JPH0152509B2 - - Google Patents

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a method for treating polyester fibers, and its purpose is to produce polyester fibers that have dramatically improved heat-resistant adhesion between the fibers and rubber. The purpose is to provide a processing method. In particular, the present invention provides a processing method that improves the rubber adhesion rate (rubber coverage) of polyester fibers when peeling polyester fibers from a composite molded product with rubber, and makes the polyester fibers flexible and excellent in fatigue resistance. It is related to. <Prior art> Polyester fibers, represented by polyethylene terephthalate fibers, have physical properties such as high strength and Young's modulus, low elongation, low creep, and excellent fatigue resistance, and are suitable for rubber reinforcement. It is widely used for composites, etc. However, polyester fibers have poor adhesion to rubber compared to polyamide fibers such as nylon 6 and nylon 6.6, and ordinary adhesive treatment does not provide the necessary strength to fully demonstrate the physical properties of polyester fibers. Adhesive performance cannot be obtained. The main reason for this is thought to be that the hydrogen bonding capacity of ester bonds in polyester is smaller than that of amide bonds in nylon. For this purpose, the surface of polyester fibers is coated with, for example, epoxy compounds,
A method of imparting adhesive properties by treating with a highly reactive substance such as an isocyanate compound has been proposed. However, when trying to improve the adhesion of polyester fibers to rubber, the treated fiber material becomes hard, making molding difficult and reducing fatigue resistance. <Object of the invention> The present invention was made against the background of the above circumstances, and the purpose of the present invention is to provide excellent performance in adhesion between polyester fiber and rubber, particularly in heat-resistant adhesion. It is in. In order to achieve this object, the present invention has been devised as a treatment method for imparting adhesive properties, particularly excellent heat-resistant adhesive properties, between polyester fibers and rubbers. <Configuration of the Invention> That is, the present invention provides (1) treating a linear aromatic polyester fiber with a first treatment agent containing a polyepoxide compound (A), a blocked polyisocyanate compound (B), and a rubber latex (C), and then treating a linear aromatic polyester fiber with a first treatment agent containing a polyepoxide compound (A), a blocked polyisocyanate compound (B), and a rubber latex (C); ·formalin·
An ethylene urea compound represented by the following general formula (D) and the following general formula (E) are added to rubber latex (RFL).
This is a method for treating polyester fibers, which is characterized by treating polyester fibers with a second treating agent containing a dicyclopentadiene phenolic epoxy compound represented by the formula D/E in a weight ratio of 40/60 to 80/20. [In the formula, R is an aromatic or aliphatic carbon hydrogen group,
n is 0.1 or 2. When n=0, the terminal group is hydrogen. ] [Here, R′, R″, R are any of H, CH ₃ , C ₂ H ₅ , and m is an integer of 0 to 10.] (2) The linear aromatic polyester has the general formula (n' is an integer from 2 to 6) A method for treating polyester fibers according to claim 1, which is a polyester whose main constituent is a repeating unit represented by (n' is an integer from 2 to 6). The present invention can be applied to any linear aromatic polyester, especially the general formula (n' is an integer of 2 to 6) is preferably used as a main component of a repeating unit, and in particular, the main glycol component is at least one type of glycol selected from ethylene glycol and tetramethylene glycol. Preferably, polyester is used. It goes without saying that the molecular weight, denier, number of filaments, cross-sectional shape, fiber physical properties, microstructure, presence or absence of additives, and polymer properties (terminal carboxyl group concentration, etc.) of the polyester fibers are not limited in any way. The polyepoxide compound used in the first treatment agent of the present invention is a compound containing at least two or more epoxy groups in one molecule in an amount of 0.2 g equivalent or more per 100 g of the compound, and includes ethylene glycol, glycerol, sorbitol, pentaerythritol, polyethylene Resorcinol bis(4
-Hydroxyphenyl)dimethylmethane, phenol-formaldehyde resin, resorcinol-formaldehyde resin and other reaction products of polyhydric phenols and the above-mentioned halogen-containing epoxides, oxidizing unsaturated compounds with peracetic acid or hydrogen peroxide, etc. The resulting polyepoxide compounds include 3,4-epoxycyclohexene epoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexenecarboxylate, bis(3,4-epoxy-6-methyl-cyclohexylmethyl)adipate, and the like. can. Of these,
