethylaminomethyl) participants are added. Part of this solution is added to ammonia and 1485 ml of tetrahydrofuran, which is initially kept at -70 ° C. by pouring on brushed, tanned pigskin. Excess applied, and the impregnated leather is 30 ml ammonia is then removed, and the polymer is heated at 66 ° C for a long time. The remaining solution is freed from catalyst residues by treatment to a solids content of 10% with a strongly basic ion exchange resin. 40 would be diluted with toluene and this solution for after the removal of volatile substances in the vacuum application as a second coating on the leather sample around 600 g of a low-melting poly are used by pouring on. After the sample was obtained for 1 hour (tetramethylene oxide) -diprimäramins (which was heated by long at 66 ° C, polished and cold with an analysis determined molecular weight of the amino end pressure of 35.15 kg / cm ^{2 for} 1 minute pressed groups is about 1400 ). 45 is, the same solution is used to apply a third A 10 weight percent solids solution in coating after the leather in the toluene of 36.5 g of the above poly (tetramethylene oxide) - the same way that after the second coating diprimäramins ( an equivalent of 0.1 of active has been applied (two light hydrogen), 19.2 g of diglycidyl ether of bisphenol A coatings are made from a commercially available (molecular weight 384, equivalent of 0.1 of 50 acrylic polymeric emulsion on the pig oxirane) and 1.92 g of 2,4,6-tri- (dimethylaminomethyl) - applied, and the sample is polished at 66 ° C and with phenol on the surface of polished, tanned a pressure of 17 , 57 kg / cm ^{2 for} 15 seconds temp side leather from cowhide spread, whereby pressed. A total coating of 8 g / 929 cm ² is deposited on 2.2 g of the solid substance on 929 cm ^2, the leather has been applied,
the. The leather is in an oven for 30 minutes 55 The final leather is very smooth and supple, dried at about 66 ⁰ C. Then it is left in front of it. It has excellent "break" properties and is extremely abrasion-resistant for two weeks of testing at room temperature. The penetration test to stay with. The abrasion resistance of this impregnated agitated water using the method of leather is excellent, tested by the resistance ASTM D-2099-62T produced no penetration when the surface was vigorously rubbed with the 60 to 22,000 series of bends, the point at the jagged edge a coin. The permeability for the test was canceled. The leather will moisture content is 32.4 g / m ² / hour if the adhesive strength of the finish and that at 22 ° C and 50% relative humidity, a value of the nature of the finish using which is sufficiently high to the wearer Comfort tested to deflection test procedures that ensure when this material is used as shoe upper leather 65 American Leather Association and the American. The untreated control sample from Society for Testing Materials for testing the Appretu leather has a permeability for vaporous ren on upholstered furniture leather with a Newark flexural moisture of 33.4 g / m ² / hour. test device (ASTM D-2097-62T) have been set up.

The finish
unattacked.

remains through 400,000 bend sequences

Example 3

The following ingredients are in a 110-1 kettle that is lined with glass and under one positive nitrogen pressure is maintained, enter:

25 parts by weight of cyclohexane 144 parts by weight of tetrahydrofuran 1.84 parts by weight of a catalyst Pyrosulfuryl fluoride.

Contains the ingredients are stirred for 5 hours at 30 ⁰ C and then introduced into a 220-1 stainless steel boiler containing anhydrous 8 parts, dissolved in 92 parts of tetrahydrofuran ammonia. After the mixture has been stirred for 2 hours, the excess ammonia and tetrahydrofuran is vacuum stripped from the polymeric product. Toluene is added to give a 30% solution of the product and this solution is slurried with 100 parts of a strong base anion exchange resin to remove any catalyst residue. The material is then filtered and vacuum dried to give 72 parts of poly (tetramethylene oxide) diprimaryamine having an associated viscosity of 0.51 in benzene at 25 ° C and an amine equivalent weight of 5400.

