Environmentally friendly impregnation system for fiber surface treatment, method for manufacturing the same, and impregnation treatment method.

Abstract

The present invention discloses an environmentally friendly impregnation system for fiber surface treatment, and its manufacturing method and impregnation method. The environmentally friendly impregnation system for fiber surface treatment of the present invention includes hydroxyacrylic resin, amino resin, epoxy resin, blocked isocyanate, accelerator, rubber latex, and deionized water. The present invention can be selectively adopted as a one-bath impregnation process or a two-bath impregnation process according to the type of fiber and the application. The present invention can effectively replace the use of toxic materials and intermediates in the conventional RFL dip, reducing the harm to human body and the environment, and can achieve the same adhesion effect as RFL.

Description

Technical Field

[0001] The present invention belongs to the field of fiber dipping treatment, and specifically relates to an environment-friendly impregnation system for fiber surface treatment, a method for producing the same and an impregnation treatment method, and is particularly applicable to rubber framework materials.

Background Art

[0002] Fiber cords and plies are widely used as reinforcing materials for rubber in products such as tires, hoses, and conveyor belts. The interfacial adhesion performance between fibers and a rubber matrix is extremely important for the reinforcing effect of fibers. Since 1935, the resorcinol-formaldehyde-latex (RFL) impregnation method has become the most effective method for improving the adhesion performance between fibers and rubber. However, both resorcinol and formaldehyde in the RFL system are toxic substances, which may cause serious toxicity to the human body and the environment. Resorcinol is prone to cause itching when it comes into contact with skin, and may also cause toxicity to the liver and cardiovascular system. Furthermore, formaldehyde poses greater harm to human health and safety than resorcinol, and is prone to induce leukemia. In 2004, it was recognized as a carcinogen by the International Agency for Research on Cancer (IARC) affiliated to the World Health Organization. Therefore, development of a novel environment-friendly fiber impregnation treatment system is urgently desired to replace the conventional RFL system.

[0003] Patents US 20150314644A 1 (WO2014091429A 1), US 2012041113A 1 (WO2010125992A 1), US 5565507A (WO9600749A 1), and CN 105839413A disclose environmentally friendly dipping solutions primarily composed of epoxy resin. US 2015314644A1 discloses an adhesive compound of rubber latex, epoxy compound, and polyamine with a molecular weight exceeding 190 daltons, where the viscosity generated between the fibrous backbone and rubber adhesive is similar to that of conventional RFL systems. US2012041113A1 discloses an impregnation solution comprising epoxy resin, amino curing agent, blocked isocyanate, and rubber latex for improving the adhesion between fibrous fabrics and rubber. US5565507A discloses an impregnation solution comprising a trifunctional or more epoxy resin and a latex containing carboxyl groups, amino groups, or pyridine groups. CN105839413A discloses an impregnation system comprising an epoxy resin, an amine-based curing agent, and a latex, the adhesive effect of which reached a level superior to RFL treatment.

[0004] Patents CN112176729A (WO2021000918A1), US2005147817A1, and US2005255773A1 disclose environmentally friendly dipping solutions primarily composed of maleic anhydride polymers. CN 112176729A discloses a dipping system comprising maleic anhydride polymer, epoxy resin, blocked isocyanate, curing agent, rubber latex, and optional filler components. Fibers treated with this dipping system exhibit excellent adhesive properties and can also achieve adhesive effects through RFL (Resistant Fiber Lamination). US 2005147817A1 discloses a dipping solution comprising semi-esterified maleic anhydride polybutadiene, carbon black, latex, etc., which can effectively enhance adhesion between fibers and ethylene propylene diene rubber. US 2005255773A 1 discloses an impregnation solution for improving the adhesion between fibers and rubber, comprising maleic anhydride polyolefin, maleimide resin, vinyl-based unsaturated carboxylate metal salt, and latex.

[0005] Patents US2015315410A1, US4472463A, and CN109097993A disclose environmentally friendly dipping solutions primarily composed of acrylic resin. US2015315410A1 discloses a dipping solution comprising a carboxyl group-containing acrylic resin, epoxy resin, blocked isocyanate, and latex, whose adhesive effect is slightly superior to that of RFL. The dipping solution described in US4472463A contains an acrylic monomer, a small amount of styrene copolymer, and latex, whose adhesive effect is slightly superior to that of the RFL dipping system. CN109097993A discloses an impregnation system comprising a self-crosslinking acrylic resin, blocked isocyanate, and rubber latex, which achieves good adhesion between rubber-dipped fabrics and rubber, achieving, or even exceeding, the impregnation effect of conventional RFL.

[0006] CN106120350A discloses an impregnation treatment system comprising tannic acid, polyamine, and latex, wherein the adhesive effect of polyester plies treated by this method is equivalent to that of RFL, and the adhesive effect at high temperatures is superior to that of RFL. CN 110284326A discloses an impregnation treatment system comprising a special amino resin (mainly benzoxazine resin), blocked isocyanate, auxiliary agents, and latex, wherein the adhesive effect of nylon fibers treated by this method can reach the level of treatment by RFL.

