WO2023224586A1 - Textile materials with high adhesion value - Google Patents

Textile materials with high adhesion value Download PDF

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Publication number
WO2023224586A1
WO2023224586A1 PCT/TR2023/050401 TR2023050401W WO2023224586A1 WO 2023224586 A1 WO2023224586 A1 WO 2023224586A1 TR 2023050401 W TR2023050401 W TR 2023050401W WO 2023224586 A1 WO2023224586 A1 WO 2023224586A1
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WIPO (PCT)
Prior art keywords
textile material
material according
resins
resin
formaldehyde
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Application number
PCT/TR2023/050401
Other languages
French (fr)
Inventor
Ezgi TAMAN ONEN
Mustafa Yasin Sen
Yucel Ayyildiz
Original Assignee
Kordsa Teknik Tekstil A.S.
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Publication date
Priority claimed from TR2022/007932 external-priority patent/TR2022007932A1/en
Application filed by Kordsa Teknik Tekstil A.S. filed Critical Kordsa Teknik Tekstil A.S.
Publication of WO2023224586A1 publication Critical patent/WO2023224586A1/en

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/55—Epoxy resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/693—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural or synthetic rubber, or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N3/042—Acrylic polymers

Definitions

  • the present invention relates to technical textile materials with high adhesion value, a novel environment-friendly adhesive dipping solution, which has been developed to obtain these textile materials, and an optimized production method.
  • the present invention relates to an environment-friendly adhesive dipping solution which provides high adhesion and to technical textile materials with a high adhesion value, and to production method of these textile materials.
  • the textile materials of the present invention can be used as reinforcement materials in rubber-containing products such as tires, belts, and pipes.
  • the textile material with high raw adhesion can be used in certain layers of the tire, such as the belt, carcass, sidewall, and bead area.
  • the said textile material may be cord fabric, which is obtained by weaving twisted raw yarns and used as reinforcement material by bonding with special adhesive mixtures in various parts of the tire, and which is a complex and composite product consisting of one or several layers.
  • Resorcinol formaldehyde latex is commonly used to ensure adhesion between textile materials and rubber-containing products.
  • the textile material is coated with RFL by being dipped in an RFL dipping, thereby increasing the adhesion of the textile materials to each other and to the rubber product.
  • the commonly used RFL dipping is obtained by dissolving resorcinol in water and adding formaldehyde and alkaline component (e.g., sodium hydroxide or ammonia), thereby obtaining an aqueous solution of the resin, which is slowly added to the latex with thorough stirring and preferably left to rest and mature for 24 hours.
  • formaldehyde and alkaline component e.g., sodium hydroxide or ammonia
  • US 8,651,157 discloses compositions and methods for improving the adhesion of textile materials.
  • the said textile material is coated with RFL as first layer, and is coated with resorcinol-formaldehyde, rosin ester, and unvulcanized rubber as the second layer.
  • RFL resorcinol-formaldehyde
  • rosin ester resorcinol-formaldehyde
  • unvulcanized rubber unvulcanized rubber
  • toluene/hydrocarbon solvents, xylene, ethyl acetate, alcohols, ethers, and mixtures thereof are used as solvents.
  • Table 1 shows the fusing and raw adhesion values of cord fabrics coated with RFL as the first layer, RFL and adhesive resin as the second layer known in the prior art.
  • Fusing refers to the mechanical adhesion between the textile material and the tire and raw adhesion refers to the mechanical adhesion between the textile materials.
  • the targeted fusing and raw adhesion values are taken as 100 and the adhesion values obtained are given as percentages. As can be seen from the table, while the fusing was higher than the desired value, the raw adhesion performance was well below the target performance. Although process changes were made between trials, the raw adhesion values were low.
  • raw adhesion refers to the adhesion value of textile materials to each other.
  • Textiles used as reinforcement materials in rubber-containing products may comprise more than one layer of textile material. Therefore, the adhesion of these textile materials to each other is as important as the adhesion to the rubber material. For example, the high level of raw adhesion prevents damage such as possible tears, especially in the bead area of the tire.
  • the objective of the invention is to obtain textile materials with high raw adhesion value by using environment-friendly chemicals (RF-Free) that do not contain resorcinol and formaldehyde chemicals, which are known to be harmful to human health and the environment.
  • RF-Free environment-friendly chemicals
  • the present invention provides a composition for adhering textile materials and the rubber-containing materials to each other.
