Activating oiling agent for polyester industrial yarn and preparation method of activating oiling agent

Abstract

The invention discloses an activating oiling agent for polyester industrial yarns. The activating oiling agent is prepared from the following components in percentage by mass: 50-65% of a smoothing agent, 10-25% of an emulsifier, 6-15% of a bundling agent, 6-9% of an antistatic agent, 0.1-2% of an antioxidant and 0.5-1% of water, wherein the smoothing agent is a synthetic ester smoothing agent. Compared with the prior art, the oiling agent disclosed by the invention has the advantages that the adhesion between a fiber base material and rubber is greatly improved, the H-extraction force can reach 60N at most, the produced activated yarn meets the adhesive force requirement of tire cords, the application field is expanded, no obvious blue smoke is generated in the spinning process, and the production environment is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of auxiliaries manufacturing in synthetic fiber processing, and relates to a polyester industrial yarn activating finishing agent and a preparation method thereof. Background Art

[0002] Since the United States successfully applied polyester fiber to cord fabric in the 1960s, the application of polyester fiber (polyester industrial yarn) has gradually expanded to fields such as tire cord fabric, conveyor belt, canvas cord fabric, and vehicle seat belt. The surface of the activated polyester industrial yarn is attached with a reactive activating finishing agent, which can form good adhesion with polymer matrices such as rubber and polyvinyl chloride, can simplify the subsequent composite molding process, and is convenient for preparing polyester fabric reinforced composites with light weight, deformability, high strength, high modulus, and good dimensional stability, and can be widely used in fields such as the automotive industry and construction engineering.

[0003] The activating finishing agent is an important auxiliary agent that endows the surface activity of polyester industrial yarn, and is generally applied with oil dynamically through a nozzle or an oil roller after fiber forming.

[0004] The finishing agents for polyester industrial yarn are divided into two categories: ordinary spinning finishing agents and activating finishing agents for high-strength fiber composite reinforcement. In recent years, with the rapid development of the chemical fiber industry in China, the development of ordinary spinning finishing agents has been successfully realized for domestic application. However, the production of high-performance activating finishing agents for fields such as high-strength fiber composite rubber, cord fabric, and impregnated advertising fabric has been monopolized by countries such as the United States and Japan, such as Takeimoto and Matsumoto. CN109735942A discloses an activated polyester industrial yarn, and the static adhesion strength between the fiber cord fabric made of 1100dtex / 192F high-modulus low-shrinkage activated polyester industrial yarn and vulcanized rubber is 49-53N, and the static adhesion strength between vulcanized rubber and the fiber cord fabric made of 1670dtex / 192F high-modulus low-shrinkage activated polyester industrial yarn is 55-62N, but its preparation process is relatively cumbersome and the cost is relatively high. The above processes have disadvantages such as high preparation cost, uncontrollable activation process, poor heat resistance, and poor adhesion performance. Therefore, it is urgent to develop a new type of polyester industrial yarn activating finishing agent. Summary of the Invention

[0005] The purpose of the present invention is to provide an environmentally friendly finishing agent with stable performance, less smoke emission, and good spinnability.

[0006] The purpose of the present invention is achieved by adopting the following technical solutions:

[0007] A polyester industrial yarn activating finishing agent is composed of the following raw materials in mass percentage: 50-65% of a smoothing agent, 10-25% of an emulsifier, 6-15% of a bundling agent, 6-9% of an antistatic agent, 0.1-2% of an antioxidant, and 0.5-1% of water; the sum of the above components is 100%; wherein, the smoothing agent is a synthetic ester smoothing agent.

[0008] Preferably, the activation oil agent for polyester industrial yarn consists of the following raw materials in mass percentages: 55-65% of a smoothing agent, 15-25% of an emulsifier, 8-12% of a bundling agent, 6-8% of an antistatic agent, 0.1-1% of an antioxidant, and 0.5-1% of water.

[0009] The smoothing agent is one or a mixture of trimethylolpropane oleate, pentaerythritol oleate, polyethylene glycol oleate, and glyceride.

[0010] Preferably, the smoothing agent is a mixture of trimethylolpropane oleate and one selected from pentaerythritol oleate, polyethylene glycol oleate, and glyceride in a mass ratio of 0.5:1 to 5:1, or a mixture of pentaerythritol oleate and one selected from polyethylene glycol oleate and glyceride in a mass ratio of 0.5:1 to 2:1.