[0007] While conventional technologies have made some improvements to the adhesion performance between fibers and rubber, they still suffer from several problems: the adhesive strength of the supplied impregnation systems does not reach the level of RFL (Resorcinol-Fiber) impregnation; procurement costs are high due to the numerous requirements of some of the materials used in the formulation; and the processes are complex. Therefore, there is a need to develop a novel, environmentally friendly impregnation system for fiber surface treatment that can replace the RFL impregnation systems currently used industrially, significantly improve the adhesion performance between fibers and rubber, and avoid the use of toxic substances such as resorcinol and formaldehyde. [Overview of the project]

[0008] In the first aspect, the present invention relates to the part by weight [Table 1] We provide an environmentally friendly impregnation system for fiber surface treatment that contains the following component.

[0009] Preferably, the environmentally friendly impregnation system for fiber surface treatment provided by the present invention is, in parts by weight, [Table 2] It contains the following ingredient.

[0010] More preferably, the environmentally friendly impregnation system for fiber surface treatment provided by the present invention is, in parts by weight, [Table 3] It contains the following ingredient.

[0011] According to some embodiments of the present invention, the environmentally friendly impregnation system for fiber surface treatment is a one-bath impregnation solution comprising, by weight, 100 parts deionized water, 1 to 30 parts hydroxyacrylic resin, 0.1 to 10 parts amino resin, 1 to 10 parts blocked isocyanate, 0.1 to 5 parts accelerator, and 50 to 180 parts rubber latex. Preferably, the one-bath impregnation solution contains epoxy resin, comprising, by weight, 100 parts deionized water, 1 to 15 parts hydroxyacrylic resin, 0.1 to 8 parts amino resin, 1 to 10 parts epoxy resin, 1 to 10 parts blocked isocyanate, 0.1 to 4 parts accelerator, and 50 to 150 parts rubber latex.

[0012] According to some embodiments of the present invention, the environmentally friendly impregnation system for fiber surface treatment is 1) A first bath impregnation solution comprising parts by weight of epoxy resin 0.5 to 2.5 parts, blocked isocyanate 3 to 10 parts, and deionized water 90 to 110 parts, and 2) a second bath impregnation solution comprising parts by weight of hydroxyacrylic resin 5 to 15 parts, amino resin 0.5 to 3 parts, accelerator 1 to 5 parts, rubber latex 80 to 200 parts, and deionized water 90 to 110 parts. Preferably, the first bath impregnation liquid described in 1) has a content of 1-2 parts by weight of epoxy resin, 5-8 parts of blocked isocyanate, and 95-105 parts by weight of deionized water, and the second bath impregnation liquid described in 2) has a content of 7-10 parts by weight of hydroxyacrylic resin, 1-2.5 parts of amino resin, 1.5-3 parts of accelerator, 100-180 parts of rubber latex, and 95-105 parts by weight of deionized water.

[0013] According to some embodiments of the present invention, the hydroxyl group content of the hydroxyacrylic resin is 2.0 to 5.0 wt%.

[0014] According to some embodiments of the present invention, the (number average) molecular weight of the hydroxyacrylic resin is 8,000 to 15,000.

[0015] According to several embodiments of the present invention, the amino resin is soluble in water or a latex emulsion and is preferably at least one selected from the group consisting of urea aldehyde resin, melamine formaldehyde resin, polyamide polyamine epichlorohydrin resin, etherified urea resin, etherified glycol uryl resin, fully methyl etherified melamine resin, polymerized partially methyl etherified melamine resin, or polymerized high imino group methyl etherified melamine resin. Preferably, the (number average) molecular weight of the amino resin may be 100 to 800.

[0016] According to some embodiments of the present invention, the epoxy resin is soluble in water or a latex emulsion and is preferably at least one selected from the group consisting of bisphenol A type epoxy resin, epoxidized novolac resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,2-propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, glycerol glycidyl ether, trimethylolpropane glycidyl ether, tetraphenolethane tetraglycidyl ether epoxy resin, sorbitol glycidyl ether, resorcinol bisglycidyl ether type epoxy resin, and bisresorcinol formaldehyde tetraglycidyl ether.

[0017] According to some embodiments of the present invention, the blocking isocyanate comprises an isocyanate and a chelating agent, the isocyanate being at least one selected from the group consisting of trimethyl-1,6-hexamethylene diisocyanate, tetramethylene diisocyanate, tetramethyl diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, isophorone diisocyanate, and diphenylmethane diisocyanate, and the chelating agent being at least one selected from the group consisting of ε-caprolactam, butanone oxime, and phenol.

[0018] According to some embodiments of the present invention, the accelerator is at least one selected from the group consisting of amine-closed dinonylnaphthalene sulfonic acid, amine-closed dinonylnaphthalene sulfonic acid, amine-closed dodecylbenzenesulfonic acid, or amine-closed p-methylbenzenesulfonic acid.

[0019] According to some embodiments of the present invention, the rubber latex has a solid content of 20 to 60 wt% and is selected from, but is not limited to, at least one of the group consisting of butadiene-vinylpyridine rubber latex such as carboxybutadiene-vinylpyridine rubber latex, styrene-butadiene rubber latex such as carboxystyrene-butadiene rubber latex, butadiene-styrene-vinylpyridine rubber latex such as carboxynitrile latex, chloroprene latex, nitrile latex, or natural latex.

