DE1959010A1 - Process for reinforcing textile clothing with thermosetting films - Google Patents

Description

Priority ι of November 27, 1968 under serial no. 779 606 and of March 7, 1969 under serial no. 805 359 in USA

The invention relates to an improved textile garment and a method of reinforcing the clothing fabric to improve wear properties or abrasion resistance and / or to improve the tear resistance. Great importance has been attached to this in the past few years been, the wear properties of textile clothing to improve. Recently, wrinkle-resistant fabrics that keep their ironed state permanently have also been Found entry in the market and find a rising one

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Interest. Process and resins to achieve a lasting Crinkle resistance, for example according to the USA patents 2,974-432 and 3,268,195 (coratron fabric) are effective and provide durable, ironed, wrinkle-proof clothing that yiele Withstands ablutions, but the resins seibat and die. heat treatments required for their full hardening often the fiber structure in a harmful way by weakening the fibers and thereby the abrasion resistance of the finished clothing. This is especially true of the clothing spots that repeated Are exposed to tensile stress, such as on the knees and elbows «

Numerous attempts have been made in the past been used to improve the abrasion resistance and tear resistance of the Textile fabric by treating it with resin material. In many cases, however, are the earlier Treatments have been unsatisfactory for one reason or another. Laminated resin films that just passed through Hot press adhered to the surface of the fabric, lift off slightly after the garment Has been subjected to cleaning operations. The binding strength of the resins on the fiber surface is / unable to withstand repeated forces, how they apply to the garment during the washing process is exercised · Often also have laminated films

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a unique dioke and stiffness that the clothing is uncomfortable and uneasy to wear.

When more heat and pressure are applied for dl · laning will cause the resin to melt and flow through the Intermediate spaces in the textile fabric for the purpose of more complete To bring encapsulation of the fibers, the resin becomes Visible in the piece of clothing, especially when it is only in isolated districts, ζ. B. at the knees of one Pair of pants is applied. As a result, the

•• the garment. When, furthermore, the spaces between the hair are filled, the cladding fabric becomes largely non-porous, which improves moisture removal or respiration and the passage of heat duroh the tissue so significantly affected that the Clothing becomes a nuisance for the wearer.

Many plastics are both thermoplastic how thermosetting on tissue, be it general, be g ·· to strengthen certain districts. In the prior art, however, the same difficulties have arisen so far, because the substances are usually obtained from a solution or an emulsion, e.g. B. at Coating the fiber or fabric with a resinous substance applied by spraying, washing or dipping will. Substances applied in this way seep through the entire tissue and its interstices. That

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Fabric is significantly stiffened and the plating is visible, which affects the appearance of the garment, especially if the plastic applied to isolated areas of the garment exposed to heavy use, such as the knee and elbow areas.

U.S. Patent 3,394,405 describes a method of reinforcing pieces of textile clothing using thermoplastic reinforcing films. In this process, a thermoplastic film is initially only lightly brewed to adhere to the inner surface of a pair of trousers in the areas to be reinforced. The patent teaches that the thermoplastic Piim be only weakly adhered in the first stage or partially mufl, that is, under application of heat and pressure between about 175 and 230 ⁰ C (350 and 45O ⁰ P) and 1.4 to 7.0 kg / cm ² (20 to 100 pounds / square inch) for 4 to 15 seconds. The patent also warns that too much heat and / or pressure can cause the thermoplastic film to melt and seep through the face of the fabric or the paser surface Temperature range from about 135 to 230 ⁰ C (275 to 450 ⁰ P) about 20 minutes long baked in order firstly to polymerize the non-iron-rendering resins that were previously in the

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Tissues have been padded out of an aqueous solution,

•. . .---. ■■■ ...... ■ -. "■■. ■ ■

and secondly, the thermoplastic film for the flowing Soften and fully adhere to the fibers to bring them through their extensive sheathing on the surfaces lying on the inside of the garment.

It has now been found to be that of a preformed thermosetting film as a reinforcement member, provided that the film has controllable flow characteristics and g is applied under appropriate heat and pressure conditions, the binding and adhesion made completely when used in just one stage or zumndeat largely completed without that one has to fear leakage of the film or other appearance of an unsatisfactory product. Of course, although it is not mandatory, the baking step can be desirable, especially in the case of non-iron fabrics, and in addition the baking step causes the thermosetting film to harden or vulcanize, which in the present case I

is needed. If & a bakeout stage is used, then the thermosetting reinforcing film can be used alone be connected and cured in one step.