  • the textile materials coated with this composition can be used in certain layers of the tire such as the belt, carcass, sidewall, and bead area.
  • a novel production process is developed. By finishing the textile material with this dipping solution, the raw adhesion value is increased.
  • the textile materials of the present invention may be woven, non-woven or knitted fabrics.
  • the said textile materials may comprise synthetic yarns, natural yarns, or the mixtures thereof.
  • the said textile material is a cord fabric.
  • the said cord fabric is composed of a textured fiber.
  • the said cord fabric is a leno weave fabric. The use of textured fiber increases the raw adhesion value and leno weave prevents the cords from extending out of the strip edges in strip cutting.
  • the textile material of the present invention, which is finished to have a high raw adhesion value comprises the following:
  • the textile material of the present invention is obtained with the following steps:
  • a textile material with high raw adhesion which is obtained with the above- mentioned method steps, can be used in the belt, carcass, sidewall, and bead area layers of the tire.
  • the said RF-Free formulation comprises water, ammonium hydroxide, polymer containing carboxylic acid functional groups, polyisocyanate, latex and epoxy.
  • This RF-Free formulation contains 0.1-2 % acrylic polymer resin (polymer containing carboxylic acid functional groups), 0.1-2% epoxy, 0.7-3% polyisocyanate, 6-21% latex by weight and in the remaining amount ammonium hydroxide as pH regulator (used to adjust the pH value to 5-11) and water.
  • the latex is a vinyl pyridine (VP) latex and/or styrene -butadiene (SBR) latex, with a solids content of 40-45 wt.%. Table 2 shows the wt.% content values of this formulation.
  • the polymer containing carboxylic acid functional groups comprises monomers containing 70-100% mol, preferably 90- 100% mol carboxylic acid groups. In a particularly preferred embodiment of the invention, the polymer containing carboxylic acid functional groups comprises a carboxylic acid monomer in an amount of 100% mol, without disregarding the different functional groups.
  • a functional acrylic resin (polymer) material containing carboxylic acid is first added to water.
  • the resin containing carboxylic acid at least one of the monomers such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, cinnamic acid, maleic acid is used.
  • the functional acrylic resin (polymer) consists of monomers containing 70-100% mol, and particularly 90-100% mol carboxylic acid groups.
  • the epoxy is added into the composition.
  • the epoxy used is water- soluble or water-based dispersion.
  • At least one of the materials such as glycidyl- based glycerol, sorbitol epoxy, phenol novolac epoxy, crezol novolac epoxy is used as epoxy.
  • the main use is not limited to these. Any water soluble or dispersible epoxy can be used within the scope of the present invention.
  • the coating material composition does not comprise an epoxy component, the adhesion between the composition and the fiber cords is reduced.
  • the polyisocyanate is water-based and comprises blocked, for example caprolactam blocked, isocyanate groups that are thermally decomposed blocked isocyanate groups.
  • the polyisocyanate is a water-based polyurethane prepolymer comprising caprolactam blocked 4,4'- methylene diphenyl diisocyanate or blocked isocyanate groups. In the absence of blocked isocyanate, the adhesion performance of the coating solution decreases.
  • latex Following the addition of polyisocyanate, latex is added.
  • the latex used comprises butadiene, styrene and preferably vinyl pyridine monomers. This is either VP latex with ratios of 15% styrene, 70% butadiene and 15% vinyl pyridine monomers or SBR latex with ratios of 25% styrene and 75% butadiene monomers.
  • the amount of solids in the latex is in the range of 40-45 wt.%.
  • the second coating composition used for forming the second coating layer comprises at least one adhesive resin, at least one unvulcanized rubber and at least one adhesion improving agent.
  • the said adhesive resin is selected from phenol-containing resins (which may be a resin selected from a group consisting of phenol formaldehyde resin, resorcinol formaldehyde condensate, condensate of phenol derivatives with aldehydes and acetylene, terpene phenolic resins, p-tert-octylphenol (PTOP) formaldehyde resins, and the mixtures thereof at different ratios), aromatic resins, hydrocarbon resins, terpene resins, indene resins, coumarone resins, resin-based resins, and mixtures thereof at different ratios.