In particular, reaction products of polyhydric alcohols and epichlorohydrin, ie, polyglycidyl ether compounds of polyhydric alcohols, are preferred because they exhibit excellent performance. Such polyepoxide compounds are usually used as floatation liquids. To make a floating liquid or solution, for example, such a polyepoxide compound as it is or dissolved in a small amount of a solvent as necessary may be mixed with a known floating agent such as sodium alkylbenzene sulfonate or sodium dioctyl sulfosuccinate. Float or dissolve using salt, nonylphenol ethylene oxide adduct, etc. Next, the blocked polyisocyanate compound used in the first treatment agent of the present invention is an addition compound of a polyisocyanate compound and a blocking agent,
The blocking component is liberated by heating to produce an active polyisocyanate compound. Examples of the polyisocyanate compound include tolylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate,
Polyisocyanates such as hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, triphenylmethane triisocyanate,
Alternatively, these polyisocyanates and a compound having two or more active hydrogen atoms, such as trimethylolpropane, pentaerythritol, etc., are combined with an isocyanate group (-NCO) and a hydroxyl group (-
Examples include polyalkylene glycol adduct polyisocyanates containing terminal isocyanate groups obtained by reacting at a molar ratio of OH) exceeding 1. In particular, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and polymethylene polyphenyl isocyanate are preferred because they exhibit excellent performance. Examples of blocking agents include phenol,
Phenols such as thiophenol, cresol, and resorcinol, aromatic secondary amines such as diphenylamine and xylidine, phthalic acid imides,
Examples include lactams such as caprolactam and valerolactam, oximes such as acetoxime, methyl ethyl ketone oxime, and cyclohexane oxime, and acidic sodium sulfite. Examples of the rubber latex used in the first treatment agent of the present invention include natural rubber latex, styrene-butadiene copolymer latex, vinylpyridine-styrene-butadiene terpolymer latex, nitrile rubber latex, chloroprene rubber latex, etc. These can be used alone or in combination. Among these, vinylpyridine-styrene-butadiene terpolymer latex shows excellent performance when used alone or when used in an amount of 1/2 or more. The first treatment agent is the above polyepoxide compound (A),
Contains block polyisocyanate compound (B) and rubber latex (C), and the weight ratio of each component (A), (B), and (C) is (A)/[(A)+(B)] is 0.05 to 0.9 ,(C)/[(A)+(B)
]
It is desirable to use it so that it is between 0.5 and 15. In particular, (A)/[(A)+(B)] is 0.1 to 0.5, (C)/[(A)+
(B)] is preferably in the range of 1 to 10. If (A)/[(A) + (B)] is out of the above range, the rate of rubber adhesion to polyester fibers will decrease. (C)/
If [(A)+(B)] is smaller than the above range, the treated polyester fiber will become hard, which may lead to a decrease in fatigue resistance, while if it is larger than the above range, adhesiveness will be reduced. The total solid content including the polyoxide compound (A), blocked polyisocyanate compound (B) and rubber latex (C) is used in an amount of 1 to 30 wt%, preferably 3 to 20 wt%, based on the weight of the fiber.
If the concentration is too low, the adhesion will decrease, and if the concentration is too high, it will become hard and the fatigue resistance will decrease. When the first treatment agent composition is used as an aqueous dispersion, the appropriate amount of the dispersant, that is, the surfactant, is 0 to 15 wt%, preferably 0 to 15 wt%, based on the total solid content of the first treatment agent.
The content is 10wt% or less, and if it exceeds the above range, the adhesiveness tends to decrease slightly. The second treatment agent of the present invention is a composition containing resorcinol, formalin, and rubber latex, and the resorcinol, formalin, and rubber latex used here is usually called RFL, and the molar ratio of resorcinol and formaldehyde is 1:0.1
-1:8, preferably 1:0.5-1:5, more preferably 1:1-1:4. Examples of rubber latex include natural rubber latex, styrene-butadiene copolymer latex, vinylpyridine-styrene-butadiene terpolymer latex, nitrile rubber latex, chloroprene rubber latex, etc.
These may be used alone or in combination. Among these, vinylpyridine-styrene-butadiene terpolymer latex shows excellent performance when used alone or when used in an amount of 1/2 or more. The blending ratio of resorcinol/formalin and rubber latex is as follows: ethylene urea compound (D) and dicyclopentadiene phenolic epoxy compound.
Depending on the addition ratio of (E), the solid content ratio is 1:1 to 1:1.
The ratio is desirably 1:15, preferably in the range of 1:3 to 1:12. If the proportion of rubber latex is too small, the treated polyester fiber material will become hard and have poor fatigue resistance. On the other hand, if the amount is too large, satisfactory adhesive strength and rubber adhesion rate cannot be obtained. The mixing ratio of ethylene urea compound (D) and dicyclopentadiene phenolic epoxy compound (E) is 40/
60 to 80/20 (weight ratio) is preferable, and the mixture is 0.5 to 30 wt%, preferably 1.0 to 30 wt%, based on the above RFL.
Added at 20wt%. If the amount of the mixture added is too small, good adhesion and rubber adhesion cannot be obtained.
