JPH01501215A - Method of coating a fibrous fabric with at least one film and combinations of starting materials for said film and products of said method and uses thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Method for coating a fibrous fabric with at least one film and for the film Combinations of starting materials and products of the process and uses thereof This invention provides a method for achieving a predetermined thickness, which is to be achieved by the preamble of claim 1. , a method of coating a fibrous fabric with at least one film, and a method of coating a fibrous fabric with at least one film; The combination of starting materials as material for the film, as well as the manufacturing process and the production of the protective fabric. It concerns its use in construction.

Reliable fabrics for protection against toxic gases, especially inexpensive for shoes and overshoes products that are desired. Traditional rubberized cloth products offer protection against toxic gases and Brominated inbutylene-isoprene polymer, which is not suitable for Bromobutyl rubber is guaranteed to be free of pores and voids if the product coated with it is However, existing products do not offer such protection against toxic gases. This was not possible with the manufacturing method known from Colema. . The essential reason for this is that manufacturing coating materials containing bromobutyl rubber air and/or gas, especially during the various mixing steps required. This is because the gas bubbles are captured and encapsulated in the coating material. and bromobutyl This is because rubber is completely air or gas tight. Currently, rubber is not flame retardant or retardant. Fabric products that are flammable and resistant to toxic gases are recommended. However, Bromo Butyl rubber is not flame retardant, so to date this problem has only been solved with bromobutyl rubber. could not be resolved by using .

Therefore, an object of the present invention is to satisfy such requirements for such fibrous fabrics. According to the present invention, this problem is solved as specified in claim 1. It is solved by the method indicated. As a material for carrying out this method, suitable Advantageous processes using starting materials of Described in Section 3. Further inventive features make the corresponding product a dependent patent claim. claim 14 or 15, while dependent claim 16 or claim 17 relates to the use of the product, and claim 18 of the method relates to the use of the product. A preferred optimum of the product manufactured by the method according to claim 16 or 17. It provides final processing.

The present invention will be explained below with the aid of figures. The figures show an outline of an apparatus for carrying out the present invention. and the ratio of roller to coating is as follows to better explain the invention: The true size is different.

For example, the fabric to be coated on the - side is coated with roller 2 (hereinafter referred to as The woven fabric 1 is passed around a back pressure roller 2). At arrows 4 and 5 As shown, the back pressure 0 - roller 2 is rotated as shown by arrow 3 in order to move the woven fabric 1. Turn around. The woven fabric 1 may be uncoated or coated with one or more films. In the latter case, each time the covering film is It is applied on top of 1.

The rubber-based covering material 6 is rotated relative to each other as shown by arrows 9 and 10. One example of charging between the applicator roller 7 and the distribution roller 8 For example, coatings based on unvulcanized bromobutyl rubber, the composition of which is given below. It is also possible to use This coating material 6 contains air bubbles 11 .

This was introduced during the manufacturing process, as will be described later.

The coating material 6 received between the distribution roller 8 and the applicator roller 7 is , of the applicator roller 7 as a coating 12 of a predetermined thickness between the rollers. The applicator roller 7 and the back pressure roller are moved in the direction of the woven fabric 1. In this way, the coating 12 also passes through the applicator. - Covering film for the woven fabric 1 that comes between the roller 7 and the back pressure roller 2 Transferred as 13.

In the final state, the coated film 13 is also exposed to a poison-resistant gas (not shown). and forms a flame-retardant film.

In order to ensure adequate pressure for the transfer of the coating 12 onto the fabric 1, the applicator - The gap S between the roller 7 and the back pressure roller 2 is larger than the thickness of the woven fabric 1 and the coating 12. It is made smaller so that the coating 12 introduced into the gap S is squeezed. In other words, The coating film 13 is thinner than the coating 12, and this pressure causes the coating film 13 to become thinner than the coating 12. To ensure proper adhesion to the fabric 1, if the fabric 1 is uncoated, the covering material 6 is attached to the fabric. 1 can also penetrate to some extent.