  • phenol-containing resins which may be a resin selected from a group consisting of phenol formaldehyde resin, resorcinol formaldehyde condensate, condensate of phenol derivatives with aldehydes and acetylene, terpene phenolic resins, p-tert-octylphenol
  • the said unvulcanized rubber is selected from polybutadiene, polyisoprene, synthetic trans-rich polyisoprene, cis-rich polyisoprene, natural rubber, poly(styrene-co-butadiene), poly(acrylonitrile-co-butadiene), chloroprene, hydrogenated styrene-butadiene rubber, hydrogenated nitrile-butadiene rubber, butyl rubber (polyisobutylene copolymers), halo-butyl rubber, and mixtures thereof at different ratios.
  • the said adhesion improving agent is selected from formaldehyde -resorcinol condensate, formaldehyde-resorcinol resin, formaldehyde-phenol condensate, novolac resins, resol resins, multi-functional epoxy resin, novolac modified epoxy resin, isocyanate compounds, blocked isocyanate resin, blocked isocyanate compounds, halogenated resorcinol-formaldehyde resin, phenolic resins, halogenated phenolic resins, melamine-formaldehyde resins, vinylpyridine rubber latex, methylene donors such as hexamethylenetetramine and hexamethoxymethylamine, organofunctional silanes, and mixtures thereof at different ratios.
  • the organic solvent in which the second adhesive coating (finishing) composition is dissolved is selected from toluene/hydrocarbon solvents, xylene, ethyl acetate, alcohols, ethers, and mixtures thereof at different ratios.
  • a textile material with high raw adhesion value which is a final product having two coating layers, is cut into strips to be used in various layers of the tire, such as the belt, carcass, sidewall, and bead area.
  • the textile materials were subjected to the first coating solution (RFL or RF-free), they were placed in ovens set at 130- 235°C, preferably 160-235°C, and then dipped in the second dipping solution (RFL) and subjected to a temperature of 100-150°C.
  • RTL first coating solution
  • Table 3 raw adhesion values which are similar in both cases and considerably lower than the target value were obtained.
  • the target adhesion value is set as 100 and the raw adhesion value is given as a percentage of the target value.
  • leno weave cord fabric comprising textured fiber was used.
  • any textile material can be used.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The present invention relates to an environment-friendly adhesive dipping solution which provides high adhesion and to technical textile materials with a high adhesion value, and to a production method of these textile materials. The said textile materials are coated with a first coating composition free of resorcinol formaldehyde (RF-Free) and dried, then the textile materials are coated with a second adhesive composition dissolved in an organic solvent. Thus, textile materials with high raw adhesion value are obtained. The said textile materials with high raw adhesion value can be used in layers of tires, such as the belt, carcass, sidewall, and bead area.

Description

TEXTILE MATERIALS WITH HIGH ADHESION VALUE
Field of the Invention
The present invention relates to technical textile materials with high adhesion value, a novel environment-friendly adhesive dipping solution, which has been developed to obtain these textile materials, and an optimized production method.
Background of the Invention
The present invention relates to an environment-friendly adhesive dipping solution which provides high adhesion and to technical textile materials with a high adhesion value, and to production method of these textile materials. The textile materials of the present invention can be used as reinforcement materials in rubber-containing products such as tires, belts, and pipes. The textile material with high raw adhesion can be used in certain layers of the tire, such as the belt, carcass, sidewall, and bead area. For example, the said textile material may be cord fabric, which is obtained by weaving twisted raw yarns and used as reinforcement material by bonding with special adhesive mixtures in various parts of the tire, and which is a complex and composite product consisting of one or several layers.
Resorcinol formaldehyde latex (RFL) is commonly used to ensure adhesion between textile materials and rubber-containing products. The textile material is coated with RFL by being dipped in an RFL dipping, thereby increasing the adhesion of the textile materials to each other and to the rubber product. The commonly used RFL dipping is obtained by dissolving resorcinol in water and adding formaldehyde and alkaline component (e.g., sodium hydroxide or ammonia), thereby obtaining an aqueous solution of the resin, which is slowly added to the latex with thorough stirring and preferably left to rest and mature for 24 hours. For example, US 8,651,157 discloses compositions and methods for improving the adhesion of textile materials. The said textile material is coated with RFL as first layer, and is coated with resorcinol-formaldehyde, rosin ester, and unvulcanized rubber as the second layer. In the second layer, toluene/hydrocarbon solvents, xylene, ethyl acetate, alcohols, ethers, and mixtures thereof are used as solvents.