Preferably, the thermosetting film consists of one relatively soft self-crosslinking and thermosetting Acrylic acid film supplied in roll form on a release paper coated with polyethylene and silicone will. The film price fluctuates between about 0.025 and

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0.25 mm and is preferably 0.05 to O _y 125 mm. Thermosetting films useful for the purposes of the invention are preferably colorless and clear, soft and pliable, and are intended to provide a surface that is durable to washing and / or dry cleaning and also provides a soft feel to the finished and reinforced fabric. If the film is delivered on release paper, as I said, it is usually much longer than the area of the garment to be reinforced, and the release paper with the PiIm is therefore first cut into plaster sizes. The patch is then placed on the area of the pants or other garment to be reinforced, and the thermosetting film is then transferred from the release paper to the area to be reinforced and bonded thereto with the application of heat and pressure. Various combinations of heat and pressure can be applied to a thermosetting film of the invention to achieve good bonding and cure. The temperatures, pressures, and heating margins for the bond will vary somewhat depending on the weight and type of fabric or garment and the dye used in it. One can use binding conditions, the temperatures from about 93 to 190 ⁰ C, preferably temperatures in the range of / about 135 to 180 ⁰ C (about 275 to 350 ⁰ F), time periods of about 3 to 35 seconds, preferably 7 to 10 seconds and Pressures from about 0.35 to 7.0 kg / cm ² (about 5 to 100 pounds / square inch), preferably about 0.35 to 0.05 kg / cm

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(about 5 tola 15 pounds / square nominal) include “Be 1st acu note that the binding temperatures are considerably lower are, as they are naoh dem.Stand der Technik e.B. after United States patent letter 3 394 405 may be applied. As a result -.lit in those used according to the invention heat-refractory films run the risk of their deterioration Dye and constriction of the tissue much smaller.

The thermosetting films which can be used in accordance with the invention are made from thermosetting materials B-stage «i.e. they are insoluble and insoluble, however In non-resistable and insoluble C-stage using suitable heat and pressure conditions as indicated above, convertible.

The terms "B-stage" and "C-stage" are used here in their recognized technical sense (compare sB Goldi & g, Polymers and Resins, pages 24-6 and 247, B. Van No strand Oo · Inc.). The thermosetting films according to the invention are further characterized by having a T ₁ (transition temperature of the 2nd order, see I. Williamson, British Plastlos 23, 87 to 90, 102 (1950)) and in a minute or less at 163 ^{Cure 0} C to the fully hardened state. The in the invention be-Torsugten thermosetting materials harden in 10 to 20 seconds at about 163 ⁰ C (325 ⁰ F) | if the temperature is reduced in stages, hardening takes place in stages

increasing periods of time. Suitable thermosetting film materials are, in addition to the already mentioned acrylic acid-reactive polymers based thereon of styrene and thus polymerizable monomers in a mixture, the attached reactive substituents, such as carboxy, sulfo, amino groups, etc. Such polymers are mentioned in US Pat. No. 3,215,647. According to this publication, the Reactive polymers also react with reactive substances that contain methylol groups or modified MethylQlgruppen, which with an alcohol from 1 to Carbon atoms, etc. have been alkylated. Examples such coreactive substances are melamine, melamine-formaldehyde condensates, guanidine, dicyandiamide, etc.

As mentioned earlier, a thermosetting resin containing some acrylic acid functions is preferred. Quite particularly preferred is a preformed thermosetting film in the B-stage which comprises a) certain linear additive copolymers having N-methylolamide and amide groups Amount ratios combined with optionally b) an aminoplast as defined below and optionally c) a catalyst such as ammonium thiocyanate or Contains maleic acid as a hardening catalyst, maleic acid is to be combined here in compounds, which deliver maleic acid under the conditions of use, like maleic anhydride.