[0020] In the second aspect, the present invention also provides a method for manufacturing an environmentally friendly impregnation system for fiber surface treatment, wherein the method is In the case of a one-bath dipping solution system, hydroxyacrylic resin, amino resin, epoxy resin and accelerator as needed are sequentially added to deionized water and stirred, then blocked isocyanate is added and stirred, and finally rubber latex is added and stirred continuously to obtain a one-bath dipping solution. Among them, the dosage of each component in parts by weight is: 100 parts of deionized water, 1 to 30 parts of hydroxy acrylic resin, 0.1 to 10 parts of amino resin, 1 to 10 parts of blocked isocyanate, 0.1 to 5 parts of accelerator, and 50 to 180 parts of rubber latex, Alternatively, In the case of a two-bath dipping solution system, 1) adding an epoxy resin to deionized water and stirring, then adding blocked isocyanate and stirring to obtain a uniform reaction solution, thereby producing the first bath impregnation solution; 2) sequentially adding hydroxy acrylic resin, amino resin and accelerator to deionized water and stirring to obtain a uniform dispersion, finally adding rubber latex and continuing stirring to obtain the second bath impregnation solution, Among them, for the first bath impregnation solution, the dosage of each component in parts by weight is 1 to 2 parts of epoxy resin, 5 to 8 parts of blocked isocyanate, and 95 to 105 parts of deionized water; for the second bath impregnation solution, the dosage of each component in parts by weight is 7 to 10 parts of hydroxy acrylic resin, 1 to 2.5 parts of amino resin, 1.5 to 3 parts of accelerator, 100 to 180 parts of rubber latex, and 95 to 105 parts of deionized water. comprising the step of:

[0021] In a third aspect, the present invention provides (A) impregnating fibers by adding them into a one-bath dipping solution, (B) drying and curing the impregnated fibers obtained in step (A). comprising the step of an impregnation treatment method for fiber surface treatment characterized by: Here, the one-bath dipping solution comprises the following components in parts by weight: 100 parts of deionized water, 1 to 30 parts of hydroxy acrylic resin, 0.1 to 10 parts of amino resin, 1 to 10 parts of blocked isocyanate, 0.1 to 5 parts of accelerator, and 50 to 180 parts of rubber latex.

[0022] According to some embodiments of the present invention, in step (A), the temperature for said impregnation is 15 to 40°C, and the time is 1 to 5 min.

[0023] According to some embodiments of the present invention, in step (B), the temperature at which the drying is carried out is 110 to 160°C, and the time is 1 to 10 minutes.

[0024] According to some embodiments of the present invention, in step (B), the curing temperature is 180-250°C and the curing time is 1-10 min.

[0025] According to some embodiments of the present invention, in step (A), the pH of the dipping solution is adjusted to be alkaline before impregnation. In some embodiments, the pH of the dipping solution is adjusted to be alkaline, preferably pH 8.0 to 11.0, with an alkaline solution such as potassium hydroxide solution or aqueous ammonia solution.

[0026] In the fourth aspect, the present invention is i) A first bath impregnation solution in which the fibers are impregnated with a first bath impregnation solution in which the amounts of each component are 0.5 to 2.5 parts by weight of epoxy resin, 3 to 10 parts by weight of blocked isocyanate, and 90 to 110 parts by weight of deionized water. After drying the fibers processed in step i), step ii) hardens them. Step iii) involves impregnating the fibers treated in step ii) into a second bath impregnation solution, the second bath impregnation solution having the following components in parts by weight: 5-15 parts hydroxyacrylic resin, 0.5-3 parts amino resin, 1-5 parts accelerator, 80-200 parts rubber latex, and 90-110 parts deionized water. Step iv) involves drying and hardening the fibers processed in step iii). The present invention provides an impregnation treatment method for fiber surface treatment, characterized by including the following step.

[0027] According to some embodiments of the present invention, in step i), the temperature for impregnation is 15 to 40°C and the time is 1 to 5 minutes.

[0028] According to some embodiments of the present invention, in step ii), the temperature at which the drying is carried out is 110 to 160°C and the time is 1 to 10 minutes.

[0029] According to some embodiments of the present invention, in step ii), the temperature at which the curing is carried out is 180 to 250°C, and the time is 1 to 10 minutes.

[0030] According to some embodiments of the present invention, in step iii), the temperature for impregnation is 15 to 40°C and the time is 1 to 5 minutes.

[0031] According to some embodiments of the present invention, in step iv), the temperature at which the drying is carried out is 110 to 160°C and the time is 1 to 10 minutes.

[0032] According to some embodiments of the present invention, in step iv), the temperature at which the curing is carried out is 180 to 260°C, and the time is 1 to 10 minutes.

[0033] According to some embodiments of the present invention, in step iii), the pH of the second bath impregnation solution is adjusted to be alkaline before impregnation. In some embodiments, the pH of the impregnation solution is adjusted to be alkaline with an alkaline solution, such as a sodium hydroxide solution or an aqueous ammonia solution, preferably to a pH of 8.0 to 11.0.

[0034] According to the processing method of the present invention, the deionized water, hydroxyacrylic resin, amino resin, epoxy resin, blocked isocyanate, accelerator, and rubber latex are the same as described above and therefore will not be explained again here.

[0035] According to some embodiments of the present invention, the fiber may be cotton fiber, rayon, polyamide fiber, polyester fiber, aramid fiber, ultra-high molecular weight polyethylene fiber, polyimide fiber, carbon fiber, or a compound twisted cord of the said fiber.

[0036] According to some embodiments of the present invention, the form of the fiber is selected from the group consisting of monofilaments, strands, twisted cords, canvases, plies, or combinations thereof.

[0037] This invention proposes a novel environmentally friendly impregnation system for fiber surface treatment, which allows for the selection and adoption of either a single-bath impregnation treatment or a double-bath impregnation treatment depending on the type and application of the fiber.

