JPS6031950B2 - Method for producing polyester fiber material with improved adhesion to rubber - Google Patents

Description

[Detailed description of the invention]

The present invention provides a polyester fiber material for rubber reinforcement that has improved adhesion to a rubber compound, and in particular has significantly improved adhesive strength reduction when exposed to high temperatures for a long time while embedded in a rubber compound. This invention relates to a method for producing a polyester fiber material for rubber reinforcement. Despite having high tensile strength, heat resistance, fatigue resistance, and dimensional stability, polyester fibers (typically polyethylene terephthalate) have been delayed in practical application because they have difficulty adhering to rubber. ) has improved its adhesion to rubber through the development of adhesive treatment methods using adhesives such as epoxy resins, isocyanate resins, ethylene urea resins, and chlorophenol resins, and today it is used in automobile tires, hoses, and belts. It has come to be widely used as a reinforcing material for rubber products such as rubber products. However, conventionally known adhesive-treated polyester fibers
Since it has the disadvantage that its adhesive strength with the rubber compound decreases significantly when exposed to high temperature for a long time in the rubber compound, its usage conditions and applications are limited. It is said that the cause of this decrease in adhesive strength in rubber compounds is the deterioration of polyester fibers due to the action of amines and moisture in the rubber compound. proposals have been made. For example, a chlortriazine compound (French Patent No. 20661 Fuba Specification), isatoic anhydride (Jiko Sho 50-36276), quicklime (Hakamoseki Sho 47-29471), etc. are added to the rubber compound. A method of blocking the action of amines and moisture in the fiber, a method of using polyester fiber with a reduced amount of carboxyl end groups to make it less likely to deteriorate (
Japanese Patent Publication No. 44-27911, Japanese Unexamined Patent Publication No. 703-1987), etc. have been proposed. However, the method of adding these agents to the rubber compound causes undesirable momme points such as blooming and deterioration of the physical properties of the vulcanized rubber, and the method of using polyester fibers with a low amount of carboxylic end groups,
However, these proposals already have the disadvantage that adhesion with rubber becomes more difficult due to the polyester fiber having a small amount of polar groups or functional groups, making it more non-polar or less functional. I have to say that it lacks sex. Further, Tokukan Sho 51-70394 proposes a method in which polyester fibers having a carboxy end group content of 1 ratio q/10 or less are subjected to epoxy compound treatment, polyisocyanate compound treatment, and resorcinol-formalin-rubber latex treatment. However, it is not practical because the polyisocyanate treatment is performed in an organic solvent system and is a three-stage dipping treatment. The present inventors have already discovered that Hakama Kosho 47
No. 1497 Publication (Japanese Patent No. 69276 Specification)
proposed a method for obtaining rubber reinforcing polyester fibers with excellent adhesive strength and adhesive fatigue resistance during high-temperature vulcanization; however, as a result of further investigation, we found that a carrier such as p-chlorophenol could be used as an adhesive. It has been found that by treatment prior to treatment or in the same manner as the adhesive, a polyester fiber material can be obtained which has significantly improved adhesive strength when exposed to high temperatures for long periods in rubber, and has developed the present invention. It's arrived. That is, the present invention does not require the use of polyester fibers having a particularly low amount of carboxyl terminal groups, and even when applied to a rubber compound having a composition commonly used for automobile tires, etc., it is possible to prevent long-term exposure to high temperatures in the rubber. This is a method for producing a polyester fiber material in which the decrease in adhesive strength is significantly improved when the adhesive strength is reduced when }An aqueous dispersion of blocked diisocyanate and/or epoxy resin and a mixed liquid of sulsorcinol-formaldehyde rubber latex are coarsely combined and processed in one or more stages to produce the polyester fiber material. Adhesion to rubber, characterized in that the first stage treatment contains at least the treatment liquid and the final stage treatment contains at least the mixture 'C'. A method for obtaining an improved polyester fiber material. The present invention will be explained in more detail below. The polyester fiber material of the present invention refers to an undrawn yarn (phenol:tetrachloroethane=
The intrinsic viscosity measured at 30qC in a 3:2 mixed solvent is usually 0.65 or higher, and the amount of carboxyl end groups is 3&q
/1 pita or less, usually 15 to 3 k/1 pita), a drawn yarn made by drawing it, a twisted cord made by twisting several pieces of it, or a woven fabric made from it. The polyester fiber material is, for example, Samurai Kosho 47-497.
