DE2136951C3 - Self-shine care products for shoes or other items made of leather, plastic or leather-like materials that are subject to bending stress - Google Patents

Description

Self-shine care products are well known from floor care. They become according to their destiny only used where the documents to be treated with them without major changes in shape are claimed. The maximum change in shape of these documents is vertical through pressure to the document, e.g. B. when walking on the floor generated. An elastic covering is used locally compressed and gradually returns to the original state after the compressive stress has disappeared Plate shape over.

Wherever the documents to be looked after are deformed significantly more, e.g. B. at Shoes or utensils made of leather. Plastic or leather-like materials, could the self-shine agents have not yet prevailed. The deformations during use often go like this % veit that the documents are properly folded and then folded back again; self-shining and Film-forming care products have so far not been able to follow such deformations without themselves To change even disadvantageously.

The applicant, a well-known shoe care agent manufacturer, has tried in vain for over 10 years to create a self-shine agent suitable for shoe treatment by modifying the floor self-shine care agent! To be developed: Well-adhering care product applications regularly lead to breaking in the folds of the creases when applied once, to the formation of layers and tears when applied several times; greater flexibility of the application inasse led to stickiness and increased dirt absorption; Better removability - for the purpose of removing the crust or removing the layers of dirt - resulted in a lack of waterproofing wedge.

The result was that self-shining care products for treating documents that were strong Are exposed to deformations, have not yet prevailed on the market. The applicant and others well-known companies have to Schuhbchandlunj! certain self-shining care products withdrawn; Such products still to be found on the market were unable to achieve any noteworthy market share. So z. B. almost all shoe care is still done with wax-based goods.

be it solvent-based pastes or emulsions. With these products, the desired shine is only created by polishing.

The previous strong one, but not satisfactory Endeavors to solve the problem, a self-shining care product, especially on an environmental basis, to maintain the documents that are exposed to strong *: deformations, in particular So for shoes from street shoes to boots

ίο made of "crumple paint" is very good for the following reasons Understandable: Such care products are usually very strongly colored (in the case of floor care products if this is not the case), these strongly colored, oil-based care products are easy to handle

to stains that are difficult to remove. After the order, another work step must be carried out, namely the Polishing, done; however, the gloss produced by the polished waxes is, depending on the stress, only of limited shelf life. the

ao tendency to absorb dirt is still relatively high with wax-based care product layers.

Of the self-shine care products for floors mentioned at the outset, those in particular have proven themselves based on a Zn or Zr complex of acrylic

a5 polymers. Wax and f-caprolactam proven to be effective as she in Chem. Abstracts, Vol. 71, 1969 under 62 352 r are described. The stated advantages relate to the basic requirements for the floor care products, such as gloss, flow, water resistance and behavior when reapplied, but say nothing about them additional requirements for documents subject to bending, such as high flexibility or simultaneous Stickiness and high adhesion to the substrate. These last mentioned points of view, which are only for the

new intended application are important, namely in the development of the earlier Techniques played practically no role; they are not mentioned in the relevant literature (cf. z. B. also N. Sood, Soap & Chemical Specialties, 1970, pp. 35 to 37).

Nothing changes in this when it says in "Coating" No. 2, 1970, p. 62, self-shine emulsions for Shoe upper leathers are also liquid wax emulsions that dry with a self-shine and are similar

The self-shine emulsions for floor care are built up. It goes on to say: "Since upper leather is more flexible than flooring materials, the remaining wax films have to be softer, more flexible and more strongly adherent to the substrate." to give the wax film the desired properties; In any case, the components given in this reference do not lead to a satisfactory result any more than those mentioned at the beginning, which have already been brought onto the market and not! enforced means.