[0038] The fibers and rubber substrate treated with the impregnation system of the present invention exhibit excellent adhesion, achieving the objective of replacing RFLs. Moreover, the fibers treated with this environmentally friendly impregnation system have minimal strength loss and do not affect their performance.

[0039] In the present invention, when subjected to a single-bath impregnation treatment, applying hydroxyacrylic resin-amino resin-rubber latex to the fiber surface causes the hydroxyacrylic resin and amino resin to react and form a resin network structure, allowing polar groups to react with the fiber, while the rubber latex particles in the network structure participate in the co-vulcanization of the rubber substrate, thereby improving the adhesion performance between the fiber backbone and the rubber. In the case of a two-bath impregnation treatment, first the fiber surface is activated with epoxy resin and isocyanate in the first bath, and then the hydroxyacrylic resin-amino resin-rubber latex is applied to the surface with the second bath impregnation solution, thereby causing the above-mentioned physical and chemical reactions between the fiber and the rubber substrate, and improving the adhesion performance.

[0040] The present invention 1. The impregnation solution of the present invention eliminates the use of resorcinol and formaldehyde, significantly reducing harm to the environment and human health. Furthermore, the preparation of the impregnation solution and the fiber impregnation process are simplified, and the reaction time is shortened, making it advantageous for industrial production. 2. All raw materials used in this invention are industrialized products, have a wide range of sources, are inexpensive, and are all water-soluble. 3. The impregnation solution does not significantly increase in viscosity even when left for a long period of time under room temperature conditions, which is advantageous for long-term storage and transportation of the impregnation solution during the impregnation and manufacturing period of fiber skeleton materials. It possesses the following advantages and characteristics. [Modes for carrying out the invention]

[0041] The raw materials used in the following examples and comparative examples were all commercially available, and here, The hydroxyacrylic resin was purchased from Guangzhou Dolphin New Materials Co., Ltd., with a number-average molecular weight of approximately 10,000 and a hydroxyl group content of 3.2 wt%. The amino resin was purchased from Zhanxin Resin (China) Co., Ltd., and has a number-average molecular weight of approximately 600 and a solids content of 80 wt%. Sorbitol glycidyl ether, CAS 68412-01-1, was purchased from Nanya Epoxy Resin Co., Ltd. ε-Caprolactam-terminated diphenylmethane diisocyanate, CAS 5101-68-8, CBI number 50, was purchased from Changzhou Keying Chemical Industry Co., Ltd., with a solid content of 50 wt% and a particle size of 1.5 μm. Styrene-butadiene-vinylpyridine latex (VP latex), number VP-15, was purchased from Jiangsu Yatai Chemical Industry Co., Ltd., with a solids content of 40 wt%. Resorcinol, CAS 108-46-3, was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., with a purity of ≥99 wt%. The formaldehyde is CAS 50-00-0, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., with a purity of 37 wt%.

[0042] The method for manufacturing the splines used in the H tensile force test in the following examples and comparative examples is as follows. Using standard GB / T 2942-2009, the standard rubber (standard rubber compound GB / T 9101-2017 was used) was completely coated onto the dip cord, which was then placed in a slab vulcanizing machine and vulcanized at a vulcanization temperature of 136°C, a vulcanization time of 50 mins, and a vulcanization pressure of 15 MPa.

[0043] The method for manufacturing the peeling force test splines in the following examples and comparative examples is as follows. The adhesive strength standard for a single dip cord of nylon 66 was measured, referencing the lift-off method developed by Jinba Jitsugyo Co., Ltd. The rubber paste formulation used for vulcanization was the same as that used in the H tensile strength test. Vulcanization temperature: 160°C, vulcanization time: 20 min, vulcanization pressure: 2.354 MPa.

[0044] The method for producing the cord tensile strength samples in the following examples and comparative examples is as follows. Standard GB / T 32108-2015 was used, and the cord strength was measured using a tensile machine after dipping. The cord in the test area was 250 mm long, and the tensile speed was 300 mm / min.

[0045] In the following examples and comparative examples, the cord tensile strength test was performed according to GB / T 32108-2015, and the H tensile force test was performed according to GB / T 2942-2009. The method for the peel force test is as follows. The dimensions of the vulcanization mold are as follows: die cavity depth 2 mm, length 250 mm, width 170 mm, width of each sample 20 mm, spacing between pieces 6 mm, leaving 10 mm on each side of the mold, and the thickness of both the lid plate and the mold bottom plate is 10 mm or more. The rubber paste formulation used for vulcanization is the same as that used in the H tensile strength test. The vulcanization process is performed at 160°C for 20 minutes at a pressure of 2.354 MPa. The vulcanization process is as follows: 1) Preheat the mold to 136°C for 15-20 minutes, then insert one cord into the groove and stretch the cord vertically. 2) Place a rubber sheet measuring 20 mm in length, 160 mm in width, and 0.5 mm in thickness near the edge of the bottom of the mold, and attach a piece of cellophane slightly larger than the rubber sheet on top of it. 3) Place a rubber sheet measuring 240 mm in length, 160 mm in width, and 1.7 mm in thickness on top of the cellophane paper, and simultaneously attach a backing of the same size. Clamp the capping and perform vulcanization. After vulcanization, allow to cool for at least 2 hours, then prune the sample and test the release force (each sample contains 5 cords). The test procedure was as follows: The cellophane-separated portion was clamped at a 180° angle between the upper and lower chucks of a tensioning machine, and stretching and peeling were performed. The tensioning machine speed was set to 300 mm / min, and the peeling length was set to (150 ± 10) mm. The average adhesive strength (N) was read from the peeling curve, and the peeling force of that single cord was calculated.