It may also be made of polyester fibers surface-activated with an epoxy compound or isocyanate compound at the stage of undrawn yarn or drawn yarn, as shown in the Japanese Patent Publication. After being treated with a compound having two or more epixoxy groups (e.g., a reaction product of polyhydric alcohols such as glycerin, propylene glycol, ethylene glycol, bisphenol A, etc., and epichlorohydrin) during the yarn or drawing process. , 15
Extremely excellent effects can be obtained when the yarn is heat-treated at 0 to 260 qo, a cord made from the yarn, or a woven fabric made from the yarn. In the present invention, in order to impart adhesion to rubber to the polyester fiber material, a treatment liquid containing a wind carrier,

[B} Aqueous dispersion of blocked isocyanate and/or epoxy resin and 'C
A mixture of lusorcinol-formaldehyde and rubber latex (hereinafter abbreviated as RFL liquid) is combined with silk and subjected to one or more multi-stage treatments. At that time, in the first stage of processing, at least the processing liquid is
It is essential that the final treatment stage contains at least the mixed liquid (C). That is, in the case of multi-stage processing of two or more stages, the first stage processing is a single process of ,■+[B-,■+{
The final stage treatment is 'q alone, 'qju [B}, {q+wind or 'C]+.
'B] Perform with Tofu treatment liquid. Treatment at any stage between the first stage treatment and the final stage treatment is carried out using a treatment solution prepared by arbitrarily combining one or more of ①, leg and ``C''.
Separately, in the case of one-stage processing, processing is carried out using a processing liquid named Kaze1'B)10[c'. When processing with a treatment liquid that is a mixture of two or more of the three treatment liquids described above, the mixing ratio can be arbitrarily selected, and the mixing ratio in 'B) The mixing ratio of blocked isocyanate and epoxy resin can also be arbitrarily selected within the range of 0/100 to 100/0. The treatment referred to here means that the polyester fiber material is applied with a wind or/and [B or/and '○ treatment liquid by a conventional method such as kiss roll, grid, spray, impregnation or coating, and then , using an oven, hot plate or heated roller, etc. for 10 minutes.
Heat treatment is performed at 0 or 26,000 for 1 second to 10 minutes. In the case of multi-stage treatment of two or more stages, the above treatment liquid application step and subsequent heat treatment step are repeated for each treatment stage.
During this treatment, the polyester fiber material may be in the form of an undrawn yarn, a drawn yarn, a twisted cord, or a woven fabric, as described above. As an example of this treatment, for example, treatment of a drawn polyester fiber yarn with a treatment liquid containing a carrier is performed by applying a spinning oil containing a carrier to the melt-spun polyester fiber yarn using a kiss roll, and then winding it up.
The heat treatment is carried out by passing between slit heaters heated to 180 to 250 q C for 5 seconds. For example, the Koju {B} treatment for twisted yarn cords is performed by immersing the Sun Yarn cord in a treatment solution containing wind and 'B} for several seconds, and then heat-treating it by passing it through an open chamber at 150°C for 2 minutes. It will be held in The processing solution containing a carrier of the present invention is one in which the carrier is dissolved, dispersed, or emulsified in water, and in addition to the carrier, it also contains auxiliary agents such as a solvent, a dispersant, an emulsifier, or a stabilizer. , paper thread oil, etc. may also be contained. The carrier referred to here is a substance that penetrates and diffuses into the polyester fiber, increases the swelling of the polyester fiber, and changes the internal structure of the fiber to make it easier for dye molecules, adhesive molecules, etc. to enter, although its mechanism of action is not fully clear. It is a substance that is thought to act, and its concept is generally well known in the field of dyeing polyester fibers with disperse dyes (for example, Nobuhiko Kuroki's ``Dyeing Theory Chemistry'' Yokosho Shoten). In the present invention, by utilizing the carrier action of the carrier,
Infiltrating the interior of the polyester fiber with an adhesive, i.e., a blocked disocyanate and/or an epoxy resin and/or an RFL, which is treated with or after treatment with the carrier-containing treatment solution (1). This is intended to bond the adhesive more firmly to the polyester fibers. When dyeing polyester fibers with disperse dyes, the carrier effect can be exerted even if the carrier is added to the dye bath containing the disperse dye (comparable treatment), or if the polyester fibers are pretreated with a carrier prior to dyeing. It is well known that this effect can be achieved even with pretreatment. In the treatment of the present invention, even if the adhesive treatment liquid {B- and/or [treatment liquid ■ which has the same rank as CI and contains a carrier (equal rank treatment), or after boiling treatment [B' and Even when treated with 'C' (pre-treatment), the effect of improving adhesion, especially the heat resistance of adhesive strength, was observed. In other words, it seems that the adhesive properties were improved because the adhesive molecules sufficiently penetrated into the polyester due to the carrier action in both the apposition treatment and the pretreatment. In the present invention, the processing liquid containing the carrier must be contained in at least the first stage processing liquid. The reason for this will be clear from the above-mentioned carrier effect and the gist of the present invention which utilizes that effect. Although wind can be included in the treatment chamber after the second stage treatment, the effect of its inclusion is small in view of the above-mentioned gist of the present invention. Furthermore, in the present invention, the final stage treatment must contain at least {C-, that is, RFL liquid. The reason is that the layer that comes into direct contact with rubber when bonding with rubber, that is, the outermost layer on the surface of the polyester fiber material after treatment,
This is because the presence of RFL in the rubber is considered to be the best for adhesion to rubber. The polyester fiber material of the present invention is treated with a treatment liquid W containing a carrier, an aqueous dispersion of a blocked disocyanate and/or an epoxy resin, and an RFL liquid. If the process is performed in two or more stages, the first
The processing of the first stage should be at least ``Ko'', and the processing of the final stage should be at least ``C''.