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- j -

The linear addition copolymers which are used in the composition according to -the invention are water-insoluble copolymers that are obtained by Emulaionamiaohpolymerisation · the mixture of a) from about 1 to 20 wt -. $> Acrylamide or methacrylamide or formaldehyde reaction products of such an amide including Äthylol - And methoxymethyl derivatives with b) at least one monomer consisting of acrylonitrile, styrene, α-methylstyrene, vinyl toluene, vinyl acetate and esters of the formula

COOR

· In this formula, η is an integer of 1 or 2 and R represents an alkyl group having 1 to 18 carbon atoms. Examples of such esters are ethyl methacrylate, butyl methaorylate, methyl aylate, ethyl acrylate, butyl aylate, t-oatyl aorylate and methacrylate and octadecyl aorylate and methacrylate. The monomers are selected so DAFL the copolymers have an apparent transition temperature T ₁ has a secondary order, which not übfrr 20 ⁰ O lies. If monomers such as acrylonitrile, methyl methacrylate and styrene, which produce homopolymers with Tj values, are used, their proportion in the mixed polymer is limited to those which are used with other monomers when used in the relevant mixed polymer such as itylaorylate / methyl aorylate © or acetyl acrylate.

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Methacrylate give a T ₁ -WePt of 20 ⁰ O or less · The molecular weight can be about 100,000 to 10,000,000.

When the imide component part of the mixed polymer consists of a Mixture of 1. either acrylamide or methacrylamide with 2. H-methylolacrylamide or N-methylol methacrylamide exists, the two substances to be used should preferably be in a molar ratio of 1 to 1, although this is not the case is essential. If the amide is used per se, it is preferably composed of methacrylamide. But when a combination of amide and N-methylolamide is used, N-methylolacrylamide is preferably used. The preferred interpolymers are those containing a chemical of amide and N-methylolamide. Appropriate one uses 1 to 6 wt. 56 amide constituent in the Mixed polymer.

The method of making the emulsion blend polymer used in the invention is disclosed in U.S. Patent 3,035,811 to Braun et al and 3,157,365 by Kine et al.} Reference is expressly made to this information here. These linear addition copolymers are optionally combined with an aminoplast condensate. The ones for use with the linear Addition copolymers useful in the practice of the invention are aminoplasts which are water-soluble when heated convertible methylol derivatives of urea, ayclisoher

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Xthylenefcarnea, cyolieohes uron, cyolieoher propylenurea, ShIo- 'urea, cyclischen ethylenthio · -

• * ■

urea, melamine »alkylmelamines, arylmelamines, arylquinimines, ohinimines, alkylquinimines and their semis without. In other words, water-soluble resins can be produced by one of the following processes: 1. reaction under conditions controlled in such a way that the degree of polyaerization is kept low, even in the monomer level, and 2. introduction of hydrophilic groups into the molecules of the polymeric condensates. One can therefore wasaerl8sliol _»f-heat convertible amino resins, such as dimethylol urea and trimethylolamine prepared by careful control of reaction conditions as in Sohildknecht" Polymer Processes, "Band X, page 305 ff {Intersoienoe Press, 1956) is indicated. Such simple methylol derivatives often have limited solubility in cold water and are not particularly durable if left to stand for a long time, because they tend to polymerize in water-insoluble polymers.

One preferred class of water-soluble aminoplasts is from the condensates of formaldehyde and the reaction products clay urea and / or melamine with a lower Alcohol such as methanol. These condensates are converted into insoluble, crosslinked polymers in the pan. So are the condensates of methozymethylureas and formaldehyde and of methoxymethylmelamines and formaldehyde

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particularly suitable for films according to the invention. The preparation of ethylene urea derivatives such as N ₁ N ¹ bis (methoxymethyl) ethylene urea is given in detail in US Pat. No. 2,373,136. The preparation of methylolmethoxymelamine is found in the cited book by Schildkneoht on page 340. The preparation of methylolmethoxymelamines is given in US Pat. No. 2,529,856 and the values cited there are incorporated by reference. The preparation of another class of compounds which is suitable for the invention, such as Ν, Ν ¹ -bis- (methoxymethyl) -urea, can be found in Bull. Chen ». Soo. Japan, Volume VI, No. 3, 239 (1936).