A 50 weight percent xylene solution containing 100 g of the above poly (tetramethylene oxide) diprimaryamine and 36.4 g of diglycidyl ether of bisphenol A (384 molecular weight, equivalent ratio of oxirane to active hydrogen is 5: 1) is prepared and for 18 hours at room temperature held in order to form a partially reacted "B-stage" adduct. .The solution is then reduced to 15% solids content .with ;. Xylene dilutes that one. contains dissolved black dye, 2.13 g of 2,4,6-tri- (dimethylaminomethyl) -phenol are added and the resulting solution is used to test samples of tanned and polished hide, tanned and brushed pig skin, unfinished synthetic leather , which contains a microporous polyurethane layer, thinly applied on a non-woven polyester fiber network, and an unfinished synthetic leather, which has a microporous, water-impermeable structure in which the particles of a rubber-like. Polyurethane are evenly distributed in a basic substance of nylon fibers and natural leather fibers. The two synthetic leather samples are treated only once with this impregnation solution and are then immediately heated at 66 ° C. for 30 minutes. After one week, they are ^{tested for their consistency at 22 °} C. and 50% relative humidity. Immediately after impregnation with the above-described solution with an aqueous 15% solid emulsion of a customary acrylic polymer for a leather finish, the ..- skin and pigskin samples are painted over before the impregnation coating has dried. These samples are heated for 15 minutes at 66 ^° C. and then for 24 hours at room temperature

dried. Two additional coatings made from the same acrylic polymer emulsion are used the same procedure is applied, and finally a nitrocellulose varnish is applied to the finished Sprayed surface. The test results are given in Table I.

Table I.

Angry Look 'persistence • Permeability Bending
resistance Substrate Impregnation
components (Coin test) for vaporous "
humidity (g / 929 cm ¹ ) very soft, excellent (g / m ² / hour) 144000 * Skin (cow skin) 4.9 ■ excellent
»" Rrucli <( 15th no cracking t / XJL · Uvllv
very soft, . excellent- 144000 * Pig skin 5.2 excellent 13th slight crack »Break« ■ very soft, · excellent ■ 144000 * Artificial 2.0 excellent 20 ■ no cracking Leather with micro "Fracture" porous poly urethane layer very soft, excellent 144000 *. Waterproof 3.5 excellent 15th Slight crack casual art "Fracture" leather

Number of bend sequences on the Bally bend meter.

Substantially similar results are obtained when the mixed resins are prepared by the method of Invention can be applied to leather from aqueous emulsions. Suitable emulsions can be based on a Number of ways to be made. So the polyether diamine and epoxy resins can be used together in one, inert, water-immiscible solvents. an approximately 50% solution can be dissolved, and this Solution can then be dissolved in water using a high powered and surface active high shear mixer Substances or protective colloids that are oil-in-water emulsions. nen are able to be emulsified. However, when the resins are prepared in this way, they tend to be for slow curing on storage and become less effective over time. Much more satisfying Results are obtained when the resins (or

209535/543

Solutions of the resins) are emulsified separately and then either combined or until application stored separately from the leather. If a curing catalyst is desired, it generally will added to the combined emulsions just prior to application. However, it is possible and sometimes Desirably, the curing catalyst to 'the resins from the Polyätherdiprimäramin before' the Emulsification process. or during the emulsification process ahrens to add. If the .Katalysator has been incorporated in this way, the Polyether diamine and epoxy resin emulsions are not combined before they are applied to the leather should be. . .

It is generally desirable to use an inert organic solvent such as benzene or toluene as use a diluent for the resins to facilitate emulsification. When the presence The solvent is considered undesirable, it can be removed by stripping it from the emulsion removed at any time after their manufacture.

The preferred flexible substrates which are treated by the method of the invention are "leather-like" substances, the natural leather or leather substitutes _r, with respect to the properties of natural leather same. For materials for shoe upper leather, microporosity is one of the desired properties for the substrates treated according to the invention, the microporosity should be sufficient to allow vaporous moisture through to an extent that is comparable to the permeability of natural leather; ie at least 10 g / m ² / hour. at a thickness of 0.127 cm determined by means of a micrometer screw by measuring between chambers of 100% and 50% relative humidity and a temperature of 25 ^° C.