[0011] More preferably, the smoothing agent is a mixture of trimethylolpropane oleate and one selected from pentaerythritol oleate, polyethylene glycol oleate, and glyceride in a mass ratio of 0.6:1 to 4.6:1, or a mixture of pentaerythritol oleate and one selected from polyethylene glycol oleate and glyceride in a mass ratio of 0.6:1 to 1.9:1.

[0012] The glyceride is one or a mixture of glyceryl trioleate, glyceryl stearate, and glyceryl laurate.

[0013] The emulsifier is one or a mixture of propylene glycol block polyether, polysorbate, sorbitan monooleate, and alkyl sulfate.

[0014] Preferably, the emulsifier is a mixture of polysorbate and at least one selected from propylene glycol block polyether, sorbitan monooleate, and alkyl sulfate, or a mixture of propylene glycol block polyether and sorbitan monooleate.

[0015] More preferably, the emulsifier is a mixture of at least one selected from polysorbate and sorbitan monooleate and at least one selected from propylene glycol block polyether and alkyl sulfate, or the emulsifier is a mixture of polysorbate and sorbitan monooleate.

[0016] Specifically, the emulsifier is a mixture of propylene glycol block polyether and polysorbate with a mass ratio of 1:1, or a mixture of propylene glycol block polyether, polysorbate and sorbitan monooleate with a mass ratio of 1:1:2, or a mixture of propylene glycol block polyether and sorbitan monooleate with a mass ratio of 1:0.9, or a mixture of alkyl sulfate and polysorbate with a mass ratio of 1:3, or a mixture of polysorbate and sorbitan monooleate with a mass ratio of 1:1.3, or a mixture of alkyl sulfate, polysorbate and sorbitan monooleate with a mass ratio of 1:2:1.5.

[0017] The propylene glycol block polyether is a polyoxypropylene and polyoxyethylene block polymer with an average molecular weight of 2200 - 2900.

[0018] In some specific embodiments, the specifications of the propylene glycol block polyether are L44, L62, L63, L64.

[0019] The propylene glycol block polyether L64 has an average molecular weight of 2900 and is a polyoxypropylene and polyoxyethylene block polymer made from propylene oxide (PO) and ethylene oxide (EO) in a molar ratio of 6:4.

[0020] The polysorbate can specifically be selected from polysorbate 60 (Tween 60).

[0021] The sorbitan monooleate can specifically be selected from Span 80.

[0022] The clustering agent is one or a mixture of several of higher fatty acid diethanolamine salts, alkylolamides, betaines, sulfonated castor oils.

[0023] Preferably, the clustering agent is an alkylolamide, or a mixture of an alkylolamide and a higher fatty acid diethanolamine salt, or a mixture of sulfonated castor oil and one selected from betaines and alkylolamides.

[0024] Specifically, when the clustering agent is a mixture of a higher fatty acid diethanolamine salt and an alkylolamide, the mass ratio of the higher fatty acid diethanolamine salt to the alkylolamide is 1:3 - 2:1; when the clustering agent is a mixture of sulfonated castor oil and one selected from betaines and alkylolamides, the mass ratio of sulfonated castor oil to one selected from betaines and alkylolamides is 1:1 - 1:2.

[0025] The higher fatty acid diethanolamine salt is oleic acid diethanolamine salt.

[0026] The alkylolamide is lauric acid diethanolamide (N,N - diethyldodecanamide).

[0027] The antistatic agent is one or a mixture of several of polyquaternium, alkyl sulfonate, and alkyl phosphate.

[0028] Preferably, the antistatic agent is alkyl sulfonate, polyquaternium, or a mixture of alkyl phosphonate and one selected from alkyl sulfonate and polyquaternium, or a mixture of alkyl sulfonate and polyquaternium.

[0029] Specifically, when the antistatic agent is a mixture of alkyl phosphonate and one selected from alkyl sulfonate and polyquaternium, the mass ratio of alkyl phosphonate to one selected from alkyl sulfonate and polyquaternium is 1:0.6 to 1:1; when the antistatic agent is a mixture of alkyl sulfonate and polyquaternium, the mass ratio of alkyl sulfonate to alkanolamide is 2:1.

[0030] The polyquaternium is selected from polyquaternium-7, and specifically can be selected from M-550.

[0031] The alkyl sulfonate is secondary alkyl sulfonate.

[0032] The alkyl phosphonate is triethanolamine monododecyl phosphate.