In an optional embodiment of the invention, the preformed thermosetting reinforcing film is baked into or stacked on top of a non woven or filamentary product and the composite of film and nonwoven product becomes Reinforcement of the garment is used in a similar way as in the cited literature parts for describes the preformed thermosetting film per se. The burn-in in the non-woven fabric delivers a more fabric-like handle for the wearer of the garment in the areas where the reinforcement takes place, and apart from the reinforcement, there is also an increased load-bearing capacity due to the increased abrasion resistance.

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Bas non-woven product or the fibrous tape can in any suitable manner e.g. by carding, "(Jarnetting or by dry deposition of the pasers be formed from an air suspension. The thin one Strips or the fleece that is obtained from a single carding can optionally be coated with a binder be treated, but it is generally necessary or expedient to place several such strips on top of one another to create a mat of sufficient thickness for the intended end use. When building ^ j Such a mat can have alternating layers of carded strips with around 60 ° or 90 ° opposite Paser alignments offset from the intermediate layers are placed one on top of the other will.

The piping from which the strips or ribbons are made are made of cellulose fibers such as cotton, rayon, Burlap, ramie and linen. Cellulose esters such as cellulose acetate, silk, wool, casein and other protein-containing fibers, polyesters such as poly (ethylene glycol terephthalate), Polyamides such as nylon, vinyl resin fibers such as copolymers of vinyl chloride and vinyl acetate and acrylonitrile polymers at 70 to 95 wt .- ^ Acrylonitrile including those commercially available under the Orion and Aorilan brands. Any bonded nonwoven strips according to U.S. Patent 3,157,562 to Kine et al. can be used as

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Base used for the pre-formed thermosetting film and the assembly of it for reinforcement of garments according to the invention. The preferred thermosetting reinforcing film is between pressure rollers with or without application of heat prior to application of the composition as reinforcement for garments laminated with the non-woven strip. The total thickness of the preformed thermosetting film and nonwoven assembly Stripe ranges from about 0.075 to 0.50 mm (about 3 to 20 mils). In a typical example, a pre-formed thermosetting film 0.05 mm thick on a non-woven backing 0.125 mm thick. Rayon applied by making the film and the strip together through a pair of press rolls. The compilation is 0.15 mm thick.

The non-woven backing can also have predominantly cellulose character. A higher quality is preferred Wood pulp. Although each nonwoven paper backing uses different densities in the invention relatively light paper, such as toilet paper, Kleenex-type facial tissue paper, wiping cloth is preferably used in the manner of the trademark Kim-Wipe. These papers can be produced with or without the addition of wet strength resins. The thickness of the paper used in accordance with the invention

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soh usually varies between 0.025 and 0.375 mm. Of the Reinforcement film with non-woven paper backing is particularly useful for some lighter fabrics where shrinkage difficulties can occur. With others It has been observed that some textile backing reinforcement films exhibit differential shrinkage «Wipe film and reinforcing fabric occurs. This difference in shrinkage leads to wrinkling in the occupied area, which is disruptive from an aesthetic point of view The reinforcement film with non-woven paper under- * situation eliminates this particular difficulty.

To support the person skilled in the art in carrying out the invention, the following procedures are intended to serve: in which all parts and percentages have increased by weight, unless otherwise specifically stated.

BBI8PHL A

Bine aqueous dispersion of 46 i "of a solid Bmulsions- ■ leohpolymeree of about 85 t 9 1 · ethyl acrylate, 10 i * acrylonitrile, acrylamide and 1.7 * 2.4 + Methylolaorylamid is prepared by Bmulsionsmlschpolymerisation. 100 parts of this emulsion are mixed with 7.1 parts of a 70% aqueous solution of tris (methoxymethyl) melamine, 1.2 parts of ammonium hydroxide, 0.5 parts of a 25% strength aqueous ammonium thioyanate solution as a catalyst and

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18.75 parts of a 4- # aqueous solution of methyl cellulose with a viscosity of 4000 ops are added. The mixture is poured onto a substrate coated with polyethylene and silicone release paper using a force Streiohmessers and about 15 minutes at a temperature of about 66 to 82 ⁰ C (150 to 180 ⁰ P) into a preformed thermosetting reinforcing film

is dried from a thickness of 0.05 mm. The film / on the release paper rolled up and ready to be cut to the appropriate size for use in special reinforcement pads.

