DE2224967A1 - REINFORCEMENT - Google Patents

Description

DEUTSCTTE GOLD AND SILVER SCHEIDEANSTALT, VOWfALS R0ES3LER 6 FRANICFURT (MAIN), VEISSFRAUEWSTRASSE 9 222A967

Stiffener

The invention relates to thermally deformable or "shaped" Stiffening materials, in addition to at least one fiber base or insert furthermore contain at least one thermoplastic material as binding agent or stiffening agent; they are used to stiffen and maintain the shape of molded Objects such as, in particular, shoes and hats, preferably from Front and back caps of shoes. In the shoe industry, the stiffening materials are often referred to as cap materials.

Numerous types of stiffening materials are known from the literature known that contain polymeric binders or stiffening agents. Organic solvents, for example, are used to temporarily soften these substances or to activate their adhesive film. or the softening occurs through the application of heat.

In the related art those reinforcement materials are due to the simpler and faster processing increasingly preferred in which the binder (Versteifungsrnittel) are adapted by Värme softened to. _"R are the structure of the binder is as low or is influenced so that after Deformation and cooling a good and constant shape and at the same time a good flexibility of the moldings is guaranteed. The already preformed stiffening materials can be provided with a layer of thermoplastic adhesive on both sides.

Those used to soften the substances or to activate them (make them sticky) the heat necessary for the adhesive is applied to the stiffening materials e.g. 13. through contact with hot deformation surfaces,

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by water vapor, by other hot gases, by infrared radiation or the like supplied.

The use of the electromagnetic high-frequency is also known Alternating fields in the area of so-called microwaves for heating food.

It is also already known to use microwave absorbers to on objects such as antennas and others in electronics or in the transmission of messages in the high frequency range Article to suppress surface wave formation and to lessen the reflection of the waves. Iron powder, carbon powder or ferrites serve as microwave absorbers. The microwave absorbers are applied to their surfaces in a conventional manner, e.g. by means of hardening plastics Article applied firmly.

It is also known with some Russians or with certain Rubbers filled with silicate fillers in the microwave field to vulcanize. This enables continuous production of rubber profiles.

It should be pointed out here that there are important differences between the ultra-high frequency (microwave field) and the usual high frequency in practical application. Thus, for example, needs for heating objects rus materials having higher or sufficient loss tangent (= the product of loss tangent and dielectric constant) in the UHF field, none of the shape of the article matched electrodes, in contrast to heating in the conventional high-frequency field (at lower frequencies). One therefore likes to speak of UHF or microwave ovens.

The transfer of the well-known micro wave technology to the

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The shoe industry and allied industries were neither obvious, nor was it easily possible, especially for the heating of stiffening materials. In the shoe industry, apart from leather, plastic or plastic, such as materials containing polyvinyl chloride, is being used to an increasing extent as an upper material. In the microwave heating of the stiffening substance but because of their Värmeetnpfindlichlceit the attached or already in places associated should not or upper materials are only slightly heated with, that is at least only heated to the extent that damage to the upper material is excluded. However, leather and in particular polyvinyl chloride or other known, in particular polar plastics are heated considerably in the microwave field with a corresponding dwell time in the oven.

Surprisingly, it has now been found that the additional incorporation of one or more active substances into the with thermoplastic impregnated or coated stiffening materials solves the problem. In this way Modified stiffening materials allow using microwaves the heating to the softening or activation temperature in a few seconds the binding, adhesive or stiffening agent, ' without the associated other materials being heated to a significant extent. With the invention it is now advantageously possible, also thermoplastics to use with relatively high softening temperatures for the production of the new stiffening materials, while so far from Reasons of the heat sensitivity of the materials to be stiffened such thermoplastics could not be used. The use of these thermoplastics with a high softening temperature also brings considerable advantages in the use of the stiffened materials, such as better stability in the warmth, for example at high summer temperatures.

The malleable or shaped stiffening material according to the invention,

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in particular shoe cap material, consists of at least one fiber toff underlay or insert and at least one thermoplastic Plastic as an inde- or stiffening agent with fillers, plasticizers contained therein, if necessary, Dyes, pigments or stabilizers against Light, heat and / or mechanical influences, individually or in groups. The stiffener optionally has an adhesive line based on thermoplastic material on one or both sides (surfaces). The new stiffening material is characterized in that in the thermoplastic at least one active substance in amounts of at least 3 parts by weight, based on 100 parts by weight of the active substance (s) containing plastic or the active substance (s) containing plastics. The active ingredients should be in a fine, even distribution in the stiffening material or in the thermoplastic plastic of the stiffening material and / or the adhesive line are present.