The object on which the invention is based therefore consisted in the selection of one for the application on shoe covers or other bending loads Utensils made of plastic or leather-like materials suitable combination of per se known components of the self-shine care products from a metal-bonded plastic dispersion based on acrylic, a styrene-maleic anhydride copolymer, a wax dispersion, permanent and temporary plasticizers, non-ionic emulsifiers, ammonia, fluorinated wetting agents

and, if necessary, a silicone defoamer by means of bridging components with one another

mer. .... ~, - can be connected. The responsive

This goal is achieved according to the invention by components are usually carboxyl groups, and

the use of a mixture of a metal- the bridging elements are polyvalent

Bound acrylic-based plastic dispersion, 5 metal ions. The dissolution of the intermolecular

a styrene-maleic anhydride copolymer, a compound occurs through complex formation on the

Hard wax dispersion, permanent, solid and metal, ζ. B. with ammonia, the resulting

porous plasticizers, non-ionic emulsifiers, metal-ammonia complex must be more stable than that

Ammonia, fluorinated wetting agents and given intermolecular bridging,

if a silicone defoamer as a self-shine care 10

medium for shoes and other bending stressed ^b ) With a solid plasticizer optimally plastic

Objects made of leather, plastic or similar leather- ^{Z! Crte resins}

similar materials. Optimal plasticizing rune means here: clearer,

The agent to be used according to the invention contains neither brittle nor tacky flexible film, the

so in combination at least ₁₅ neither plastic nor elastic, but largely form-

a) an aqueous plastic dispersion which should be consistently flexible when it is applied. It has been found that drying intermolecularly but reversibly results in ^the mixing conditions required according to the invention and that their molecular nature 8 ^and s ^{en to} achieve maximum plasticization - in particular due to a content of acid - of certain resins can easily be determined experimentally.

group - swelling processes at the phase sequence ^{and that the selection} 8 ^erade , ^{so] ch} J ^T

makes possible · resin mixtures essential for the production of the

b) a resin solution that is with a solid soft agent according to the invention.

wheeler to an optimum Filmbilduno ^The PLA described ^recently soft solid

Caprolactam fulfills these requirements

c) a hard wax dispersion. ² S particularly good. What was surprising, however, was that he did

- applied in the appropriate proportion - initially

The agent to be used according to the invention is the resin itself, but then also the coatings

So through a special selection and combination of the entire care product, the necessary extra-

of three different, per se known granular flexibility, which in the

marked components that was not required in this combination 30 previous forms of application

a previously unknown and not to be expected - and therefore practically ignored,

give the effect. The new agent outperforms the _u . ...

Current state of the art in the field of ^c) Hartwachsd.spers.onen

Care of substrates that are subject to severe deformations are contained in practically all inspection 35 hard wax; the choice of waxes score. This applies to both the conventional and itself is not necessarily significant for the remedy, common care today, e.g. B. Shoe- In other words, care products that match the above materials by using oily pastes, you can use or of emulsions, one component of which is produced from a different suitable hard wax Represents oil phase, but also for the already known 40, z. B. are microcrystalline paraffins, natural products with self-shine effect. waxes or polyethylene waxes are suitable. The three main components of the waxes suitable according to the invention, however, include those with which These means are described in more detail below. particularly good care product properties can be achieved

, ". . , .... "Can. The present description is limited

a) Be, drying, reversibly crosslinking, at _{phase f djese} *>

in addition to this information about the main

In addition to the acrylic-based in aqueous medium _{, it should be noted} that of course the other

spergiert which correspond to the prior art, ^ ^ _{sonstj Zusä VQR a "em dyes}

chend plast.fiz.ert can be incorporated, including funds

It has been shown that such a plastic 5 ° ^to regulate the hydrophilic character. It has

dispersion then optimally shows the intended purpose that the desired removability of the

fills when the emulsion droplets are sufficiently small care agent, which in principle is achieved by

and by swelling in an alkaline environment that the intermolecular crosslinking by complex

their surfaces can be changed in such a way that education can be canceled again by

the interfaces become more or less diffuse. 55 restricts hydrophilic substances from being permanent

Such emul hydrophilicity, to be selected according to the invention, e.g. ethylene oxide adducts on nonpolar ones

Sions are largely visually clear (see-through) and hydrocarbons, can be amplified, namely

easy to recognize by it. Plastic emulsions which - under certain conditions - without inadmissible

these types are commercially available recently; sige reduction in water resistance.

they were used for the production of so-called clear proportions

Polishes designed for floor care.