[0033] The antioxidant is one or a mixture of several of tris(nonylphenyl) phosphite, pentaerythritol diphosphite distearate (antioxidant 618), tris(2,4-di-tert-butylphenyl) phosphite, and sodium hypophosphite.

[0034] A preparation method of a polyester industrial yarn activation finishing agent includes the following steps:

[0035] Step (1): At a temperature of 20-30 °C, add a leveling agent, an emulsifier, a bundling agent, and an antistatic agent and stir evenly.

[0036] Step (2): Add an antioxidant and water to the mixed material obtained in step (1), stir evenly at a temperature of 20-30 °C, and filter to obtain the polyester industrial yarn activation finishing agent.

[0037] In step (1), the stirring time is 40-60 min.

[0038] In step (2), the stirring time is 40-60 min.

[0039] Compared with the existing industrial yarn finishing agent, the beneficial effects of the present invention are:

[0040] (1) In the production process of existing activated yarns, there is a problem of low heat resistance. In the finishing agent of the present invention, emulsifiers such as propylene glycol block polyether or the combined use of fatty acid ester and propylene glycol block polyether are added, and these additives improve the stability and heat resistance of the finishing agent, making it stable at high temperatures.

[0041] (2) The sizing agent contains a large amount (at least half of the total amount of the sizing agent) of a smoothing agent, which is beneficial to reducing the friction between fibers and results in a relatively low broken-end rate of the tow during the production process.

[0042] (3) The sizing agent of the present invention greatly improves the adhesion between the fiber substrate and the rubber. In particular, by using polysorbate containing an ether bond and diethanolamide laurate containing a hydroxyl group, the adhesion between the fiber substrate and the rubber can be enhanced through van der Waals forces and hydrogen bonds. The H-extraction force can reach up to 60 N at most, enabling the produced activated filaments to meet the adhesion requirements for tire cord, thus expanding the application fields.

[0043] (4) No obvious blue smoke is generated during the spinning process of the sizing agent, which improves the production environment. Detailed Embodiments

[0044] To make the objectives, technical solutions, and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments.

[0045] Example 1

[0046] The raw materials and mass percentages of the sizing agent for polyester industrial filaments are as follows:

[0047] Trimethylolpropane trioleate (smoothing agent) 40%, polyethylene glycol 400 monooleate (PEG400MO, smoothing agent) 20%, propylene glycol block polyether L64 (emulsifier) 10%, polysorbate 60 (emulsifier) 10%, diethanolamide laurate (bundling agent) 10%, secondary alkyl sulfonate SAS-60 (antistatic agent) 4%, triethanolamine monododecyl phosphate (antistatic agent) 4%, tris(nonylphenyl) phosphite (antioxidant) 1%, water 1%.

[0048] The preparation method of the sizing agent for polyester industrial filaments in this example includes: putting the smoothing agent, emulsifier, bundling agent, and antistatic agent into a reaction kettle, stirring at a temperature of 20 - 30°C for 60 min until evenly mixed, then putting the antioxidant and water into the reaction kettle, and continuing to stir at a temperature of 20 - 30°C for 60 min until evenly mixed, filtering and discharging to obtain the finished product of the sizing agent for polyester industrial filaments, and sealing it.

[0049] Example 2

[0050] The raw materials and mass percentages of the sizing agent for polyester industrial filaments are as follows:

[0051] Trimethylolpropane oleate (smoothing agent) 46%, pentaerythritol oleate (smoothing agent) 10%, sodium dodecyl sulfate (emulsifier) 6%, polysorbate 60 (emulsifier) 18%, lauric acid diethanolamide (bundling agent) 9%, oleic acid diethanolamine salt (bundling agent) 3%, secondary alkyl sulfonate SAS-60 (antistatic agent) 7%, tris(nonylphenyl) phosphite (antioxidant) 0.3%, pentaerythritol diphosphite dioctadecyl ester (antioxidant) 0.2%, water 0.5%.

[0052] The preparation method of the activating finishing agent for polyester industrial yarn in this example is the same as that in Example 1.

[0053] Example 3

[0054] The raw materials and mass percentages of the activating finishing agent for polyester industrial yarn are as follows:

[0055] Triglyceride oleate (smoothing agent) 30%, trimethylolpropane oleate (smoothing agent) 20%, polyethylene glycol 400 monooleate (smoothing agent) 15%, propylene glycol block polyether L64 (emulsifier) 5%, polysorbate 60 (emulsifier) 5%, span S-80 (emulsifier) 10%, betaine (bundling agent) 5%, sulfonated castor oil (bundling agent) 3%, secondary alkyl sulfonate SAS-60 (antistatic agent) 4%, polyquaternium-7 (M-550, Jinan Shengxuan Chemical Co., Ltd., the same below; antistatic agent) 2%, sodium hypophosphite (antioxidant) 0.2%, pentaerythritol diphosphite dioctadecyl ester (antioxidant) 0.2%, water 0.6%.