When feeding the coating 12, just upstream of the applicator roller 7, a back pressure roller A protrusion of the covering material 6 is formed on the upper side of the woven fabric 1 relative to the woven fabric 2 . This protrusion is covered with When the cover 12 is squeezed, the air bubbles are pushed back and collect in the protrusion as shown at 11. Ru. When carrying out the method, the rotational speed of each roller is supplied as a coating 12 The coating material f16 is the same as the amount of coating material leaving as each coating film 13. It is clear that this should be regulated accordingly.

If the gap S between the applicator roller 7 and the back pressure roller 2 is From covering material 6 based on mobutyl rubber, relatively thick film (approximately 1 cm or more) Yes, such as those commonly used for overshoes and protective clothing) in one step. Experience has shown that this thick film is The lum was found to contain no air bubbles.

If we consider the cross section of such a thick film and compare it with coating material 6. and near the top and bottom of the outer surface of this thick film, the number of air bubbles There is a decrease, but there are still bubbles close to the center. This phenomenon occurs in porous materials. Effects known when compressing (foams, sand, ceramics to be sintered) can be compared with. In all these cases, the applied pressure is the pressure surface ( (top and bottom) to a limited depth of the material, and the center of the material is There will be little or no pressure effect.

If the coating film is very thin and the applicator roller 7 and back pressure roller 2 The pressure caused by If there is overlap between the It has been found that the inclusion of air bubbles 11 can be avoided. Therefore, the applicator roller The gap S between 7 and the backpressure roller 2 is made very thin. desired final thickness Regardless, the covering film 13 is made relatively thin. Thereby, the covering flap Even air bubbles near the center of the film can be removed from the bulge 14 to the outside, as shown at 15. and burst into the atmosphere over time. Typically, the thickness of the covering film The diameter is 0.7ww, preferably 0.3■.

This is contrary to the traditional method of increasing the sealing effect by increasing the thickness. In addition, in the present invention, the sealing effect is increased by reducing the thickness of the film. It is.

In order to simultaneously vulcanize the coating film, a distribution roller 8 and an applicator are used. The roller 7 can also be heated, so that the coating material 6 is at approximately the same or higher temperature. The back pressure roller 2 is preheated and kept at a temperature slightly higher than room temperature.

Alternatively, after applying the covering film, the covering fabric may be processed in a known manner. Heat may be applied to vulcanize the coated film.

According to this, it is obvious that it is not possible to obtain a film of the planned thickness. The thickness of the covering film cannot be adjusted in any way beyond a certain value. It is the body. So the whole film is formed from several individual films. i.e. one or more coatings are applied until a film of desired thickness is obtained. As a result, thicker films are produced.

To obtain the desired flame retardancy, the material must be further coated, or if coated more than once. In the above case, the final coating material is flame retardant, preferably flame retardant rubber. used. This chemical composition will be explained later.

To carry out the method of the invention, pure cotton, e.g. g/+” plain weave can be used.

It is also possible to coat textiles obtained from other natural or synthetic materials.

To carry out the method of the invention, preferably the flame retardant film is a toxic gas resistant film. In a more preferred method, a toxic gas resistant film is bonded to the film. Bromobutyl rubber (brominated isobutylene-isoprene polymer) and In some methods, the flame retardant film is bonded by a suitable adhesive method. In this case, the block This process also involves a solvent solution of lomobutyl rubber being bonded to a toxic gas resistant film. The solvent is preferably a hydrocarbon in which the bromobutyl rubber is easily dissolved, e.g. In the range 80-110℃ = SBP speed with DIN standard 51630-51636 There is Lit U etc.

Preferred materials for the first or m-side covering film for carrying out the invention are: At least 40% by weight of bromobutyl rubber (brominated inbutylene-isoprene) at least 10% by weight of silicon dioxide, at least 10% by weight of sodium aluminum-aluminum silicate, and at least activated carbon, zinc dioxide, sulfur Contains additives, vulcanization accelerators, antioxidants, plasticizers and fillers.