The plastic dispersion should also be composed in such a way that the quantities suitable for the new care product are in additional proportions when it dries - based on about 20% active wetting, but this cross-linking reversibly redissolved the same constituents in aqueous dispersion or loosening can. This technique was also used for the 65 solution - as follows:

Floor care developed. The effect is in the a) plastic 5 to 20, preferably 7 to 13 parts,

Usually it is sufficient that the plastic dispersion b) resin 0.5 to 5, preferably 1 to 2 parts,

contains reactive groups in the molecule which c) wax 1 to 10, preferably 2 to 5 parts.

This is followed by the plasification of the plastic and the resin

permanent plasticizers 1 to 7. preferably 2 to 5 parts,

of which solid plasticizer 0.5 to 1.5. preferably 1 part, based on 1 part of skin

D ^; . ° se constituents are essential for the agent according to the invention. The remaining proportions are not significant and are used to fine-tune the product properties.

The following proved to be beneficial:

Nonionic emulsifier 0.5 to 4. preferably 1 to 2 parts,

temporary plasticizer 0.5 to 4, preferably 1 to 2 parts,

Ammonia solution (30% 'g) 0.5 to 4, preferably 1 to 2 parts,

fluorinated wetting agent (10%) 0.5 to 3, preferably 0.75 to 1.5 parts,

Silicone defoamer 0.05 to 0.3, preferably 0.1 to 0.2 parts.

Depending on the desired degree of effectiveness of the product, the formulations according to the invention can also be used in stronger dilution and possibly also in higher concentrate «"; the specified Conditions then change accordingly.

raw materials

The following commercially available raw materials have proven to be suitable:

a) For the plastic dispersions:

Acrylate copolymers or copolymers and mixed polymers with monomers of the type: acrylic acid or methacrylic acid methyl ester, Ethyl ester, butyester, acrylonitrile, acrylamine, methacrylic acid, styrene and polyacrylate metal complex products.

For plastic plasticization:

1. Dibutyl phthalate.

2. Tributoxyethyl phosphate.

In practice, preference was given to the plasticizer tributoxyethyl phosphate.

b) For the resins

Styrene-maleic anhydride resins of relatively low molecular weights have proven to be most suitable between 1500 and 300Ö, especially with an average molecular weight of about 2000 and an average acid number of 200 to 300.

For resin plasticization:

Execution with solid plasticizer caprolactam.

Leave the quantitative ratios to be selected during plasticizing to achieve the optimum through simple series tests on the result of the film properties obtainable from the mixtures easily determine.

c) For the waxes

Various hard waxes are suitable, e.g. B.

1. Emulsion polymeric polyethylene wax emulsion.

2. Special wax composition.

Literature: Technical Service Bulletin "Petrolite 246", from May 10, 1969, Petrolite Corp., Bareco Division, Tulsa, Oklahoma, USA.

Parts

Wax composition 20

»Emulsifier« *) 4

Ammonia (25%) 3.6

Water 72.4

*) "Emulsifier" is a non-ionic emulsifier based on an ethylene oxide adduct with the chemical Designation nonylphenoxy-polyethoxy-ethanol.

The wax is melted at 115 to 118 ° C and gradually the boiling water, which shortly beforehand has been mixed with the necessary amount of ammonia was admitted.

jo According to the manufacturer, it is the special wax composition based on a maleic acid-grafted hard wax copolymer a wax mixture of two components, one of which is largely linear and the other one has a highly branched hydrocarbon chain. The maleic acid is probably in this graft polymer in multiple blocks of two to three units. The Maleinsäuieblöckc are statistical Distributed over the wax molecules in such a way that some of the wax molecules are also free of maleic acid blocks is. The result of this block copolymerization is reflected in the information given at the beginning physical data.

3. Polyolefin oxidation wax with largely linear Carbon chain and relatively high acid number.

Such oxidates are obtained by known methods, e.g. B. by oxidation of molten-jnPolyolefin Copoiymerisaten in aqueous dispersion. A large part of the carboxylic acids formed is present as dicarboxylic acids, which have an average Have a molecular weight of about 2000 and a density close to 1.

The physical data are as follows: Fixed point 105 to 115 ° C; Acid number 40 to 70; Saponification number 70 to 130; Penetration 0 to 2; Viscosity at 140 ° C: 200 to 50OcP.