[0056] The preparation method of the activating finishing agent for polyester industrial yarn in this example is the same as that in Example 1.

[0057] Example 4

[0058] The raw materials and mass percentages of the activating finishing agent for polyester industrial yarn are as follows:

[0059] Trimethylolpropane oleate (smoothing agent) 40%, triglyceride oleate (smoothing agent) 21%, propylene glycol block polyether L64 (emulsifier) 10%, span S-80 (emulsifier) 9%, lauric acid diethanolamide (bundling agent) 6%, sulfonated castor oil (bundling agent) 6%, polyquaternium-7 (antistatic agent) 7%, tris(nonylphenyl) phosphite (antioxidant) 0.2%, sodium hypophosphite (antioxidant) 0.3%, water 0.5%.

[0060] The preparation method of the activating finishing agent for polyester industrial yarn in this example is the same as that in Example 1.

[0061] Example 5

[0062] The raw materials and mass percentages of the activating finishing agent for polyester industrial yarn are as follows:

[0063] Pentaerythritol oleate (smoothing agent) 38%, polyethylene glycol 400 monooleate (smoothing agent) 20%, Span S-80 (emulsifier) 13%, polysorbate 60 (emulsifier) 10%, sulfonated castor oil (bundling agent) 4%, betaine (bundling agent) 6%, polyquaternium-7 (antistatic agent) 3%, triethanolamine monododecyl phosphate (antistatic agent) 5%, pentaerythritol diphosphite dioctadecyl ester (antioxidant) 0.4%, water 0.6%.

[0064] The preparation method of the activation finishing agent for polyester industrial yarn in this example is the same as that in Example 1.

[0065] Example 6

[0066] The raw materials and mass percentages of the activation finishing agent for polyester industrial yarn are as follows:

[0067] Triglycerol oleate (smoothing agent) 40%, pentaerythritol oleate (smoothing agent) 24%, polysorbate 60 (emulsifier) 8%, Span S-80 (emulsifier) 6%, sodium dodecyl sulfate (emulsifier) 4%, lauric acid diethanolamide (bundling agent) 3%, oleic acid diethanolamine salt (bundling agent) 6%, secondary alkyl sulfonate SAS-60 (antistatic agent) 3%, triethanolamine monododecyl phosphate (antistatic agent) 4%, sodium hypophosphite (antioxidant) 1%, water 1%.

[0068] The preparation method of the activation finishing agent for polyester industrial yarn in this example is the same as that in Example 1.

[0069] Comparative Example 1

[0070] The raw materials and mass percentages of the activation finishing agent for polyester industrial yarn are as follows:

[0071] Triglycerol oleate (smoothing agent) 30%, pentaerythritol oleate (smoothing agent) 16%, polysorbate 60 (emulsifier) 12%, Span S-80 (emulsifier) 9%, sodium dodecyl sulfate (emulsifier) 4%, lauric acid diethanolamide (bundling agent) 6%, coconut oil fatty acid diethanolamide (bundling agent) 13%, secondary alkyl sulfonate SAS-60 (antistatic agent) 4%, triethanolamine monododecyl phosphate (antistatic agent) 4%, sodium hypophosphite (antioxidant) 1%, water 1%.

[0072] The preparation method of the activation finishing agent for polyester industrial yarn is the same as that in Example 1.

[0073] The spinning performance of the finishing agent in Comparative Example 1 was investigated. The broken end rate of the tow was 2.3%, which was relatively high compared with the six examples.

[0074] The activation finishing agents prepared in Examples 1 - 6 were investigated, and the results are shown in Table 1.

[0075] Table 1. Quality Indexes of Activating Oil Agent

[0076]

[0077] The spinning performance of the activating oil agents prepared in Examples 1 - 6 of the present invention, imported oil agent, and domestic oil agent on the spinning machine was investigated, and the results are shown in Table 2.