Example4

A composition .for a coating that. for use on "leather, - 'cracked any leather. or.' various synthetic leather substrates is suitable, is prepared by mixing together 800g'Poly- (fetramethylenoxyd) -diprimäramin eipem with molecular weight of 12 500 and 250 000. einer'Viskositat the mass vö'h cP'bei 66 ⁰ C, 171 g of the diglycidyl ether of bisphenol A with an epoxy equivalent of 192.342 g of the glycidyl ether-.vom meta-pentadecenylphenol and 1967 g of xylene.This solution is stirred overnight to ensure homogeneity and the viscosity is then .870 cP-; fcei 25 ° C...! "

"To 200 g of this 40% solution | in a 1-liter beaker 24 g of leather dust and 3 g of tri- (dimethylammomethyl) phenol are added. and the Mixture is stirred with a three-bladed paddle wheel driven by an air motor, until all of the leather dust is well dispersed.

The above mixture is applied to a water-impermeable sheet material made of a crosslinked polyether polyurethane latex [made from toluene diisocyanate, polypropylene glycol ' ^: with a molecular weight of 1500 and enough triol (by "molecular weight 425") of propylene oxide and methylolpropane to achieve a crosslinking density of "1 crosslinking to create a molecular weight of the polymer of 10,000], leather fibers and nylon fibers (0.635 cm average length, 1.5 denier)

in a ratio of the solids weight of 6: 2: 1 each using a knife applicator with an opening of 0.051 cm. After air drying for 18 hours, the coating is cured in an oven at 66 ° C for 5 hours. The resulting coating has a cohesive, black, matt appearance. It has a moisture vapor transmission rate (MVT) of 15.0 g / m ² / hour and can be bent 191,000 times on the Bally bending machine before failure occurs.

Other coating solutions are made using the same solution of diamine and epoxy resins made by adding equal amounts of other pigments and fillers. These solutions are made by a colloid mill (Morehouse Model A-200) with a processing set of 4 mills and are then applied to the same waterproof film that has been applied above The results are summarized in the table below.

Pigment or
25 '' filler Bally bend
to
Failure MVT
g / rrr / h ■ Wood flour: '
Corn on the cob dust ...
30 soot
Cork, 90 meshes.
Iron oxide 93,000
190,000
93,000
191,000
191000 ' .16.5
20.4
7.5
18.0
6.0

The leather dust used in this and the following examples has been obtained by polishing the hair side of chrome-tanned cowhide. It has a water content of 9% ^UQ d and a fat content of 5%. All leather dust is sent through a 20-mesh screen before use.

. Example 5

A coating solution for use on leather or fabric is made by dissolving 1000 parts of poly (tetramethylene oxide) diprimaryamine with a molecular weight of 9500 and a viscosity of 95,000 ocP at 66 ° C., 243 parts of diglycidyl ether from bisphenol A and 343 parts of glycidyl ether of meta-pentadecenylphenol in 2380 parts of a xylene mixture. manufactured. The solution: mix overnight to ensure homogeneity. A film cast from this solution has, after curing for 4 days at room temperature, a tensile strength of 308 kg / cm ² and a longitudinal elongation to tearing of 526%. .

To 200 g of this reaction mixture in a 1 liter beaker, 26.7 g of leather dust and -3 g of Tn (dimethylaminomethyl) phenol are added using a three-blade paddle wheel to achieve a uniform dispersion. The resulting viscous mixture is applied to the water-impermeable film of Example 4 and to a medium-weight, chrome-tanned piece of cowhide with a knife applicator using an opening of 0.0508 cm. After drying in air, the curing is carried out by 5stündiges heating of the coated web material in an oven at 66 ⁰ C. The coating has a black, soft, matte appearance.