As a rule, the same coating material is used for the next and subsequent coatings. Alright may also use natural rubber depending on the desired or required functionality of the final product. . That is, one or more bromobutyl rubbers are covered with one or more natural rubbers. It can also be overcoated, the process usually using known coating materials in a known manner. be able to.

Preferred flame retardant coating film materials for use in the practice of this invention include natural rubber, Select from polybutadiene rubber, styrene-butadiene rubber, and mixtures thereof. At least 10% by weight of exposed rubber and less sodium-aluminum silicate. at least 20% by weight, as well as activated zinc dioxide, magnesium oxide, ammonium trioxide Timon, zinc borate, coumaron-indene resin, vulcanization accelerator, antioxidant, para Contains finwax, plasticizers and fillers.

Examples of preferred toxic gas resistant coating materials that may be used include bromobutyl rubber. 0% by weight or more, 18% by weight or more as precipitated pure silicic acid with a particle size of 15-20 μl. Silicon dioxide above, as precipitated hydrate with a particle size of 20-50 μl, not less than 18% by weight of sodium-aluminum silicate, approximately 3.7% by weight polybutyl as a plasticizer. Tenpolymer, about 2.5% activated carbon as active filler and about 2.5% by weight % active zinc, about 0.7% by weight of pentaerythritol ester as resin, About 0.5% by weight of stearic acid as a lubricant and about 0.7% by weight as a vulcanization retarder. Mercaptobenzothiazole sulfide, about 0.2% by weight as a vulcanization accelerator Morpholine disulfide, about 0.2% by weight dipentamethylene as sulfur supply agent thiuram hexasulfide, and about 0.5% by weight of porium as an antioxidant. Contains Litrimethyldihydroquinoline.

Vulcanization can occur in the absence of sulfur if a sulfur supply agent is added.

To use this coating material composition, mix each component in a Banbury mixer at 60-100% Mix for approximately 10 minutes at 05°C and then apply this coating material to the desired use. The distribution roller 8 and the applicator roller 7 are heated to a temperature of about 100 to 125, for example. ℃, while the back pressure roller 2 is maintained at 30-40℃.

When mixing the components of this coating material, air or gas will inevitably be mixed and small It is dispersed in the form of bubbles. Apart from the influence of other impurities that may be present, In conventional products, the impermeability of the cover to gases, especially toxic gases, is impaired by , these bubbles.

In a first example of a flame retardant film that is preferably used, chloroprene rubber 33 At least 15% by weight of sodium chloride as kaolinite with a particle size of 2 μm Luminium silicate, particle size 20-50μ as true precipitated hydrate, not less than 7% by weight Sodium-aluminum silicate, approximately 8% by weight natural rubber, approximately 5% by weight polysilicate. ribtagene rubber, about 4% by weight antimony trioxide as flame retardant, about 3% by weight Styrene-butadiene rubber, approximately 3% by weight of tricresyl phosphatide as a nonflammable plasticizer approximately 2% by weight of active zinc oxide as an active filler, approximately 2% as a plasticizer % coumaron-indene resin, approximately 2% by weight magnesium oxide as chlorine acceptor. about 1% by weight of 1-methyl-cyclohexyl xylenol as an antiaging agent. derivative and about 1% by weight of 2,2-methylene-bis(4-methyl-6-tert - butylphenol), about 1% by weight zinc salts of organic fatty acids as a mixed additive, light Approximately 1% by weight of paraffin wax as a stabilizer and approximately 1% by weight of sulfur as a vulcanizing agent. , about 0.5% by weight mercaptobenzothiazole, about 0.3% by weight mercapto Benzothiazole sulfide, about 0.3% by weight of thiuramo as a vulcanization accelerator Contains nosulfide and about 0.3% by weight of di-)luidine-guanidine A second example used for flame retardant films containing 33% or more by weight of chloropropyl Rengum, containing more than 19% by weight of sodium chloride as 2 μl of kaolinite in terms of particle size. Luminium silicate, 6% by weight or more of sodium chloride as 11-fold precipitated hydrate Luminium silicate, approximately 5% by weight antimony trioxide as flame retardant, non-flammable Approximately 3% by weight of tricresyl phosphate as plasticizer, approximately 3% by weight as chlorine acceptor % magnesium oxide, approximately 3% by weight zinc borate as a flame retardant, and active filler. about 2% by weight of active zinc oxide, about 2% by weight of coumaron-indene as a plasticizer. 1-methyl-cyclohexyl of xylenol at about 1% by weight as a resin and anti-aging agent. about 1% by weight of 2,2-methylene-bis-(4-methyl-6'-t ert-butylphenol), approximately 1% by weight organic acid zinc salt as a mixed additive, light Approximately 1% by weight of paraffin wax as a stabilizer and approximately 1% by weight of sulfur as a vulcanizing agent. , about 0.5% by weight of mercaptobenzothiazole, about 0.3% by weight of mercapto Benzothiazole sulfide, about 0.3% by weight of thiuramo as a vulcanization accelerator containing nosulfide and about 0.3% by weight of di-o-toluidineanidine. Ru.