This wax can be converted into an ionic or a non-ionic type with the aid of known techniques Wax emulsion are transferred. Like the wax emulsion already mentioned, this is used in the one according to the invention Recipe used.

4. High montan wax based ester wax

Hardness and high acid number.

Physical data: Fixed point 84 to 89 ° C; Acid number 85 to 95; Saponification number 130 to 145.

The production takes place in the manner known for montan wax derivatives. The emulsion from this Wax is produced in the manner already indicated and used in the manner according to the invention.

d) Other additions

1. Nonionic emulsifier, e.g. B. Nonyl-Phenol-Polyglykoläthcr with about 10 attached Ethylcnoxydcinhciten,

2. Temporary plasticizer, τ. Β. Diethylene glycol monoethyl ether,

3. Wetting agents, e.g. B. fluorinated carboxylic acids,

4. Defoamers, e.g. B. silicone defoamers.

Manufacturing

The products according to the invention are manufactured with the aid of the abovementioned raw materials as follows:

The plastic emulsion is presented and at 70 ° C with the recipe amount of water and Ammonia solution added; then the permanent plasticizer is added.

The resin is dissolved in ammonical water, the solids content of this solution is 10%>. These The 80% aqueous solution of the solid plasticizer is added to the solution.

The entire resin solution becomes the entire plastic dispersion added.

The finished or previously prepared wax emulsion is then added to this mixture.

This is followed by the conditioning additives.

This manufacturing specification is not binding. Various changes are possible without impairment of the result.

Recipe

Work is carried out according to the following rule, which - seen as a whole - meets the specified properties best corresponds to; an exchange of the raw materials as indicated above is however - with a slight change the properties - possible.

O _n solid

Polyacrylate metal complex 22.5 9.0 g

Water, distilled 43.4 -

Ammonia solution (25 ° oig) 1.5 -

Tributoxyethyl phosphate 2.25 2.25 »

Styrene maleic anhydride resin H-- U 2 3

Caprolactam (80 "/" ig) 1.5 1.2 g

Wax composition (20 °) 15.0 3.0 g

Diethylene glycol ethyl ether 1.5 1.5 g

Wetting agent (fluorocarboxylic acid) 1.0 -

Silicone defoamer ^Q , ¹⁵ 0-15 g

100.00 18.22 g If applicable:

Non- ionic emulsifier UOQ U ⁰⁰

101.00 19.22 g

The advantages of the care product according to the invention are as follows:

1. Comparison with conventional shoe care products

a) polishing

There is no need for polishing at all.

b) Order

The care product is applied at least as effortlessly as the conventional one Oil or emulsion based agents. The job can can also be done on slightly damp shoes (shoes that have been used after use can also be treated are still slightly damp in the rain or have been cleaned with a damp cloth to remove dirt).

c) Admission

The care product is eagerly absorbed by the leather as a hydrophilic fiber. The consequence of this is an extremely short drying time, the shoe can be used just 1 minute after application will.

The good absorption of the aqueous emulsion by the leather results in a deep care of the leather , ίο The pore filling represents a permanent basic protective layer.

d) repair effect

Damage to the leather covering is compensated for particularly well, since the porous leather is essential absorbs more care products than the leather that is still covered or has already been cared for. at If colored care products are used, the damaged area will be enriched with color; the »Ο The result is an automatic mending effect.

e) water resistance

After the care film has dried on, the water resistance is at least as good as that of oil- »5 pastes and better than the wax-oil-based care emulsions (of the conventional type).

f) water diffusion

Despite this good water resistance and the excellent pore filling there is no absolute seal the leather surface instead. The molecular passage of water, in other words, the Water diffusion is still possible. The leather or the leather-like material can "breathe"; the Foot moisture continues to be released to the outside.

g) dirt pick-up

The dirt pick-up is significantly lower than with all conventional care products. The dirt adhesion is much weaker, the need for cleaning is lower and the cleaning as a result easier.

h) New order

The care layer is loosened a little with each new order, the adhesion of the new care layer is therefore excellent, there are no unsightly transitions between the old and the new care layer on. As a result of the loosening effect, the layer is formation almost impossible or increased for very long maintenance times.

i) Distance

A complete removal of old care history is possible at any time using the remedy itself lent, the pore filling is retained, the leather as a result, it is not "drained".

k) maintenance intervals

The maintenance intervals become significantly longer when the agent according to the invention is used. In practice, a reduction to Vs to ¹ Ao d maintenance procedures was found.