19 20

Bally Bend MVT. . , "

Example8

"Impermeable to water

P ₀ Jj ₆ 114 000 15.3 E ^me solution is obtained by mixing together

Cowhide piece ........... 500,000 26.3 450 g poly (tetramethylene oxide) diprimaryamine with

5 a molecular weight of 9800, 107 g diglycidyl

Example 6 ether of bisphenol A, 26.2 g of both natural

Petroleum jelly as well as lanolin and 1823 g xylene

Leather dust is provided with sufficient sulfonated. After a day of mixing, 500 g of this Nipple oil treated in water to put the fatty liquor reaction mixture in a 1 liter beaker, content of the leather dust to 20 percent by weight, which is equipped with a mixer, and 42 g heights. After complete mixing, the leather dust and 3 g of tri- (dimethylarninometnyl) phenol Slurry evaporated to dryness. These are added. After the reaction leather dust is in an epoxydiamine solution, as has been well dispersed in mixture, is further example 5, mixed in to form a viscous coating; mixed by passing the mixture through a colloid solution to result, which on a piece of cow skin, on a 15 mill with a set size of less than 1 mm, hairy cowhide and on a cotton ben. The mixture is then put on (a) water-twill (72 x 48 thread count) is applied. impermeable film made of polyurethane latex, leather-These Coatings are dried and fiberized as above and nylon fibers (as in Example 4) are made hardens. The bending results according to B a 11 y and which has been, (b) a carded network of 70% MVT data are shown in Table 20 below nylon and 30% polypropylene fibers with a shown: nonionic rubbery polyether polyurethane

Bally-Bend MVT has been impregnated, (c) a piece of cotton

Twill cloth and (d) on cleaned hairy cowhide

i ^{U (} Z. "■■ - Ί„ „™ ¹ Jr, raised. After drying overnight, become

Cowhide stucco 500 000 22.6 _{25 the coatings by storing in an} oven for 5 hours

Cleansed hairy _{at 66} <, _{c redeemed The flexibility} according to B a 11 y

^Cowhide 500 000 10.7 _{and the permeability through} i _for vaporous moisture

. . the coated products will be

SSEI game 'Table reproduced.

150 g poly (tetramethylene oxide) diprimaryamine with 30 Bally curve MVT

a molecular weight of 9500 with 36.3 g ^ ₇ , ,, _.

Diglycidyl ether from bisphenol A and 54 g glycidyl water impermeable

ether, from meta-pentadecenylphenol to a very _T ^ ⁰ ^ : ''"',"V.' · > öüuuu 1,0

viscous mixture mixed. This reaction- Impregnated carded

mixture is ^{heated to 66 0} C and then on a 35 _Ώ ^Netzw ?, ^r * \; ······> ° £ ™ °? 2

Piece of cow skin using a knife on tra- BaumwoH-Kopertuch .... > 760,000 7.1

gers and an opening of 0.018 cm. After cleaned hairy ^ «" _nn n _1Ä ,

standing overnight the coating becomes 66 ° C. Cowhide > 853,000 16.3

Cured for 3 hours. The product obtained has In some cases, waterproof sub-

an MVT of 12 g / m ² / hour and a flexibility 40 strate of the above type applied, which is a low

after B a 11 y of 425,000 bends before the upward bending resistance, z. B. a flexibility after

occur from mistakes. B a 11 y of 10,000 bends. After

The same reaction mixture is used in the same application of the coating to these samples

Way pulled up on a cleaned, hairy cowhide. Resistance to bending of the waterproof film

and hardened, with a soft excellent leather-45 being improved by a factor of 10 or more. In

similar finish is produced. The product has had similar attempts to the coated products,

MVT of 6 g / m ² / hour and a flexibility according to when the size of the colloid mill is 3 mm or larger,

B a 11 y of 500,000 bends without failure. higher MVT values.