The invention also relates to the use of those described above Stiffening materials as shoe cap material or as a fitting piece, if necessary in a preformed shape, for stiffening in particular the front and back caps, preferably the back caps, of shoes.

As active substances in the context of the invention, first and foremost, carbon blacks are to be mentioned. The active substances also include soot preparations and fluid compounds such as, for example, the gray pigments which are produced in accordance with British patent code 1 13920. > ·

It could not be foreseen that stiffening materials containing ituss in sufficient quantities, preferably evenly distributed in oil, could be heated to working temperature in the UHF field in just a few seconds without damaging the stiffening materials. In this sense, the working temperature is the temperature at which the dor Vnrstpj -Tung = * * .tof T is so soft. ti £ ·. £ ·. s or can be easily molded or preformed. Hey the Schvhher—

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BATH

position · the stiffening material can then be described as "soft". Soot -in sufficient amount in this context means in an amount that causes in a few, for example 3 »^ or up to 6 seconds, the necessary softness or lightness Deformability of the stiffening material is achieved in the UHF field; The amount of the kiss, here based on the amount of plastic of the binding agent or adhesive, is also dependent on the type or quality of the soot,

Although in principle all of the many types of soot tested can be used there are qualitative differences in the dielectric heating of the stiffening material. So in In many cases Flame and Furnace Russians are better than Gas Russians; these differences therefore relate to the manufacturing method the Russian. In other cases, stiffeners are in

. highly structured or referred to as so-called conductive Russians Russ varieties better, which means that they work faster in the UHF field, for example. Add to that the choice of thermoplastics during dielectric heating the stiffening material plays a role. The more polar the plastic, the higher the heating that can be achieved of the stiffener at the same time; so heats

_ play the stiffening material with the same type and amount of soot Based on polyvinyl chloride in the UHF field at the same time to a higher temperature than a stiffening material based on homopolyinererri styrene.

However, it was by no means to be expected that stiffening materials with, for example, 25 parts by weight of furnace soot with BET surfaces in the range between 50 and 150 m ² / g per 100 parts by weight of thermoplastic binders (solids content) would be 2, Allow 5 k1v ^r power to heat up to the working temperature in 3 seconds while

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bound or in contact material, such as leather, stays practically cold.

Another group of active substances are graphites.

The quantities of the active substances must be sufficient to achieve a rapid land! If possible, the same: wet dielectric heating. For practical reasons, the lower limit is approximately 3 parts by weight per 100 parts by weight of the thermoplastic material. The upper limit of the amounts to be introduced into the stiffening materials is not essential for the effect in the UHF field. Larger proportions have a stronger or faster effect, smaller proportions less intense or slower, depending on whether you are referring to temperature or time. These upper limits are rather given by the difficulties involved in incorporating larger quantities, in the case of Russians, depending on the type of soot, and also by the "dilution" of the binding, adhesive and / or adhesive. Stiffening agent by large amounts and / or by too high or too rapid heating of the stiffening substance, amounts over about 40 parts by weight generally no longer improve the desired effect to the extent ρ in which the disadvantages of a higher use increase, such as the decrease in the The stiffening effect, the flexibility and the binding effect of the stiffening substance, depending on the type (selection) of the active substance, the upper limit can be pushed far beyond if desired, for example up to two or three times the amount of plastic. Preferably, the amounts are between about 10 and 30 parts by weight per 100 parts by weight of plastic. In practice, 25 parts by weight are used with advantage, especially when using Russians. The Ge \ v ^r T parts are always based AIIF the weight (lOO Ge weight parts) of the thermoplastic material and dex plastics, which are containing the active substance (s), used to impregnate and or or for coating the Versteiftingsstoffes (solid content ).