A sample of the thermosetting film on the release paper of the appropriate size is bonded to an area of cotton garment fabric intended for the manufacture of garments such as shirts or pants. The district is the one that is said to be subject to greater stress than other districts of the fabric. The thermosetting film and a period of 7 seconds has prevented · deliver these conditions in the cotton garment fabric under a pressure of 0.35 kg / cm (5 pounds / square inch), a temperature of 16O ⁰ C (F 320 ⁰⁾ excellent Bond between the reinforcement and the fabric fibers. The release paper is removed, and as & reinforced fabric for 10 minutes at about 150 ⁰ C (300 ⁰ F) The cured · β postcure causes only the curing of the films, drop-off ^ hn but not

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in addition, to flow. See the table below the surprising increase in abrasion resistance compared to cotton garment fabric without reinforcement and with the preformed thermosetting film on top of it *

TABLE A

Frequency of failure using a Wyzenbeok abrasive device, cloth rubbed against canvas.

Operations Cotton Garment Inspection 2000 (Hole, Formed) Reinforced cotton clothing fabric

with thermosetting film) 10,000 (some wear

recognizable. but no look)

From the table above it can be seen that the Abrasion resistance of the cotton clothing fabric by at least

is increased by a factor of 5. The film stays

also after several washes and dry cleanings i

undamaged.

Similar results are obtained with the ammonium thioeyanate. maintain a catalyst.

EXAMPLE B

Using the pre-formed thermosetting film of the

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Example A are the knee areas of a pair of pants made of 65 i> Dacron polyeater and 35 l * rayon, which has been pretreated with non-iron resins according to the information in the above-mentioned patents by Warnook, by binding the thermosetting film to the knee areas of the inside of the fabric Reinforced for 7 seconds at 16O ⁰ O (32O ⁰ P) and 0.35 kg / cm ² (5 pounds / square inch). The trousers were washed in a Maytag Waseher at 60 ⁰ C ⁽⁰ HO P) with Eide detergent. The appearance of the pants and the condition of the patch or thickened area without any post-treatment after 40 washes is excellent. Sin another pair of pants is post-cured for 10 minutes at 160 ⁰ C (320 ⁰ P), and the appearance of the pants and of the allocated area is the same after 40 washes as in the non naohgehärteten tissue. The pants withstood 2167 test cycles in a Stoll flexural abrasion test up to break, which means an increase of 42 # compared to the same pants without any reinforcement.

The preformed thermosetting resin can also be applied to other fabrics and garments and, if desired, at lower temperatures of e.g. B. 120 ° C (250 ° P), for example, on school and play pants made of 50 i * polyester and 50 i » cotton, with see similar improved results in abrasion resistance in the reinforced areas and good durability, ie preservation

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the good properties and the reinforcement effects show after numerous waaohings and / or dry cleanings.

EXAMPLE O

Bine wäaarige dispersion of 60 i> Feetetoff thylaorylat a Bmul atone mieohpolymere from about 85.9 # A ", 10 i» acrylonitrile, 1.7 i> i acrylamide and 2.4 »methylolacrylamide is prepared by Bmuleionemiechpolymerisation. 125 parts of this emulsion are 9.2 parts of a 70 # aqueous solution of penta- (methoxymethyl) melamine, one part of ammonium hydroxide and 18.75 parts of a 4 # aqueous solution of methyl cellulose with a viscosity of 4,000 cps are added poured onto coated with polyethylene and silicone force release paper and (190 ⁰ F 150) and dried to provide about 15 Hinuten at about 65 ° to 88 ° 0 to a preformed thermosetting Yeretärkungsfilm of about 0.05 mm thickness on the kraft paper. The combination of film and release paper is then coated onto a 0.125 mm thick rayon nonwoven fabric by running the combination and rayon nonwoven backing through nip rolls The nonwoven fabric and thermosetting film is then stripped from the release paper and applied to the garment or the area of fabric to be reinforced

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applied by placing the film surface dee Sohioht-βtoffee against the inner surface dee to be reinforced Area. The non-woven surface remains in a position where it is the leg or something else Touches the area of the wearer.

The nonwoven fabric and film laminate is used to reinforce the inner knee of a pair of Enaben game horns by placing them on them under 0.35 kg / cm (5 pounds / square inch) for 7 seconds. 160 ⁰ C (320 ⁰ F) ties up. They show increased abrasion resistance and also a pleasing fabric-like feel on the wearer's knee on very cold and hot, humid days. The load-bearing strength of the trousers in the reinforced areas is also improved by the laminate made of non-woven material and film compared to the reinforcement by the film alone.