However, since resorcinol and formaldehyde components are harmful to the environment, there is a need to develop coatings that do not contain such components. Besides, the targeted adhesion values cannot be obtained with RFL coating. Table 1 shows the fusing and raw adhesion values of cord fabrics coated with RFL as the first layer, RFL and adhesive resin as the second layer known in the prior art. Fusing refers to the mechanical adhesion between the textile material and the tire and raw adhesion refers to the mechanical adhesion between the textile materials. In this table, the targeted fusing and raw adhesion values are taken as 100 and the adhesion values obtained are given as percentages. As can be seen from the table, while the fusing was higher than the desired value, the raw adhesion performance was well below the target performance. Although process changes were made between trials, the raw adhesion values were low.
Table 1 Physical properties of cord fabrics coated with RFL as the first layer, and RFL and adhesive resin as the second layer.
Figure imgf000003_0001
Therefore, there is a need to develop textile materials which are free of environmentally harmful components such as resorcinol and formaldehyde, and have improved raw adhesion values compared to the state of the art. As described above, raw adhesion refers to the adhesion value of textile materials to each other. Textiles used as reinforcement materials in rubber-containing products may comprise more than one layer of textile material. Therefore, the adhesion of these textile materials to each other is as important as the adhesion to the rubber material. For example, the high level of raw adhesion prevents damage such as possible tears, especially in the bead area of the tire.
Objectives of the Invention
The objective of the invention is to obtain textile materials with high raw adhesion value by using environment-friendly chemicals (RF-Free) that do not contain resorcinol and formaldehyde chemicals, which are known to be harmful to human health and the environment.
Detailed Description of the Invention
The present invention provides a composition for adhering textile materials and the rubber-containing materials to each other. The textile materials coated with this composition can be used in certain layers of the tire such as the belt, carcass, sidewall, and bead area. Within the scope of invention, in addition to a dipping composition, a novel production process is developed. By finishing the textile material with this dipping solution, the raw adhesion value is increased.
The textile materials of the present invention may be woven, non-woven or knitted fabrics. The said textile materials may comprise synthetic yarns, natural yarns, or the mixtures thereof. In a preferred embodiment of the invention, the said textile material is a cord fabric. In a more preferred embodiment of the invention, the said cord fabric is composed of a textured fiber. In a more preferred embodiment of the invention, the said cord fabric is a leno weave fabric. The use of textured fiber increases the raw adhesion value and leno weave prevents the cords from extending out of the strip edges in strip cutting. The textile material of the present invention, which is finished to have a high raw adhesion value, comprises the following:
- a textile material,
- a first coating material free of resorcinol formaldehyde (RF-Free) on at least one surface of the textile material, and
- an adhesive composition which is dissolved in an organic solvent as a second finishing coating applied on the first coating material.
The textile material of the present invention is obtained with the following steps:
- obtaining a textile material,
- dipping the textile material in a resorcinol formaldehyde-free (RF-Free) dipping solution to form the first coating layer,
- drying the textile material which was dipped in RF-Free dipping solution at a temperature of 130-235°C, preferably 160-235°C,
- dipping the dried textile material in a second coating solution composition dissolved in organic solvent to form a second coating layer, and
- drying the second coating layer (Cement coating) at a temperature of 100- 150°C.
A textile material with high raw adhesion, which is obtained with the above- mentioned method steps, can be used in the belt, carcass, sidewall, and bead area layers of the tire.
In one embodiment of the invention, the said RF-Free formulation comprises water, ammonium hydroxide, polymer containing carboxylic acid functional groups, polyisocyanate, latex and epoxy. This RF-Free formulation contains 0.1-2 % acrylic polymer resin (polymer containing carboxylic acid functional groups), 0.1-2% epoxy, 0.7-3% polyisocyanate, 6-21% latex by weight and in the remaining amount ammonium hydroxide as pH regulator (used to adjust the pH value to 5-11) and water. Here the latex is a vinyl pyridine (VP) latex and/or styrene -butadiene (SBR) latex, with a solids content of 40-45 wt.%. Table 2 shows the wt.% content values of this formulation.
Table 2 RF-Free dipping recipe
Figure imgf000006_0001
* The % value given refers to the purity value. For example, 41% of VP latex is
VP latex and the remaining 59% is water.
In one embodiment of the invention, the polymer containing carboxylic acid functional groups comprises monomers containing 70-100% mol, preferably 90- 100% mol carboxylic acid groups. In a particularly preferred embodiment of the invention, the polymer containing carboxylic acid functional groups comprises a carboxylic acid monomer in an amount of 100% mol, without disregarding the different functional groups.