The initially flat, foil-like or sheet-like stiffening materials

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are conventionally made in sheet form. As a fiber material textile fiber structures such as woven fabrics, fleeces, knitted fabrics, etc. made of natural and / or or synthetic fibers, including blended fabrics and including the use of mixed webs or fiber blends for the production of the textile structures, preferably made of cotton, rayon, polyester, polyacrylonitrile, polyamide, etc. The stiffening materials can also consist of a basic and a Cover fabric and made up of two or more textile fiber structures be. Particularly in the case of preformed heel caps used for shoes, leather fibers or other fiber waste will.

For the impregnation or coating of the textile fiber structures thermoplastics preferred, such as homo- or copolymers of styrene, styrene-butadiene or styrene-acrylonitrile copolymers, especially those with a high styrene content, Styrene-acrylate-co- or styrene-acrylonitrile-butadiene terpolymers, also Pol3> -chlorobutadienes, polyvinyl esters such as polyvinyl acetates, Polyacrylates or polymethacrylates, also polyvinyl chlorides (including post-chlorinated polyvinyl chlorides), Polyvinylidene chlorides, nitrile rubbers, ethylene-vinyl acetate-co- or terpolymers and ionic resins, both individually and as a mixture. If necessary, the thermoplastics Natural resins, phenolic resins, maleic resins, modified colophony resins or the like known resins may be blended in usual amounts. The above are used for the basic impregnation Plastics mostly used as a dispersion. If desired, you can the abovementioned and, if appropriate, other customary auxiliaries are also used in customary amounts. Possibly can also be known Mitte.1 for the production of Foam may also be used. Contain very suitable dispersions Copolymers of styrene and butadiene, of acrylic acid esters,

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such as butyl acrylate, with monomers such as vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, acrylonitrile, acrylamide and / or acrylic acid. The dispersions in question
are made in a familiar way.

The stiffening material can be coated on one or both sides with a so-called adhesive line based on thermoplastic, that is, plastic that can be activated by heat, for example based on
Polychlorobutadiene, polyvinyl acetate, polyacrylic acid esters, ethylene-vinyl acetate polymers or nitrile rubber may be provided. If desired, and often with advantages, other resins can be added to the thermoplastic of the adhesive line, for example natural resins, phenolic resins, maleic resins, modified rosins or similar known resins, specifically in
usual amounts. This adhesive line is used to bond the
Stiffening material with the substrate to be stiffened. The active substances according to the invention can be incorporated into this adhesive line alone or at the same time. It is also possible using suitable binders, the active substances as
To introduce intermediate layers between the adhesive line and the actual stiffening material.

The fillers, which can be mixed with the binder in the usual amounts, are the solid, powdery ones known in the relevant technology! Substances of natural or artificial origin. Likewise, the dyes, pigments, plasticizers and stabilizers are relevant groups of substances that are also available in customary amounts and on
known manner can be incorporated into the binders.

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Examples

For impregnation of the. Fiber web becomes a carbon black plastic dispersion used. For this purpose, the soot (20 parts by weight) is first mixed in a 3> 3 percent by weight aqueous solution Wetting agent based on a non-ionic fatty alcohol derivative (80 parts by weight) dispersed. This soot dispersion is now one of the thermoplastics of various origins is stirred into the dispersion so that 25 or 12.5 parts by weight of carbon black per 100 parts by weight of the thermoplastic can be used.

The impregnation of a 300 g / in ² heavy cotton fabric roughened on both sides is carried out with the dispersion described. Liehe manner carried out so that after the drying of the fabric at about 120 ⁰ C, a final weight of about 800 g / m ^{2 is} achieved.

The following table I shows the various types of carbon black used. The plastic dispersion according to Example 9 (Table II) was used for this. In example K , a dispersion with 12.5 parts by weight of carbon black, in all other examples with 25 parts by weight of carbon black per 100 parts by weight of thermoplastic was used.

In Examples 9 to 12 (Table II) dispersions were with different plastics, but with the same carbon black that was also used according to Example 3, in amounts of 25 parts by weight used on 100 parts by weight of plastic.

The stiffening fabrics according to Examples 1 to 12 were in a Microwave oven with a power · of 1.2 K ¥ and one Frequency of 2 ^ 50 MHz placed. After a dwell time of 3 seconds in the In the oven, the originally hard materials are soft and easily deformable. Immediately after taking it out of the UHF oven, the

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The surface temperature of the stiffening materials was measured, the same initial temperature of which was the room temperature _β . These temperatures are listed in the last columns of Tables I and II. For comparison, a softening agent which had been impregnated with the dispersion according to Example 9 but without carbon black content showed no measurable heating and no softening after a residence time of 10 seconds in the microwave oven.