EXAMPLE · D

An aqueous dispersion according to Example C is poured onto the polyethylene and silicone coated kraft release paper and dried for about 15 minutes at about 66 to 88 ⁰ C (150 to 19O ⁰ F) to form a preformed thermosetting reinforcement film about 0.05 am thick on the To give release paper. The combination of film and release paper is then made to a 0.075-0.10 am thick

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stacked nonwoven paper from the Peerless Paper Mill of Oaks, Pennsylvania. The paper has a base weight of 5.9 kg (13 pounds) (500 sheets by 610 914 mm or 24 inches 36 inches) with a unit weight of 0.0212 kg / m ² (0.039 pounds / square yard). The coating is carried out by letting the film-release paper combination and non-woven tissue paper go through pressure rollers which are operated at about 15 tons of pressure and a temperature in the range of about 24 to 132 ^° C. (75 to 270 ^° I ¹ ). The laminate made of non-woven. The fabric and thermosetting film is then stripped from the release paper and applied to the garment or fabric in the area to be reinforced by pressing the film surface of the laminate against the inside of the area to be reinforced. The surface of the nonwoven tissue paper is in a position that it touches the leg or other surface of the wearer. Garments reinforced with the combination of non-woven paper and film show increased abrasion resistance and also better aesthetic appearance. The patch does not show any wrinkling after 16 washes in a Maytag Wäseher operated (up to 160 ⁰ F about 140) with Tide detergent at a temperature of about 60 to 70 ⁰ C. As indicated in Example C, the tear resistance is also improved.

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Claims (14)

PAIENIiBSPROOHB Textile fabric characterized by a preformed reinforcing thermosetting film on one part its surface, which is exposed to greater stress than other areas or parts of the fabric. 2. Textile clothing atuck characterized by a pre-formed reinforcing thermosetting film on one Part of its surface that is subject to greater stress than other areas or parts of the garment. 3. textile garment piece according to claim 2, characterized in that the pre-formed thermosetting reinforcement film has a non-woven strip of fibrous material on it has a side that corresponds to the wearer of the Kleidungsτ Piece can come into direct contact. 4. Textile garment according to claim 3, characterized in that the non-woven fiber strip is made of rayon. 5. Garment according to claim 3, characterized in that the non-woven fibrous strip made of paper consists. 009823/1800 6. Garment according to claim 2, consisting of one Pair of hats with non-iron hairs and mino at least one in it · before curing the non-iron making Harie crease. 7. The method of Law gain a · Teitilkleidungeetüokee, characterized in that one Dafi on the hidden inner surface or inner fiber surface of a local area of the garment a preformed thermosetting or thermosetting Verstärkungefilm Λ sum adhesion and stapling brings by apply the thermosetting reinforcing film to the patch at a temperature in the range of about 93 to 190 * 0 (about 200 to 375 ⁰ F) under a pressure of about 0.35 to 7.0 kg / cm ² (about 5 to 100 pounds / square Inches) for a period of about 3 to 35 seconds. 8. The method according to claim 7, characterized by since the garment consists of a pair of trousers " and the local area to be strengthened to the Kneeling the pants is located. 9. The method according to claim 8, characterized in that the dal Bi detemperatur in Bereioh of about 135-177 * C (about 275 to 35O ⁰ F), the pressure in the range of about 0.35 to 1.05 kg / o * ² ( about 5 to 15 pounds / square 009823/1800 Inches and the length of time is in the range of about 7 to 10 seconds 10. The method according to claim 7, characterized in that that the garment is subjected to a post-curing. · 11. The method according to claim 7 »characterized in that φ that the thermosetting reinforcement film is not one has woven fiber stripes on one side, which comes into direct contact with the skin of the wearer of the garment. 12. The method according to claim 7, characterized in that the pre-formed thermosetting plastic reinforcement film. made of one modified with melamine self-crosslinking emulsion copolymer film. 13. The method according to claim 11, characterized in that that the non-woven fibrous strip consists of paper. 14. The method according to claim 11, characterized in that that the non-woven fiber strip is made of rayon. C09823 / 1800