Films of the invention can have two coatings.

The first or textile side coating is 0.6-0.7 mi thick and the second or outer coating is 0.6-0.7 mi thick. The side coating is 0.4 to 0.3 wa thick.

As an example, when using cotton plain weave with a weight per unit area of 250 g/x2 For example, a coated fabric with a thickness of 1.10 to 1.20 yz can be obtained. Ta. For the sole of the shoe, make it thicker or add an extra outer layer, e.g. , 5 to 2.51 fields are used.

The manufacture of the desired product, e.g. shoes, is carried out after applying a flame-retardant outer coating, and the product is Finally, for example at 135-14Q"C for about 1 hour, optionally under gas pressure and and/or vulcanization by heating under pressure of several atmospheres (several bars).

This so-called final vulcanization allows the rubber-based adhesives used in some cases to become rubber layer, while the solvent used is one that does not penetrate the outer layer by diffusion. are dispersed throughout the film.

The coating was carried out to form two layers of coating film on the coating fabric to a thickness of 1.151 Jl. If a covering material is used, this fabric can be made of iberite or lewisite at 8 o'clock at 37°C. I didn't let it pass for more than a moment.

Agony international search report CH8700128 SA 18751

Claims (1)

[Claims] 1. A preheated, unvulcanized coating material (6) is applied to at least one side of the fibrous fabric (1). , the coating material is applied to the applicator roller (7) and the distribution roller ( 8), is taken up by the applicator roller (7), and the applicator The fabric (1) is guided between the tar roller (7) and the back pressure roller (2). fibrous fabric immediately upstream of the applicator roller (7) The fibrous fabric is coated with a film of desired thickness, on which a bulge (14) of coating material is formed. In the coating method, the first coating film is applied to the fibrous fabric (1) as a first phase. a second coating film is applied to the fibrous fabric (1) in a second phase, the coating The films together form the overall covering film (13), with the desired film Regardless of the thickness of the applicator roller (7) and the back pressure roller (2) The gap (S) between is covered by the applicator roller (7) and the back pressure roller (2). The pressure exerted on the covering film passes from the surface of the film through the center of the film. It is adjusted so that it meets near the center and sometimes overlaps, and A covering film containing gas bubbles applied onto the more fibrous fabric (1) The coating film is compressed between the licator roller (7) and the back pressure roller (2) and A gas bubble (11) sealed near the center of the chamber is substantially pushed into the bulge (14). A method characterized in that it is returned and optionally released to atmospheric pressure. 2. at least one toxic gas resistant film in the first phase and in the second phase At least one flame retardant film is applied to the fibrous fabric (1), the film being Claim 1 characterized in that the entire film (13) is The method described in section. 3. To form the multilayer coating material 6, several toxic gas resistant films and A flame retardant film is applied to the fibrous fabric (1) and together the entire film (13) A method according to claims 1 and 2, characterized in that forming. 4. Each coating film is then vulcanized to form a fibrous fabric (1). Claim 2, characterized in that they are irreleasably bonded to form a multilayer coating. The method described in Sections and 3. 5. Each element (toxic gas resistant film and flame retardant coating film) is peeled off. Claims 2 and 3, characterized in that they are irreversibly joined together. Method described. 