[0046] Example 1

[0047] A protective impregnation treatment system for fiber surface environments, the formulation for the single-bath method, with the proportions of each component in parts by weight, is as follows: [Table 4]

[0048] The method for producing the impregnation solution is as follows: The hydroxyacrylic resin, amino resin, and accelerator listed in the formulation are sequentially added to deionized water, and the solution is vigorously stirred with an electric stirrer for 3 hours. Then, the blocked isocyanate is added and stirred for 1 hour, and finally, the rubber latex is added to this solution, and vigorous stirring is maintained for 2 hours to obtain a one-bath impregnation solution.

[0049] The impregnation treatment method is as follows: The fiber cord is impregnated in the impregnation solution for 1 minute at room temperature, and then dried and cured in an oven. The drying temperature is 150°C, the drying time is 2 minutes, the curing temperature is 220°C, and the curing time is 2 minutes.

[0050] Example 2

[0051] A protective impregnation treatment system for fiber surface environments, the formulation for the single-bath method, has the following proportions of each component in parts by weight: [Table 5]

[0052] The method for preparing the impregnation solution is as follows: The hydroxyacrylic resin, amino resin, and accelerator listed in the formulation are sequentially added to deionized water, and the solution is vigorously stirred with an electric stirrer for 2 hours. Then, the blocked isocyanate is added and stirred for 30 minutes, and finally, the rubber latex is added to this solution and vigorously stirred for 1 hour to obtain a one-bath impregnation solution.

[0053] The impregnation treatment method is as follows: The fiber cord is impregnated in the impregnation solution at room temperature for 1.5 minutes, and then dried and cured in an oven. The drying temperature is 150°C, the drying time is 3 minutes, and the curing temperature is 210°C, the curing time is 3 minutes.

[0054] Example 3

[0055] The fiber surface environmental protection impregnation treatment system, for a single-bath method, has the following proportions of each component based on parts by weight: [Table 6]

[0056] The method for preparing the impregnation solution is as follows: Add the hydroxyacrylic resin, amino resin, and accelerator listed in the formulation to deionized water in sequence, and vigorously stir the solution with an electric stirrer for 1.5 hours. Then add the blocked isocyanate and stir for 30 minutes, and finally add the rubber latex to this solution and maintain vigorous stirring for 1.5 hours to obtain a single-bath solution.

[0057] The impregnation treatment method is as follows: The fiber cord is impregnated in the impregnation solution at room temperature for 1 minute, and then dried and cured in an oven. The drying temperature is 150°C, the drying time is 1.5 minutes, the curing temperature is 225°C, and the curing time is 1.5 minutes.

[0058] Example 4

[0059] A protective impregnation treatment system for fiber surface environments, the formulation for the single-bath method, with the proportions of each component in parts by weight, is as follows: [Table 7]

[0060] The method for producing the impregnation solution is as follows: Add the epoxy resin described in the formulation to deionized water and stir for 1.5 hours to obtain a homogeneous dispersion. Then, sequentially add the hydroxyacrylic resin, amino resin, and blocked isocyanate and stir for 2 hours. After that, add the accelerator and stir for 1 hour, and finally add the rubber latex and continue stirring for 2 hours to obtain a one-bath impregnation solution.

[0061] The impregnation treatment method is as follows: The fiber cord was impregnated in the impregnation solution at room temperature for 1 minute, and then dried and cured in an oven. The drying temperature was 160°C, the drying time was 2 minutes, the curing temperature was 210°C, and the curing time was 2 minutes.

[0062] Example 5

[0063] A protective impregnation treatment system for fiber surface environments, the formulation for a single-bath method, is as follows, with the proportions of each component in parts by weight: [Table 8]

[0064] The method for producing the impregnation solution is as follows: The epoxy resin described in the formulation is added to deionized water and stirred for 1.5 hours to obtain a homogeneous dispersion. Then, the hydroxyacrylic resin, amino resin, and blocked isocyanate are added sequentially and stirred for 1.5 hours. After that, an accelerator is added and stirred for 1.5 hours, and finally the rubber latex is added and stirring is continued for 2 hours to obtain a one-bath impregnation solution.

[0065] The impregnation treatment method is as follows: The fiber cord was impregnated in the impregnation solution at room temperature for 1.5 minutes, and then dried and cured in an oven. The drying temperature was 150°C, the drying time was 2 minutes, and the curing temperature was 225°C, with a curing time of 2 minutes.

[0066] Example 6

[0067] A protective impregnation treatment system for fiber surface environments, the formulation for a single-bath method, is as follows, with the proportions of each component in parts by weight: [Table 9]

[0068] The method for producing the impregnation solution is as follows: The epoxy resin described in the formulation is added to deionized water and stirred for 1.5 hours to obtain a homogeneous dispersion. Then, the hydroxyacrylic resin, amino resin, and blocked isocyanate are added sequentially and stirred for 2 hours. After that, an accelerator is added and stirred for 1.5 hours, and finally the rubber latex is added and stirring is continued for 2 hours to obtain a one-bath impregnation solution.

[0069] The impregnation treatment method is as follows: The fiber cord is impregnated in the impregnation solution at room temperature for 2 minutes, and then dried and cured in an oven. The drying temperature is 160°C, the drying time is 1.5 minutes, and the curing temperature is 220°C, the curing time is 1.5 minutes.