Within the scope of the invention, in the production of coating material for textile materials, a functional acrylic resin (polymer) material containing carboxylic acid is first added to water. For the resin containing carboxylic acid, at least one of the monomers such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, cinnamic acid, maleic acid is used. In the preferred embodiment of the invention, the functional acrylic resin (polymer) consists of monomers containing 70-100% mol, and particularly 90-100% mol carboxylic acid groups. After the pH value is adjusted to the desired level, the epoxy is added into the composition. In a preferred embodiment of the invention, the epoxy used is water- soluble or water-based dispersion. At least one of the materials such as glycidyl- based glycerol, sorbitol epoxy, phenol novolac epoxy, crezol novolac epoxy is used as epoxy. However, the main use is not limited to these. Any water soluble or dispersible epoxy can be used within the scope of the present invention. When the coating material composition does not comprise an epoxy component, the adhesion between the composition and the fiber cords is reduced.
Polyisocyanate is then added to the composition. In a preferred embodiment of the invention, the polyisocyanate is water-based and comprises blocked, for example caprolactam blocked, isocyanate groups that are thermally decomposed blocked isocyanate groups. At least one of the tetramethylene diisocyanate, hexamethylene diisocyanate ( 1 ,6-diisocyanatohexane), diphenylmethane4,4’ -diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, aromatic diisocyanates containing 2,4- or 2,6-tolylene diisocyanate, tetramethylxylene diisocyanate, p-xylene diisocyanate, 2,4’- or 4-4’- diisocyanatediphenylmethane, 1,3- or 1,4-phenylene diisocyanate is used as polyisocyanate. In a preferred embodiment of the invention, the polyisocyanate is a water-based polyurethane prepolymer comprising caprolactam blocked 4,4'- methylene diphenyl diisocyanate or blocked isocyanate groups. In the absence of blocked isocyanate, the adhesion performance of the coating solution decreases.
Following the addition of polyisocyanate, latex is added. The latex used comprises butadiene, styrene and preferably vinyl pyridine monomers. This is either VP latex with ratios of 15% styrene, 70% butadiene and 15% vinyl pyridine monomers or SBR latex with ratios of 25% styrene and 75% butadiene monomers. The amount of solids in the latex is in the range of 40-45 wt.%.
Within the scope of the invention, the second coating composition used for forming the second coating layer comprises at least one adhesive resin, at least one unvulcanized rubber and at least one adhesion improving agent. Of these main components:
The said adhesive resin is selected from phenol-containing resins (which may be a resin selected from a group consisting of phenol formaldehyde resin, resorcinol formaldehyde condensate, condensate of phenol derivatives with aldehydes and acetylene, terpene phenolic resins, p-tert-octylphenol (PTOP) formaldehyde resins, and the mixtures thereof at different ratios), aromatic resins, hydrocarbon resins, terpene resins, indene resins, coumarone resins, resin-based resins, and mixtures thereof at different ratios.
The said unvulcanized rubber is selected from polybutadiene, polyisoprene, synthetic trans-rich polyisoprene, cis-rich polyisoprene, natural rubber, poly(styrene-co-butadiene), poly(acrylonitrile-co-butadiene), chloroprene, hydrogenated styrene-butadiene rubber, hydrogenated nitrile-butadiene rubber, butyl rubber (polyisobutylene copolymers), halo-butyl rubber, and mixtures thereof at different ratios.
The said adhesion improving agent is selected from formaldehyde -resorcinol condensate, formaldehyde-resorcinol resin, formaldehyde-phenol condensate, novolac resins, resol resins, multi-functional epoxy resin, novolac modified epoxy resin, isocyanate compounds, blocked isocyanate resin, blocked isocyanate compounds, halogenated resorcinol-formaldehyde resin, phenolic resins, halogenated phenolic resins, melamine-formaldehyde resins, vinylpyridine rubber latex, methylene donors such as hexamethylenetetramine and hexamethoxymethylamine, organofunctional silanes, and mixtures thereof at different ratios.
In a preferred embodiment of the invention, the organic solvent in which the second adhesive coating (finishing) composition is dissolved is selected from toluene/hydrocarbon solvents, xylene, ethyl acetate, alcohols, ethers, and mixtures thereof at different ratios. In one embodiment of the invention, a textile material with high raw adhesion value, which is a final product having two coating layers, is cut into strips to be used in various layers of the tire, such as the belt, carcass, sidewall, and bead area.