6. Bromobutyl rubber (brominated isobutylene- Isobrene polymer)-based materials are used, and flame-retardant coating films are mainly used. It is applied as a solvent solution of bromobutyl rubber, and it can be bonded or vulcanized to create a toxic-resistant rubber. Claims 2 to 5 characterized in that: The method described above. 7. The fibrous fabric (1) is pure cotton fiber, for example, the weight per unit area is about 250 g/ Patent claim, characterized in that it consists of a plain weave of m2 or of natural or synthetic material The method according to any one of items 1 to 6. 8. Output for each toxic gas resistant coating film and flame retardant coating film. a) the toxic gas-resistant coating material is at least 40% by weight; % of bromobutyl rubber (brominated isobutylene-isoarene polymer), at least 10% by weight of silicon dioxide, at least 10% by weight of sodium-aluminum Silicates, as well as at least activated carbon, activated zinc oxide, sulfur supply agent, vulcanization accelerator b) the flame retardant coating material contains a small amount of At least 30% by weight of chloroprene rubber, natural rubber, polybutadiene rubber, styrene at least one selected from the group consisting of N-bukjie gum and mixtures thereof. 0% by weight rubber, at least 20% by weight sodium-aluminum silicate Hydrate, as well as active zinc oxide, magnesium oxide, antimony trioxide, boric acid Zinc, coumarose bean resin, vulcanization accelerator, antioxidant, paraffin wax Claim 2, characterized in that it contains a plasticizer and a filler. to the method described in any of paragraphs 6 to 6. 9. a) 50% by weight or more of bromobutyl rubber as a toxic gas-resistant coating material; 18 wt. of silicon dioxide as precipitated pure silicic acid with a particle size of 15-20 um %that's all, Sodium-aluminum as a precipitated hydrate with a particle size of 20-50 um 18% by weight or more of silicate, about 3.7% by weight of polybutene polymer, about 2.5% by weight of polybutene polymer; weight% activated carbon, about 2.5% by weight of active zinc oxide, Approximately 0.7% by weight pentaerythritol ester, approximately 0.7% by weight Mercato benzothiazole sulfide, approximately 0.5% by weight stearic acid, About 0.5% by weight polytrimethyldihydroquinoline, about 0.2% by weight morpholin about 0.2% by weight of dipentamethylenethiuram hexasulfide id is used, as well as b) As a flame retardant coating material, 33% by weight or more of chloroprene rubber, As kaolinite with a particle size of approximately 2um, sodium-aluminum containing 15% by weight or more Musilicate, More than 7% by weight of sodium-alcohol as a precipitated hydrate with a particle size of 20-50 um. Minium silicate, approximately 8% by weight natural rubber, Approximately 5% by weight polybutadiene rubber, about 4% by weight antimony trioxide, Approximately 3% by weight styrene-butadiene rubber, approximately 3% by weight tricresyl phosphate , about 2% by weight of active zinc oxide, Approximately 2% by weight of coumarose bean resin, approximately 2% by weight of magnesium oxide, about 2% by weight zinc borate, about 1% by weight of the 1-methyl-cyclohexyl derivative of xylenol; About 1% by weight of 2,2-methylene-bis(4-methyl-6-tert-butylphenylene) Nord), Approximately 1% by weight of organic acid zinc salt, Approximately 1% by weight paraffin wax, Approximately 1% sulfur by weight, about 0.5% by weight mercaptobenzothiazole, about 0.3% by weight mercaptobe ndzothiazole sulfide, approx. 0.3% by weight thiuram monosulfide, approx. 0.3% by weight of di-O-toluidineanidine is used. , the method according to claim 8. 