I) consumption

The consumption of care products is extremely low, with a 15 to 20% care product of the specified type it is 0.35 to 0.4 g per ski

509621 /;

couple: that means that with 100 ecm of care products 250 brushing passes are possible. The consumption when using conventional care products is around twice as high. With conventional care products, however, only part of the applied dry substance remains on the leather, a significant, usually larger part is removed again during polishing. It has been shown, however, that the care effect always occurs when the agent according to the invention is used a nuance, in some cases significantly better than when using conventional products. This finding is particularly interesting because such materials are becoming increasingly important to win.

Result

With significantly improved properties in the use and handling of the invention By means of a substantial saving in working time and effort in the maintenance process, an essential one Saving of care work in general through greatly reduced care frequency and a reduced Consumption of shoe care products reached.

2. Comparison with self-shine care products available on the market

Such funds are difficult to find on the market. Three agents could be found on the German market made, one of which was of American origin.

These funds were checked together with another medium of French provenance. Thereby »5 the following was found:

Medium 1: The medium is very uneven in the order. The kink resistance is extremely poor.

Means 2: The product is not waterproof at all. Even after drying for several days the agent is rinsed off with water alone; there is a strong risk of fouling.

Agent 3: The agent is insufficiently waterproof, insufficiently kink-resistant, disadvantageous in terms of dirt absorption.

Agent 4: The agent is elastic, but very sticky and consequently shows a high level of dirt absorption and is poorly waterproof.

All of these products have so considerable deficiencies in mostly several properties that they have the Requirements for a self-shine care product that can compete with conventional care products should not be able to meet. The application of these products in practice has confirmed this, because the consumer practically only uses the conventional means.

The treatment of novel, leather-like materials

Shoes, clothing, handbags and the like today partly from so-called plastic materials, partly from new, leather-like, synthetic materials Materials made.

The maintenance of these materials can also be ir conventional care products. Care of heavily structured and differently colored Objects made of leather, plastic or leather-like materials

Shoes, leather clothing, handbags and similar items today are often made of different colors Composite materials. They also often consist of more or less thin, adjacent or spaced apart braided strips or are perforated, etc. The use of conventional care products very often causes great difficulties here, since polishing is practically impossible or there are maintenance products - Debris — settle in the folds or the individual Colors cannot be treated separately.

With the care agent according to the invention - either colorless or colored - can also Carry out maintenance here practically always and almost effortlessly. A prophylactic protection with the Agent according to the invention prevents wear and tear and can maintain the shoe as long as it is at all is mechanically stable. Objects, such as handbags, can be cared for properly because they cause coloring Abrasion excluded even when using colored care products of the type according to the invention

Staining

The formation of stains occurs with the conventional, colored care products as well as with some of the Self-shining care products known at the time pose a problem.

This is not the case with the new remedy. After the care product has dried on, there is no staining more is possible. If the cleaning agent is rubbing heavily, the abrasive particles will wear off but no longer color, although they are colored themselves (the color can no longer be applied to another "Pull up" the object).

Fresh care product of the type according to the invention can, since it is an aqueous emulsion, can be removed without difficulty with clean water; dried-on care product can be used Loosen the care product yourself and rinse. Most suitable for re-dissolving the non-colored (colorless) care product.

Claims (2)

Patent claims: 1. Using a mixture of a metal-bonded Plastic dispersion based on acrylic, a styrene-maleic anhydride copolymer, a hard wax dispersion, permanent, solid and temporary plasticizers, non-ionic. Emulsifiers, ammonia, fluorinated wetting agents and optionally a silicone defoamer as a self-shine care product for shoes or other items made of leather that are subject to bending stress. Plastic or leather-like materials. 2. Use of a mixture according to claim 1, characterized in that as permanent Plasticizer f-caprolactam is used.