Two different trials were conducted to compare the state of the art with the use of the first coating material of the present invention. In Trial 1, the newly developed “resorcinol and formaldehyde-free” formulation (RF-free) was used as the first coating solution and RFL solution containing a rosin ester-based adhesive resin was used as the second coating solution. In Trial 2, standard RFL was used as the first coating solution and RFL solution containing a rosin ester based adhesive resin was again used as the second coating solution. After the textile materials were subjected to the first coating solution (RFL or RF-free), they were placed in ovens set at 130- 235°C, preferably 160-235°C, and then dipped in the second dipping solution (RFL) and subjected to a temperature of 100-150°C. As shown in Table 3, raw adhesion values which are similar in both cases and considerably lower than the target value were obtained. In Table 3, the target adhesion value is set as 100 and the raw adhesion value is given as a percentage of the target value.
Table 3 Comparison of RF-Free composition with the state of the art
Figure imgf000009_0001
In the next study, trials were carried out to compare the effect of the second coating with the state of the art. RFL and RF-Free coated textile materials produced at operating scale were coated with rubber pulp which was also produced at operating scale. In other words, the fabrics the first coatings of which were RFL and RF-Free were coated with rubber pulp as the second coating by a method known in the art as cementing. In cementing, after the rubber pulp is dissolved in a suitable organic solvent, the textile material is coated with this solution and in the next step, the solvent is evaporated by placing the textile material in ovens at a certain temperature.
In Trial 3, standard RFL was used as the first coating solution and rubber pulp (cement) dissolved in organic solvent was used as the second coating solution. In Trial 4, the newly developed "resorcinol and formaldehyde-free" formulation (RF- Free) was used as the first coating solution and rubber pulp (cement) dissolved in organic solvent was used as the second coating solution. As can be seen in Table 4, as a result of this study, it has been observed that the textile material first coating of which is RF-Free showed much better performance than the textile material, which is used in the state of the art and first coating of which is RFL. In two different raw adhesion methods, the textile material containing RF-Free formulation showed approximately 40-60% higher results. In Table 4, the target adhesion value was set as 100 and the raw adhesion value was given as a percentage of the target value.
Table 4 Comparison of RF-Free composition with cemented coatings known state of the art
Figure imgf000010_0001
In the said trials, leno weave cord fabric comprising textured fiber was used. However, the person skilled in the art will appreciate that any textile material can be used.

Claims

CLAIMS A coated textile material, characterized in that it comprises:
- a textile material,
- a first coating composition free of resorcinol formaldehyde (RF-Free), which is applied on at least one surface of the said textile material, and
- a second adhesive composition, which is dissolved in organic solvent applied on the said first coating composition. A coated textile material according to claim 1, characterized in that the said first coating composition free of resorcinol formaldehyde (RF-Free) comprises acrylic polymer resin, epoxy, polyisocyanate, latex, ammonium hydroxide, and water. A coated textile material according to claim 2, characterized in that the said acrylic polymer resin is polymer resin comprising carboxylic acid functional groups. A coated textile material according to claim 3, characterized in that the said acrylic polymer resin is a polymer resin consisting of monomers containing 70- 100% mol carboxylic acid functional groups. A coated textile material according to claim 3 or 4, characterized in that the said monomers containing carboxylic acid functional groups are selected from acrylic acid, metacrylic acid, itaconic acid, crotonic acid, cinnamic acid, maleic acid, and the mixtures thereof at different ratios. A coated textile material according to any one of the preceding claims, characterized in that the said epoxy is in the form of a water-soluble epoxy or water-based dispersion. A coated textile material according to claim 6, characterized in that the said epoxy is selected from glycidyl-based glycerol, sorbitol epoxy, phenol novolac epoxy, crezol novolac epoxy, and the mixtures thereof at different ratios. A coated textile material according to any one of the preceding claims, characterized in that water-based polyisocyanate which has thermally decomposed blocked isocyanate groups is used as the said polyisocyanate. A coated textile material according to claim 8, characterized in that the said polyisocyanate is selected from tetramethylene