[0070] Comparative Example 1

[0071] Comparative Example 1 is a conventional RFL impregnation treatment, and the RFL composition is as shown in the table below. [Table 10]

[0072] The production of RFL is as follows: First, sodium hydroxide is added to deionized water according to the above formulation and stirred for 10 minutes. Resorcinol is then added and stirred for another 10 minutes. After that, aqueous formaldehyde is added and stirred at room temperature for 6 hours to obtain a homogeneous reaction solution. Finally, butadiene-vinylpyridine goumalatex is added and stirred at room temperature for 2 hours, during which time aqueous ammonia is added to obtain the final RFL impregnation solution.

[0073] The RFL impregnation treatment method is as follows: The fiber cord is impregnated in the impregnation solution for 1 minute at room temperature, and then dried and cured in an oven. The drying temperature was 150°C and the drying time was 3 minutes, while the curing temperature was 220°C and the curing time was 3 minutes.

[0074] In Application Examples 1-6 and Application Comparative Example 1, different fiber cords were treated with a single-bath method. The cords used in Application Examples 1-1, 2-1, 3-1, 4-1, 5-1, 6-1, and Application Comparative Example 1-1 were nylon 6 cords (1170 dtex / 2), while the cords used in Application Examples 1-2, 2-2, 3-2, 4-2, 5-2, 6-2, and Application Comparative Example 1-2 were nylon 66 cords (1400 dtex / 2).

[0075] For different fiber cords that underwent impregnation treatment in Application Examples 1-6 and Application Comparative Example 1, test samples were prepared according to the above method, and H pulp tests, peel tests, and cord strength tests were performed. The test results are shown in Table 1.

[0076] [Table 11(1)] [Table 11(2)]

[0077] From the results in Table 1, it was found that the two types of fiber cords in Application Examples 1-3 exhibited almost the same H-pulling performance and peel strength as those treated with RFL in the Comparative Application Examples. Based on this, the addition of epoxy resin, i.e., the treatment effect in Application Examples 4-6, further improved the adhesive effect of these two types of fiber cords compared to the adhesive performance of the Comparative Application Examples with RFL. Furthermore, from the cord strength test results, the fibers treated with this method did not suffer significant strength loss and were not affected in their use. In summary, this novel environmentally friendly impregnation system exhibits excellent adhesive effect between fibers treated with a single bath and the rubber substrate, and can effectively replace the RFL impregnation system.

[0078] Example 7

[0079] An environmentally friendly impregnation treatment system for fiber surface treatment, in which the proportions of each component in the two-bath method formulation are as follows in parts by weight. [Table 12]

[0080] The preparation of the dipping solution is as follows: In the first step, the water-soluble epoxy resin described in the formulation is added to deionized water and stirred for 15 minutes, then the blocked isocyanate is added and stirred for 1 hour to obtain a homogeneous reaction solution, thereby producing the first bath impregnation solution. In the second step, the hydroxyacrylic resin described in the formulation is added to deionized water and stirred for 1.5 hours to obtain a homogeneous dispersion, then the amino resin and accelerator are added and stirred for 30 minutes, and finally the rubber latex is added and stirring is continued for 1.5 hours to obtain the second bath impregnation solution.

[0081] The dipping process is as follows: First, the fiber cord is placed in the first bath impregnation solution and impregnated at room temperature for 2 minutes, then dried at 130°C for 1 minute, and cured at 210°C for 2 minutes. After that, the fiber is placed in the second bath impregnation solution and impregnated at room temperature for 2 minutes, then dried at 130°C for 2 minutes, and finally cured at 210°C for 2 minutes, allowing the impregnation solution to adhere to the fiber surface.

[0082] Example 8 An environmentally friendly impregnation treatment system for fiber surface treatment, in which the proportions of each component in the two-bath method formulation are as follows in parts by weight. [Table 13]

[0083] The preparation of the dipping solution is as follows: In the first step, the water-soluble epoxy resin is added to deionized water and stirred for 1 hour, then the blocked isocyanate is added and stirred for 30 minutes to obtain a homogeneous reaction solution, thereby producing the first bath impregnation solution. In the second step, the hydroxyacrylic resin described in the formulation is added to deionized water and stirred for 2 hours to obtain a homogeneous dispersion, then the amino resin and accelerator are added and stirred for 1 hour, and finally the rubber latex is added and stirring is continued for 1.5 hours to obtain the second bath impregnation solution.

[0084] The dipping process was as follows: First, the fiber cord was placed in the first bath impregnation solution and impregnated at room temperature for 1 minute, then dried at 130°C for 1.5 minutes, and cured at 210°C for 2 minutes. After that, the fiber was placed in the second bath impregnation solution and impregnated at room temperature for 1 minute, then dried at 160°C for 1.5 minutes, and finally cured at 210°C for 2 minutes, allowing the impregnation solution to adhere to the fiber surface.

[0085] Comparative Example 2

[0086] Comparative Example 2 is a treatment using the conventional RFL two-bath method, and the formulation of the conventional RFL two-bath method is as follows. [Table 14]

[0087] The impregnation solution was prepared as follows: First, the water-soluble epoxy resin described in the formulation was added to deionized water and stirred for 15 minutes, then the blocked isocyanate was added and stirred for 1 hour to obtain the first bath impregnation solution. Then, according to the formulation, sodium hydroxide was added to the deionized water and stirred for 10 minutes, then resorcinol was added and stirred for 10 minutes, and finally an aqueous formaldehyde solution was added and stirred at room temperature for 6 hours to obtain a homogeneous reaction solution, and finally butadiene-vinylpyridinegoulalatex was added and stirred at room temperature for 2 hours, during which time aqueous ammonia was added to finally obtain the RFL impregnation solution.