} is an essential requirement. The object of the present invention cannot be achieved without any of the above essential requirements. For example, when processing one stage with Kazeju'C', after processing the first stage with ■, processing the second stage with {C', the first stage with leg + {q
If you process the second stage with 'B-' after processing the stage, job 10 [C]
In the case of one-stage treatment with the legs, or in the case of the second-stage treatment with the legs after the first stage treatment, the adhesive performance, especially the adhesive strength retention ability when exposed to high temperatures for a long time in rubber, is important. is low. The reason for this is not clear, but if the treatment that satisfies the above-mentioned essential requirements of the present invention is performed, some synergistic effect will occur between the three treatment liquid components; It is believed that the improvement in adhesion to rubber, which is the objective of the invention, can be achieved. Specific examples of the carrier of the present invention include benzoic acid, methyl benzoate, propyl benzoate, benzoic acid derivatives such as m-nitrobenzoic acid, salicylic acid derivatives such as salicylic acid, methyl salicylate, and phenyl p-bromsalicylate. phthalic acid, phthalic acid derivatives such as ethyl phthalate, ketones such as acetophenone, propiophenone, benzophenone, phenol, p
-Chlorphenol/P-nitrophenol, o-phenylphenol, 2,4,6-tribromophenol,
Phenol derivatives such as m-cresol and resorcinol, aromatic ethers such as anisole and p-fromanisole, monochlorobenzene, p-dichlorobenzene,
Halogenated benzenes such as 1,3,5-trichlorobenzene, p-dibromobenzene, methylnaphthalene, Q-
Naphthalene derivatives such as fromnaphthalene, di- and triphenylmethane derivatives such as diphenyldichloromethane, triphenolchloromethane, triphenylcarbinol, diphenyl, 4,4-dioxydiphenyl, 4
・Diphenyl derivatives such as 4'-diaminodiphenyl,
Tricresyl phosphate, general formula, (where m and n are o or positive integers, and the average of m is 1
, the average of n is 1) and p-
Examples include reaction products of chlorophenol and formaldehyde. Among them, preferred examples are p-chlorophenol, o-
Examples thereof include phenol derivatives such as phenylphenol, halogenated benzenes such as mo/chlorobenzene and trichlorobenzene, and reaction products of resorcin, p-chlorophenol, and formaldehyde represented by the above-mentioned one-prong formula. Among the preferred examples, particularly preferred examples are resorcinol and pook. It is a reaction product of phenol and formaldehyde. The reason why phenol derivatives and halogenated benzenes are preferable is not clear, but p-chlorophenol, o-phenylphenol, torchlorbenzene, etc. are said to have an excellent carrier effect when dyeing polyester with disperse dyes. Since this is the carrier used, it is believed that the carrier effect is excellent for the treatment of the present invention. Although it is not clear why the reaction product of resorcinol, p-chlorophenol, and formaldehyde is particularly preferable, it belongs to the above-mentioned preferred phenol derivatives containing p-chlorophenol that have excellent carrier effects, and moreover, The above 'B and/or 'C', especially '
It is thought that this is because it forms a strong bond with the song and/or [C', since it is thought that it reacts with the solcin-formalin condensate in C}. The adhesion rate of such a carrier to the polyester fiber material is preferably 0.1% to 5.0% by dry weight. If it is less than 0.1%, the effect of improving adhesive strength cannot be obtained sufficiently, and if it is less than 5.0%,