[0078] Table 2. Investigation Results of Spinning Performance on the Spinning Machine

[0079]

[0080] Note: The imported oil agent is F - 2169 oil agent (Takemoto Co., Ltd., Japan), and the domestic oil agent is HDG - 2146 oil agent (Zhejiang Huangma Chemical Industry Group Co., Ltd.); the specification of polyester industrial yarn is 1110 dtex / 192 f, and the spinning oil agent is applied with 18% emulsion; the test method for the smoking temperature: visual inspection; the test method for the volatilization amount (140 °C, 2 h, %): oven method; the test method for the blue smoke emission situation: visual inspection; the test method for the coking situation on the hot roller: visual inspection; the test method for the H - extraction force: GB / T 2942—2009.

[0081] As can be seen from Table 1, the activating oil agent of the present invention has the characteristics of high stability, no delamination, and no precipitation, and its physical and chemical indexes are not much different from those of the imported oil agent. As can be seen from Table 2, the H - extraction forces of Examples 1, 2, and 6 are relatively large, which is due to the action of polysorbate and lauric acid diethanolamide. Polysorbate contains a large number of ether bonds with weak polarity, and lauric acid diethanolamide contains hydroxyl groups. The two can improve the adsorption effect through van der Waals forces and hydrogen bonding. The heat - resistant performance of the spun yarn prepared with the activating oil agent of the present invention on the spinning machine is better than that of the domestic oil agent and reaches the level equivalent to that of the imported oil agent. Moreover, the smoking, coking situations, and the bonding performance between polyester filaments and rubber are significantly better than those of the domestic oil agent, indicating that the oil agent of the present invention can fully meet the spinning requirements.

[0082] The above - mentioned are only the preferred embodiments of the present invention, and do not impose any formal restrictions on the technical solutions of the present invention. Any simple modifications, equivalent changes, and modifications made to the above - mentioned embodiments based on the technical essence of the present invention are all within the protection scope of the present invention.

Claims

1. A polyester industrial yarn activation oil agent, characterized in that: It is composed of the following components in percentage by mass: 50-65% of a smoothing agent, 10-25% of an emulsifier, 6-15% of a sizing agent, 6-9% of an antistatic agent, 0.1-2% of an antioxidant, and 0.5-1% of water; wherein the smoothing agent is a synthetic ester smoothing agent.

2. The polyester industrial yarn activating oil agent according to claim 1, characterized in that: It is composed of the following components in percentage by mass: 55-65% of a smoothing agent, 15-25% of an emulsifier, 8-12% of a bundling agent, 6-8% of an antistatic agent, 0.1-1% of an antioxidant, and 0.5-1% of water.

3. The polyester industrial yarn activating oil agent according to claim 1 or 2, characterized in that: The lubricant is one or a mixture of trimethylolpropane oleate, pentaerythritol oleate, polyethylene glycol oleate and glyceride.

4. The polyester industrial yarn activating oil agent according to claim 1 or 2, characterized in that: The emulsifier is one or a mixture of propylene glycol block polyether, polysorbate, sorbitan monooleate, and alkyl sulfate.

5. The polyester industrial yarn activating oil agent according to claim 1 or 2, characterized in that The emulsifier is a mixture of polysorbate and at least one selected from propylene glycol block polyether, sorbitan monooleate, and alkyl sulfate, or a mixture of propylene glycol block polyether and sorbitan monooleate.

6. The polyester industrial yarn activating oil agent according to claim 1 or 2, characterized in that: The sizing agent is one or a mixture of higher fatty acid diethanolamine salt, alkyl alcohol amide, betaine and sulfonated castor oil.

7. The polyester industrial yarn activating oil agent according to claim 6, characterized in that: The alkyl alcohol amide is lauric acid diethanolamide.

8. The polyester industrial yarn activating oil agent according to claim 1 or 2, characterized in that: The antistatic agent is one or a mixture of polyquaternary ammonium salt, sodium alkyl sulfonate and alkyl phosphate.

9. The polyester industrial yarn activating oil agent according to claim 1 or 2, characterized in that: The antioxidant is one or a mixture of tris(nonylphenyl)phosphite, pentaerythritol dioctadecyl diphosphite, tris(2,4-di-tert-butylphenyl)phosphite and sodium hypophosphite.

10. A method for preparing the polyester industrial yarn activating oil agent according to claim 1, characterized in that: The following steps are involved: Step (1), at a temperature of 20 to 30° C., adding a smoothing agent, an emulsifier, a sizing agent and an antistatic agent and stirring them uniformly; Step (2), adding antioxidant and water to the mixture obtained in step (1), stirring evenly at a temperature of 20 to 30° C., filtering, and obtaining a polyester industrial yarn activation oil agent.

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