[0088] The dipping process is as follows: First, the fiber cord is placed in the first bath impregnation solution and impregnated at room temperature for 1 minute, then dried at 130°C for 3 minutes, and cured at 220°C for 3 minutes. After that, the fiber is placed in the second bath impregnation solution and impregnated at room temperature for 2 minutes, then dried at 130°C for 3 minutes, and finally cured at 220°C for 3 minutes, allowing the impregnation solution to adhere to the fiber surface.

[0089] Application Examples 7-8 and Application Comparative Example 2 both involve treating different fiber cords using the two-bath method. The cords treated in Application Examples 7-1, 8-1, and Application Comparative Example 2-1 are nylon 66 cords (1400 dtex / 2), the cords treated in Application Examples 7-2 and 8-2, and Application Comparative Example 2-2 are aramid cords (1670 dtex / 2), the cords treated in Application Examples 7-3 and 8-3, and Application Comparative Example 2-3 are polyester cords (1440 dtex / 2), and the cords treated in Application Examples 7-4 and 8-4, and Application Comparative Example 2-4 are aramid / nylon 66 twisted cords (A1670 dtex / 2 + N2100 dtex / 1).

[0090] For the different fiber cords that underwent impregnation treatment in Application Examples 7-8 and Application Comparative Example 2, test samples were prepared according to the method described above, and H pulp tests, peel tests, and cord strength tests were performed. The test results are shown in Table 2.

[0091] [Table 15]

[0092] The results in Table 2 show that the H pull-out force and peel force of the different fiber cords in Application Examples 7-8 both exceeded the adhesive effect of RFL in the Comparative Application Examples. In particular, in Application Examples 7-1 and 7-2, when nylon 66 cord (1400 dtex / 2) was treated using the two-bath method, the adhesive effect after impregnation treatment was superior to that of the one-bath method. Furthermore, the cord strength test results showed that the strength loss to the fibers after treatment with this two-bath method was not significant and did not affect their use. In summary, this novel environmentally friendly two-bath impregnation system exhibits an excellent adhesive effect between the treated fibers and the rubber substrate, and can effectively replace the RFL impregnation system.

[0093] The embodiments described above are merely preferred embodiments of the present invention and do not limit the invention in any other way. Any modifications or equivalent changes or improvements made to the above embodiments, insofar as they do not depart from the claims of the present invention in technical substance, remain within the scope of the protection of the claims of the present invention.

Claims

1. An environmentally friendly impregnation system for fiber surface treatment, wherein by weight, Deionized water, 100 copies Hydroxyacrylic resin 1 to 30 parts Amino resin 0.1 to 10 parts Blocked isocyanates: 1-10 parts Accelerator 0.1 to 5 parts Rubber latex 50-180 units It contains the following ingredients: The amino resin is at least one selected from the group consisting of urea aldehyde resin, melamine formaldehyde resin, polyamide polyamine epichlorohydrin, etherified urea aldehyde resin, etherified glycol uryl resin, fully methyl etherified melamine resin, polymerized partially methyl etherified melamine resin, or polymerized high imino group methyl etherified melamine resin. The accelerator is at least one selected from the group consisting of amine-closed dinonylnaphthalene sulfonic acid, amine-closed dinonylnaphthalene sulfonic acid, amine-closed dodecylbenzenesulfonic acid, or amine-closed p-methylbenzenesulfonic acid. An environmentally friendly impregnation system for fiber surface treatment, characterized by the following features.

2. In the heavy section, Deionized water, 100 copies Hydroxyacrylic resin 1 to 15 parts Amino resin 0.1 to 8 parts Epoxy resin 1 to 10 parts Blocked isocyanates: 1-10 parts Accelerator 0.1 to 4 parts Rubber latex, 50-150 units The environmentally friendly impregnation system according to claim 1, characterized by containing the following component.

3. The environmentally friendly impregnation system according to claim 1, characterized in that the hydroxyacrylic resin has a hydroxyl group content of 2.0 to 5.0 wt% and a number average molecular weight of 8,000 to 15,000.

4. The environmentally friendly impregnation system according to any one of claim 2, characterized in that the epoxy resin is at least one selected from the group consisting of bisphenol A type epoxy resin, epoxy novolac resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, 1,2-propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, diglycidyl ether, glycerol glycidyl ether, trimethylolpropane glycidyl ether, tetraphenolethane tetraglycidyl ether epoxy resin, resorcinol bisglycidyl ether type epoxy resin, or bisresorcinol formaldehyde tetraglycidyl ether.

5. The environmentally friendly impregnation system according to any one of claims 1 to 3, characterized in that the blocked isocyanate comprises an isocyanate and a chelating agent, the isocyanate being selected from the group consisting of trimethyl-1,6-hexamethylene diisocyanate, tetramethylene diisocyanate, tetramethyl diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-benzene diisocyanate, 1,4-benzene diisocyanate, isophorone diisocyanate and diphenylmethane diisocyanate, and the chelating agent being at least one selected from the group consisting of ε-caprolactam, butanone oxime and phenol.