10. a) 50% by weight or more of bromobutyl rubber as a toxic gas-resistant coating material; 18 wt. of silicon dioxide as precipitated pure silicic acid with a particle size of 15-20 um %that's all, Sodium-aluminum as a precipitated hydrate with a particle size of 20-50 um 18% by weight or more of silicate, about 3.7% by weight of polybutene polymer, about 2.5% by weight of polybutene polymer; weight% activated carbon, about 2.5% by weight of active zinc oxide, Approximately 0.7% by weight pentaerythritol ester, approximately 0.7% by weight Mercato benzothiazole sulfide, approximately 0.5% by weight stearic acid, About 0.5% by weight polytrimethyldihydroquinoline, about 0.2% by weight morpholin about 0.2% by weight of dipentamethylenethiuram hexasulfide id is used, as well as b) As a flame retardant coating material, 33% by weight or more of chloroarene rubber, As kaolinite with a particle size of approximately 2um, sodium-aluminum containing 19% by weight or more Musilicate, More than 11% by weight of styrene-Bukudier rubber, precipitated hydrate with particle size 20-50um As a substance, at least 6% by weight of sodium-aluminum silicate, about 5% by weight of antimony trioxide, about 3% by weight tricresyl phosphate, about 3% by weight magnesium oxide, about 3% by weight zinc borate, Approximately 2% by weight of active zinc oxide, Approximately 2% by weight coumarose bean resin, approximately 1% by weight 1-methyl of xylenol - cyclohexyl derivative, About 1% by weight of 2,2-methylene-bis(4-methyl-6-tert-butylphenylene) Nord), Approximately 1% by weight of organic acid zinc salt, Approximately 1% by weight paraffin wax, Approximately 1% sulfur by weight, about 0.5% by weight mercaptobenzothiazole, about 0.3% by weight mercaptobe ndzothiazole sulfide, approx. 0.3% by weight thiuram monosulfide, approx. characterized in that 0.3% by weight of di-o-toluidineanidine is used. , the method according to claim 8. 11. The starting material of characteristic a) as a toxic gas-resistant coating material is defined in claim 7. Characteristic b as a flame-retardant coating material according to any one of Items 8 and 9. ) is defined in any one of claims 7, 8 or 9. 9. A method according to claim 8, characterized in that it is used by. 12. Each coating material (6) undergoes a coating step in which the temperature is increased to approximately 60-120°C. Claims 1 to 3 are characterized in that the mixture is mixed for about 10 minutes prior to The method described in any of items up to 11. 13. At each coating stage, rollers 2, 7 and 8 are heated and distributed The roller (8) and applicator roller (7) are maintained at approximately 100-125°C. and the back pressure roller (2) is maintained at about 30-40°C, A method according to any one of claims 1 to 12. 14. Coated textiles, in particular by the method according to claim 1 or claim 7. An article characterized in that it is a coated cotton fabric in the form of a cotton fabric (1) produced by 15. A coated fabric, in particular produced by the method according to claim 11. An article characterized in that it is a coated cotton fabric in the form of a coated cotton fabric (1). 16. textiles to produce textile products with protection against toxic gases and flame retardancy. Claim 14 or Claim 14, characterized in that a textile fabric (1) is used. Use of articles manufactured by the method described in Section 15. 17. Manufactures shoes, boots, pants, and other products that protect against toxic gases and are flame retardant. Claim 1, characterized in that the fiber fabric (1) is used for producing Use of an article manufactured by the method described in paragraph 14 or paragraph 15. 18. Cloth products, especially boots, shoes, pants, etc., are further processed after they are actually manufactured. , additionally vulcanized by heating to about 135-140°C for about 1 hour under pressure. Produced by the method according to claim 16 or 17, characterized in that Use of manufactured goods.