On the other hand, if the amount added is too large, the viscosity of the processing agent will increase significantly, making it difficult to process the fiber material. Moreover, the adhesion force and rubber adhesion rate reach a saturation value, and the effect of eliminating the amount of the mixture added does not increase, and the cost only increases, and the fiber material after treatment becomes extremely hard and loses strength. The disadvantage is that The ethylene urea compound added to the second processing agent is represented by the following general formula (D). [R is an aromatic or aliphatic hydrocarbon residue. n is an integer of 0 to 2, and when n=0, the terminal group is hydrogen. ] Representative compounds include aromatic and aliphatic isocyanates such as octadecyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, metaxylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate, triphenylmethane triisocyanate, and ethylene. Reaction products with imines are mentioned, and in particular aromatic ethylene urea compounds such as diphenylmethane diethylene urea give good results. Similarly, the dicyclopentadiene phenolic epoxy compound added to the second treatment agent is represented by the following general formula (E). Here, R′, R″, and R are either H, CH ₃ , or C ₂ H ₅ , and m is an integer of 0 to 10. Various compounds that satisfy the above (E) can be considered, but
Good results are obtained using a material with a molecular weight of 1200 to 1300 and an epoxy value of 4.0 to 4.5/Kg. In the present invention, ethylene urea compound (D) and dicyclopentadiene phenolic epoxy compound
(E) have a catalytic effect on each other; in the case of ethylene urea compounds, the ethyleneimine ring opens, and in the case of dicyclopentadiene phenolic epoxy compounds, the epoxy rings open and react, increasing adhesion at the same time. It increases the cohesive force of the adhesive itself and as a result forms strong chemical bonds with amines generated in the rubber, thereby preventing adhesive deterioration. The above-mentioned second processing agent is usually adjusted to contain a solid content of 10 to 25% by weight. In order to attach the first treatment agent and the second treatment agent to the polyester fiber material, any method such as contact with a roller, application by spraying from a nozzle, or immersion in a bath liquid can be adopted. The amount of solid content deposited on the polyester fiber is 0.1 to 10% by weight, preferably 0.5% by weight as the first treatment agent composition.
~5% by weight, 0.5~10 as the second treatment agent composition
It is preferable to apply it in an amount of 1 to 5% by weight, preferably 1 to 5% by weight. In order to control the amount of solid content attached to the fibers, means such as squeezing with a pressure roller, scraping with a scraper, blowing off with air, suction, and beating with a beater may be used. In the present invention, after the polyester fiber is treated with the first treatment agent, the temperature is 50°C or more and 10°C or more lower than the melting point of the polyester fiber, preferably 220°C or more.
It is dried and heat-treated at a temperature of 260°C, then treated with a second treatment agent, and dried and heat-treated at a temperature of 120°C or higher and below the melting point of the polyester fiber, preferably 180-250°C. If the drying and heat treatment temperature is too low, adhesion with rubber will be insufficient, while if the temperature is too high, the polyester fibers will melt or fuse, or the strength will be significantly reduced, making it impossible to put it to practical use. <Effects of the Invention> Compared to conventional methods, the fibers treated by the method of the present invention can be molded with rubber without impairing their moldability.
Improves heat-resistant adhesion and peel strength and durability. <Example> Hereinafter, the present invention will be specifically described with reference to Examples. In the Examples, the heat resistance in rubber, cord peeling adhesive strength, T adhesive strength, and inter-ply peeling force were determined as follows. <Heat resistance in rubber> This indicates the strength retention rate after vulcanization in rubber. The cord was taken out from the sulfurized rubber at 170°C for 3 hours, the tensile strength at break was determined at a speed of 200 mm/mm, and the retention rate was determined by comparing it with the initial strength. <Cord peeling adhesive strength> This indicates the adhesive strength between the treated cord and rubber. Five cords are buried near the surface layer of the rubber sheet,
The force required to peel five cords from the rubber sheet at a speed of 200 mm/mm after vulcanization at 150° C. for 30 minutes under pressure is expressed in kg/5 cords. <T adhesive strength> This indicates the adhesive strength between the treated cord and rubber. The cord is embedded in a rubber block, cured under pressure at 150°C for 30 minutes, and then the force required to pull out the cord from the rubber block at a speed of 200 mm/mm is expressed in kg/cm. <Peeling force between plies> Indicates the adhesive force with the treated cord. After embedding 2 plies of treated cords in rubber as a crossbrie (cord density: 27 cords/inch) at a 90 degree angle and vulcanizing at 150°C for 30 minutes, both plies were peeled off at a tensile speed of 200 mm/mm. The force required to do so is expressed in kg/inch. <Rubber adhesion rate> This is a measure of the adhesion of rubber to fibers.
The cord peeled off from the rubber during the inter-ply peel force measurement described above was observed with the naked eye, and the portion of the cord surface to which the rubber was attached is expressed as a percentage. Examples 1 to 3, Comparative Ratios 1 to 4 6 g of Denacol EX-611 (manufactured by Nagase Sangyo Co., Ltd., sorbitol polyglycidyl ether) was added as a surfactant to Neocol SW-30 (Daiichi Kogyo Seiyaku Co., Ltd.).