6. The environmentally friendly impregnation system according to any one of claims 1 to 3, characterized in that the rubber latex has a solid content of 20 to 60 wt% and is at least one selected from the group consisting of butadiene-vinylpyridine rubber latex, styrene-butadiene rubber latex, butadiene-styrene-vinylpyridine rubber latex, chloroprene rubber latex, nitrile rubber latex, or natural rubber latex.

7. A method for manufacturing an environmentally friendly impregnation system for fiber surface treatment, wherein the method is as follows: (1) In the case of a one-bath dipping solution system, the process includes sequentially adding hydroxyacrylic resin, amino resin, epoxy resin (if necessary), and an accelerator to deionized water and stirring, then adding blocked isocyanate and stirring, and finally adding rubber latex and continuing to stir to obtain a one-bath impregnation solution, wherein the amounts of each component used are, by weight, 100 parts deionized water, 1 to 30 parts hydroxyacrylic resin, 0.1 to 10 parts amino resin, 1 to 10 parts blocked isocyanate, 0.1 to 5 parts accelerator, and 50 to 180 parts rubber latex. or (2) In the case of a two-bath dipping system, the process includes the steps of: 1) adding a water-soluble epoxy resin to deionized water and stirring, then adding a blocked isocyanate and stirring to obtain a homogeneous reaction solution, thereby obtaining a first bath impregnation solution; 2) sequentially adding a hydroxyacrylic resin, an amino resin, and an accelerator to deionized water and stirring to obtain a homogeneous dispersion, and finally adding a rubber latex and continuing to stir, thereby obtaining a second bath impregnation solution, wherein the first bath impregnation solution contains 1 to 2 parts by weight of epoxy resin, 5 to 8 parts of blocked isocyanate, and 95 to 105 parts by weight of deionized water, and the second bath impregnation solution contains 7 to 10 parts by weight of hydroxyacrylic resin, 1 to 2.5 parts of amino resin, 1.5 to 3 parts of accelerator, 100 to 180 parts of rubber latex, and 95 to 105 parts by weight of deionized water. The amino resin is at least one selected from the group consisting of urea aldehyde resin, melamine formaldehyde resin, polyamide polyamine epichlorohydrin, etherified urea aldehyde resin, etherified glycol uryl resin, fully methyl etherified melamine resin, polymerized partially methyl etherified melamine resin, or polymerized high imino group methyl etherified melamine resin. The accelerator is at least one selected from the group consisting of amine-closed dinonylnaphthalene sulfonic acid, amine-closed dinonylnaphthalene sulfonic acid, amine-closed dodecylbenzenesulfonic acid, or amine-closed p-methylbenzenesulfonic acid. A method for manufacturing an environmentally friendly impregnation system for fiber surface treatment, characterized by the following:

8. An impregnation treatment method for fiber surface treatment, The process of impregnating the fibers in a one-bath impregnation solution (A), Step (B) involves drying and hardening the impregnated fibers obtained in step (A), Includes, Of these, the amount of each component used in one bath impregnation solution is, by weight, 100 parts deionized water, 1 to 30 parts hydroxyacrylic resin, 0.1 to 10 parts amino resin, 1 to 10 parts blocked isocyanate, 0.1 to 5 parts accelerator, and 50 to 180 parts rubber latex. The amino resin is at least one selected from the group consisting of urea aldehyde resin, melamine formaldehyde resin, polyamide polyamine epichlorohydrin, etherified urea aldehyde resin, etherified glycol uryl resin, fully methyl etherified melamine resin, polymerized partially methyl etherified melamine resin, or polymerized high imino group methyl etherified melamine resin. The accelerator is at least one selected from the group consisting of amine-closed dinonylnaphthalene sulfonic acid, amine-closed dinonylnaphthalene sulfonic acid, amine-closed dodecylbenzenesulfonic acid, or amine-closed p-methylbenzenesulfonic acid. An impregnation treatment method for surface treatment of fibers, characterized by the above.

9. An impregnation treatment method for fiber surface treatment, Step i), in which the fibers are impregnated by placing them in a first bath impregnation solution, and the amounts of each component used in the first bath impregnation solution are 0.5 to 2.5 parts by weight of epoxy resin, 3 to 10 parts by weight of blocked isocyanate, and 90 to 110 parts by weight of deionized water. Step i) Dry the treated fibers, then step ii) harden them. Step ii) The treated fibers are impregnated in a second bath impregnation solution, wherein the amounts of each component used in the second bath impregnation solution are 5 to 15 parts by weight of hydroxyacrylic resin, 0.5 to 3 parts of amino resin, 1 to 5 parts of accelerator, 80 to 200 parts of rubber latex, and 90 to 110 parts of deionized water. Step iii) Step iv) involves drying and hardening the fibers processed in step iii). This process includes, The amino resin is at least one selected from the group consisting of urea aldehyde resin, melamine formaldehyde resin, polyamide polyamine epichlorohydrin, etherified urea aldehyde resin, etherified glycol uryl resin, fully methyl etherified melamine resin, polymerized partially methyl etherified melamine resin, or polymerized high imino group methyl etherified melamine resin. The accelerator is at least one selected from the group consisting of amine-closed dinonylnaphthalene sulfonic acid, amine-closed dinonylnaphthalene sulfonic acid, amine-closed dodecylbenzenesulfonic acid, or amine-closed p-methylbenzenesulfonic acid. An impregnation treatment method for surface treatment of fibers, characterized by the above.

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