diisocyanate, hexamethylene diisocyanate ( 1 ,6-diisocyanatohexane), diphenylmethane4,4’ -diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, aromatic diisocyanates containing 2,4- or 2,6-tolylene diisocyanate, tetramethylxylene diisocyanate, p-xylene diisocyanate, 2,4’- or 4- 4 ’-diisocyanatediphenylmethane, 1,3- or 1,4-phenylene diisocyanate and the mixtures thereof at different ratios. A coated textile material according to any one of the preceding claims, characterized in that the said latex is vinyl pyridine (VP) latex and/or styrenebutadiene (SBR) latex. A coated textile material according to any one of the preceding claims, characterized in that the first coating composition free of resorcinol formaldehyde (RF-Free) comprises 0.1-2 % acrylic polymer resin, 0.1-2% epoxy, 0.7-3% polyisocyanate, 6-21% latex by weight, ammonium hydroxide in an amount to adjust the pH value between 5-11, and water in the remaining amount. A coated textile material according to any one of the preceding claims, characterized in that the said second adhesive composition comprises at least one adhesive resin, at least one unvulcanized rubber, and at least one adhesion improving agent. A coated textile material according to claim 12, characterized in that the said adhesive resin is selected from phenol-containing resins (which may be a resin selected from a group consisting of phenol formaldehyde resin, resorcinol formaldehyde condensate, condensate of phenol derivatives with aldehydes and acetylene, terpene phenolic resins, p-tert-octylphenol (PTOP) formaldehyde resins, and the mixtures thereof at different ratios), aromatic resins, hydrocarbon resins, terpene resins, indene resins, coumarone resins, resin-based resins, and the mixtures thereof at different ratios. A coated textile material according to claim 12, characterized in that the said unvulcanized rubber is selected from polybutadiene, polyisoprene, synthetic trans-rich polyisoprene, cis-rich polyisoprene, natural rubber, poly(styrene-co- butadiene), poly(acrylonitrile-co-butadiene), chloroprene, hydrogenated styrene-butadiene rubber, hydrogenated nitrile-butadiene rubber, butyl rubber (polyisobutylene copolymers), halo-butyl rubber, and the mixtures thereof at different ratios. A coated textile material according to claim 12, characterized in that the said adhesion improving agent is selected from formaldehyde-resorcinol condensate, formaldehyde-resorcinol resin, formaldehyde-phenol condensate, novolac resins, resol resins, multi-functional epoxy resin, novolac modified epoxy resin, isocyanate compounds, blocked isocyanate resin, blocked isocyanate compounds, halogenated resorcinol-formaldehyde resin, phenolic resins, halogenated phenolic resins, melamine-formaldehyde resins, vinylpyridine rubber latex, methylene donors such as hexamethylenetetramine and hexamethoxymethylamine, organofunctional silanes, and the mixtures thereof at different ratios. A coated textile material according to any one of the preceding claims, characterized in that the said organic solvent is selected from toluene/hydrocarbon solvents, xylene, ethyl acetate, alcohols, ethers, and the mixtures thereof at different ratios. A method of producing a coated textile material according to any one of claims
1 to 16, characterized in that it comprises the following steps: - obtaining a textile material,
- dipping the textile material in a resorcinol formaldehyde-free (RF-Free) solution of the first coating composition,
- drying the textile material which is dipped in RF-Free solution at a temperature of 160-235 °C, - dipping the dried textile material in a second solution of adhesive composition dissolved in organic solvent, and
- drying the second coating layer at a temperature of 100-150°C.
PCT/TR2023/050401 2022-05-16 2023-04-28 Textile materials with high adhesion value WO2023224586A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014091376A1 (en) * 2012-12-13 2014-06-19 Kordsa Global Endustriyel Iplik Ve Kord Bezi Sanayi Ve Ticaret Anonim Sirketi A dipping material for cord fabrics and a production method thereof
EP3258008A1 (en) * 2016-06-14 2017-12-20 Continental Reifen Deutschland GmbH Method for producing a reinforcing support, reinforcing support and vehicle tyre
EP3992357A1 (en) * 2019-07-03 2022-05-04 Beijing University of Chemical Technology Composition for surface treatment of fibers and fiber treatment method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014091376A1 (en) * 2012-12-13 2014-06-19 Kordsa Global Endustriyel Iplik Ve Kord Bezi Sanayi Ve Ticaret Anonim Sirketi A dipping material for cord fabrics and a production method thereof
EP3258008A1 (en) * 2016-06-14 2017-12-20 Continental Reifen Deutschland GmbH Method for producing a reinforcing support, reinforcing support and vehicle tyre
EP3992357A1 (en) * 2019-07-03 2022-05-04 Beijing University of Chemical Technology Composition for surface treatment of fibers and fiber treatment method

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