Add 4 g of 30% aqueous solution of dioctyl sulfosuccinate sodium salt (manufactured by Co., Ltd.) and melt uniformly. Add this to 805g of water while stirring, and add Denacol to 805g of water.
Uniformly dissolve EX-611 in water. Next, Hiren MP (manufactured by DuPont, 44-diphenylmethane diisocyanate phenol block)
A dispersion obtained by mixing 14 g of Nenacol SW-30, 4 g of Nenacol SW-30, and 42 g of water in a ball mill for 24 hours, and Nitupol 2518GL (manufactured by Nippon Zeon Co., Ltd., 40% by weight of vinylpyridine-styrene-butadiene terpolymer floating in water) Add 125g of compound) and mix evenly. The obtained liquid mixture is used as a first treatment agent. In addition, 60 g of resorcinol formalin initial condensate (40% acetone solution) reacted with an acidic catalyst was added to the aqueous solution obtained by adding 10 g of 10% caustic soda aqueous solution and 30 g of 28% ammonia aqueous solution to 260 g of water and stirring well. and stir thoroughly to disperse. Next, 240 g of Nitzpol 2518GL (manufactured by Nippon Zeon Co., Ltd., vinylpyridine-styrene-butadiene terpolymer latex 40% water floatation liquid) and Nitzpol
100g of Lx-112 (manufactured by Nippon Zeon Co., Ltd., 40% styrene-butadiene copolymer floating in water) and 200g of water.
Dilute with The above-mentioned resorcisin/formalin initial condensation dispersion is slowly stirred into this diluted solution, and 20 g of formalin (37% aqueous solution) is added and mixed uniformly. Next, add 14 g of diphenylmethane diethylene urea to this mixture.
An aqueous dispersion obtained by stirring and mixing 5 g of Neocol SW-30 and 36 g of water in a ball mill for 24 hours is added and mixed. Next, 7.2 g of DIPP epoxy DCE-400 (manufactured by Sanyo Kokusaku Pulp Co., Ltd., dicyclopentadiene phenolic polymer epoxy compound) was dissolved in toluene in advance, and Nenacol P (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was dissolved in toluene.
0.1 g of dioctyl sulfosuccinate sodium salt) and 0.6 g of methylcellulose were added and dissolved in 28 g of water with stirring, and the resulting mixture was mixed. shall be. [η] = 0.89 polyethylene terephthalate was melt-spun and stretched according to a conventional method to obtain a 1500 denier/
After obtaining a multifilament of 192 filaments, continue to combine the two multifilaments with 40×
A cord of 3000 denier to 384 filament was obtained by twisting with 40T/10cm. These cords were immersed in the first treatment agent using a computer treater (tire cord treatment machine manufactured by CA Ritzler Co., Ltd.), and then heated at 150°C.
The sample is dried for 2 minutes at 230°C, and then heat treated at 230°C for 1 minute. Next, after being immersed in a second treatment agent, it is dried at 150°C for 2 minutes, and then heat-treated at 230°C for 1 minute.
In the treated polyester tire cord, the solid content of the first treatment agent is 2.2wt%, and the solid content of the second treatment agent is 2.5wt%.
% was attached. The treated cord thus obtained was embedded in a pre-vulcanized rubber containing a carcass containing natural rubber as the main component, and vulcanized at 150°C for 30 minutes (initial value) and at 170°C for 90 minutes (heat resistance value). The above experiment was repeated with various weight ratios of the ethylene urea compound (D) and dicyclopentadiene phenolic epoxy compound (E) as shown in Table 1. The experimental results are shown in Table 1. 【table】

Claims (1)

[Scope of Claims] 1 Linear aromatic polyester fiber is made of polyepoxide compound (A) blocked polyisocyanate compound
(B) and rubber latex (C), and then treated with a resorcinol-formalin rubber latex (RFL) containing an ethylene urea compound represented by the following general formula (D) and a rubber latex (C). A second compound in which a dicyclopentadiene phenolic epoxy compound was added at a weight ratio of D/E = 40/60 to 80/20.
A method for treating polyester fibers, which comprises treating with a treatment agent. [Here, R is an aromatic or aliphatic hydrocarbon residue, and n is 0, 1 or 2. When n=0, the terminal group is hydrogen. ] [Here, R′, R″, R are any of H, CH ₃ , C ₂ H ₅ , and m is an integer of 0 to 10.] 2 The linear aromatic polyester has the general formula [n' is an integer from 2 to 6. ] The method for treating polyester fiber according to claim 1, wherein the polyester fiber has a repeating unit represented by the following as a main component.