Claims (4)

J 2 articles etc. are used not only to improve their patent claims, but also to improve their properties. Such finishes are mainly called 1. A process for the manufacture of a material that is polymerized together with a binder to impregnate or cover the leather fibers together and to improve their elasticity, abrasion resistance, flexible fibrous, porous sheet material and resistance to penetration by the formation of a hardened product from dirt and liquids . In the early amino compounds and epoxies in the inner leather finishing technique, a large number of natural structure of the web material or as a coating borrowed products, such as animal glue, casein or on top, characterized in that albumin, as a binding agent or finishing material, a mixture was used on the web material or a turns. In order that synthetic polymers have become an adduct of (1) a bar obtained by pre-reaction, other suitable finishes in water-insoluble polyether polyprimary amine have been developed. Gum-like polyacrylates and polymers of molecular weight at least 1000 are urethanes because of their ease of use, and having a terminal primary amino group, 15 their relative effectiveness in imparting elasticity, abrasion resistance and neighboring immediately to each end of the polyether portion, and with recurring groups, resistance to water and ordinary organic, at least a larger part of which consists of recurring solvents as particularly well-suited attached units of oxytetramethylene have been seen. Even in film form they have a relatively and at most a smaller part of recurring high expansion capacity, a property that consists of oxyalkylene or thioalkylene units with 2 to 6 straight-chain carbon atoms for keeping the shape of shoe upper leathers in the event of sustained stress is essential.
In spite of their many excellent properties, permanent primary amino groups, polyacrylates and polyurethanes still have certain —OC ₄ H ₈ NH ₂ , the named polyether part has disadvantages. Films formed from polyacrylates are less than about 3 weight percent nitrogen susceptible to abrasion or wear. Although the secondary amine atoms and less than about polyurethanes are characterized by resistance to wear and tear, they are in amine, and (2) an epoxy resin in a sensitive condition Oxirane equivalence greater than 1, the equivalency not being compatible with water. Therefore, they require the valence ratio of oxirane to active water - use of special solvents, which are expensive primary amine between 1: 1 and 20: 1 and are often toxic and / or flammable. In this, with or without further inert solvent, the moisture content of the leather or in an aqueous emulsion, and the (3) must be carefully adjusted within narrow limits if they contain an epoxy curing catalyst, so that sufficient bonding of the sensitive poly is applied, and one in or on the web urethane material hardens in situ during the subsequent hardening stages. ■ 'to secure. The need to harden the poly 2. The method according to claim 1, characterized thereby, urethane also complicates the process because the draws that a mixture is applied, the rate of cure and the amount of resin added Contains leather fibers or leather dust. 40 management must be checked. Ambient temperature 3. The method according to claim 1 or 2, characterized door and moisture conditions affect this characterized in that as curing conditions to be impregnated. One high temperature and one Speed "or to pulling sheeting such high ^humidity! Speed with a polyurethane finish or impregnation and the degree of cure, and occasionally can or a polyurethane coating is used. 45 thereby a hardened finish can be produced that 4. The method according to claim 1 or 2, characterized in that it is hard and brittle and for flaking or cracking characterized in that one is to be impregnated either during shoe manufacture or later or the sheet material to be covered tends to wear leather while wearing the finished shoe, turns. Cracked leather and other types of leather with un- • ...- 50 desired surface properties can be achieved through Impregnation and / or coating are improved, by creating a synthetic epidermal layer will. The problems of adhesive strength, appearance, the permeability to vaporous moisture, 55 of the flexural strength etc. make it difficult to The invention relates to a method for achieving the desired results and for the Manufacture of a commercially suitable product with a polymeric material. Similar propregnated or coated flexible, fibrous, bleme are made in the processing of leather substitutes porous sheeting, e.g. B. leather, leather or a suitable synthetic substrate mesh Substitute, leather fiber-containing sheet material 60 network to overcome. or other fibrous, porous substrates, by design. U.S. Patent 3,130,069 are coatings formation of a hardened product from amino compounds known for leather. Epoxy resins so far are not very genes and epoxies in the inner structure of the webs have been well suited as coatings for leather if the materials or in at least one coating thereon. original properties of leather, to which the Finishes and impregnating agents will usually be preserved fig applied to tanned animal hides that are supposed to. So are in the said USA. Patent Shoe upper leather, for furniture upholstery, for hand- initially described the many problems that one faces bags, wallets, belts, luggage, clothing in a treatment of leather with hardened poly-