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Table I.

May be
game
No. name of
Russes • Class · des
Russes * Oil requirement
(FP) in Middle T.
size
Arithm.
middle ; acrid
in do
Above
Surface Surface
from EM
calculated ie in
/after
BET ^ Temperature in ⁰ C
after 3 seconds
in the UHF oven 1 Flame black 101 oxidized
Lamp soot 280
■ 95 I60 19th 21
ι 75 30985 2
.-- ■ O
'''' J Printex A
Corax 3 HS Furnace
Soot
Furnace
Soot higher
structure 300
430 kl
27 53
33 63
9k k6
78 70
70 0/0053 k
5 Corax 3 HS
Printex 30 dto,
Furnace
Soot 430
¹
4oo 27
27 33
33 9k
9k 78
78 70
1 δ Printex 300 Furnace
Soot 360
• 27 33 9k 78 65 7 - Corax L Furnace
Rxass 560 23 32 93 150 70 ¹ ^ ³
ro
K) 8th "SPF 35 Furnace
Soot 77 70 pounds
CD

'DBP adsorption in ml / 100 g.
ASTM iodine adsorption: 80.6 mg / g

Table II

at
game
No. Trade name
of latex Ch.em. Together
setting of the
Plastic
in latex Ratio of
Copolymers - PH value
of
latex Particle size \
in microns Temp. In ° C
after 3 sec.
in UHF
oven ί ⁹ Pliolite latex
151 Styrene butadiene
Copolymer 85:15 io, 3 0.1-0.15 70 ! 10 Styrofan 2 D Poly-styrene (100) 8 -11 0.1 65 ! ii Mowilith D Polyvinyl
acetate (100) 3-5 1-3 100 I ¹²
ί Acronal l60 D '
. Acrylic acid ester
Copolymer! Sat 5-7 105

■ ⁺ ) Acvr

Acronal ΐβθ D is a ^ O ^ & ige- plasticizer and solvent-free aqueous dispersion of a Plastic based on an acrylic ester copolymer with a weakly anionic character. Manufacturer BASF, Ludwigshafen.

For the use of the objects according to the invention, which are initially produced in web form on conventional devices, fitting pieces are cut out or punched out and sharpened (that is, they are sharpened by the edges). These fittings are connected to the substrate to be stiffened, in shoemaking, for example, with the upper, in places, for example, sewn, or _o inserted in a pocket between the shaft materials of said composite material in a microwave oven is then introduced in front of the pinching or before the molding in Ultra-high frequency field now heats the stiffening material fitting piece in a few seconds, whereby the thermoplastics of the stiffening material soften or the adhesives on the surface become adhesive without the materials to be stiffened being heated up which is damaging to them. The fitting pieces can also be dielectrically heated by themselves and then deformed.

The UHF energy is supplied, for example, by a magnetron that operates at the officially approved frequency of 2 ^ 50 MIIz ^.

The stiffening materials according to the invention serve for stiffening, Support and permanent shape retention of preferably front and rear parts of shoes, for stiffening and shape retention of Headgear such as hats or caps or parts thereof or of Handbag goods.

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Claims (5)

Claims 1. Mouldable or shaped stiffening material, in particular Shoe cap material, consisting of at least one fiber material or insert and at least one thermoplastic Plastic with fillers that may be contained therein, Plasticizers, dyes, pigments and / or stabilizers against light, heat and / or mechanical influences, which optionally has a thermoplastic based adhesive line on one or both Has sides, characterized in that at least one active substance in quantities in the thermoplastic material of at least 3 parts by weight per 100 parts by weight of the plastics containing the active substances is. 2. stiffening material according to claim 1, characterized in that that the plastic contains carbon black as an active substance. 3. stiffening material according to claims 1 and 2, thereby • indicates that the plastic is one or more Russians with a relatively high internal surface area, eaten by BET, preferably highly structured carbon black, in finer, more uniform Distribution contains " H. Stiffening material according to claims 1 to 3> characterized in that it is present as a cut or punched fitting piece, optionally preformed. 5. Use of a Versteifungentof.fes according to one of claims 1 to h as a shoe cap material. 3.5.1972 PL / Gt-Pr 30985 0/005 3