If the amount is larger than that, the adhesive strength may actually decrease. As an example, after treating a polyester woven paper twisted yarn cord with an aqueous dispersion of a reaction product of resorcinol, p-chlorophenol, and formaldehyde (Valkabond E manufactured by Varnax), a docaprolactam block of polymethylene polyphenylysocyanate was treated. FIG. 1 shows the relationship between the adhesion rate and the adhesive force of the reaction product of resorcinol as a carrier, p-chlorophenol, and formaldehyde when treated with a mixed treatment solution of an aqueous dispersion and an RFL solution. The aqueous dispersion 'B' of blocked isocyanate and/or epoxy resin, which is the second treatment liquid of the present invention, refers to the blocked isocyanate and epoxy resin illustrated below, either separately or mixed together in advance. It is then prepared by dispersing it in water using a method such as a Pall mill using auxiliary agents such as surfactants, thickeners, and antifoaming agents. The blocked diisocyanates used in the present invention include, for example, monoisocyanates such as phenylisocyanate, dichlorophenyl isocyanate, naphthalene monoisocyanate, n-butyl isocyanate, tolylene diisocyanate, and vitriol diisocyanate. Diisocyanate, dianisidine diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, m-phenylene diisocyanate, m-xylene diisocyanate, alkylbenzene diisocyanate, 1-chlorobenzene-2,4-diisocyanate, cyclohexylmethane diisocyanate, 3,3-dimethoxydiphenyl Methane-4,4'-diisocyanate, 1-nitrobenzene-2,4-diisocyanate, 1-alkoxybenzene-2,4-diisocyanate, ethylene diisocyanate, propylene diisocyanate, cyclohexylene-1
・2-diisocyanate, 3,3-dichloro-4,4'
-biphenylene diisocyanate, diphenylene diisocyanate, 2-chlorotrimethylene diisocyanate, butylene-1,2-diisocyanate, ethylidene diisocyanate, diphenylmethane-4,4-diisocyanate, diphenylethane diisocyanate, 1,5
Diisocyanates such as naphthalene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, diphenylmethane triisocyanate, butane-1.
2,2-triisocyanate, trimethylolpropane tolylene diisocyanate teradduct, 2,4,4'
- Triisocyanates such as diphenyl ether triisocyanate, represented by the general formula, n = 0, 1, 2,
One or more polyisocyanate compounds such as polyfunctional isocyanates such as polymethylene polyphenylisocyanate (including the case of crude diphenylmethane diisocyanate) which is a mixture of 3, 4, etc., and phenol, for example. , phenols such as thiophenol, cresol, and resorcinol, tertiary alcohols such as t-butanol, t-pentanol, and t-butanethiol, aromatic amines such as diphenylamine, diphenylnaphthylamine, and xylidine, ethyleneimine, propyleneimine, etc. Ethyleneimines, imides such as succinimide and phthalimide, active methylene compounds such as acetoacetate, acetylacetone, and malonic acid ester, 2
-Mercaptans such as mercaptobenzothiazole and t-dodecylmercaptan, lactams such as prolactam, 6-butyromulactam, y-butyromulactam, and 8-bropiolactam, urea, diethylene urea, thiourea, etc. Oximes such as acetoxime, cyclohexanone oxime, penzophenone oxime, methyl engineered ethyl ketone oxime, diaryl compounds such as carbazole, phenol naphthylamine, N-phenylxylidine, bisulfites, boric acids, Q - It is obtained by reacting one or more inocyanate blocking agents such as pyrrolidone by a known method. Among them, particularly preferred blocked isocyanates are:
The isocyanate component is a polyisocyanate that at least partially contains molecules having three or more isocyanate groups, such as triphenylmethane triisocyanate, trimethylolpropane tolylene diisocyanate tertiary adduct, etc. Examples include those obtained by blocking polyfunctional polyisocyanates such as triisocyanates and polymethylene polyphenylisocyanate with the blocking agent described above. It is not clear why polyisocyanate blocks containing at least a portion of molecules having three or more isocyanate groups are particularly preferable, but after the blocking agent dissociates, three-dimensional polyisocyanate molecules with three or more functional groups are used. It seems that the formation of a network structure is effective in improving the heat resistance of adhesive strength. Among the above particularly preferred blocked diisocyanates, more preferred are those in which the blocking agent is the lactams, oximes, or ethyleneimines of the above examples,
Examples include those obtained by blocking triphenylmethane IJ isocyanate and polymethylene polyphenyl isocyanate with ethyleneimine, caprolactam, and methyl ethyl ketone oxime. The reasons why lactams and oximes are particularly preferred as blocking agents are that the dissociation temperature of these blocking agents is close to the heat treatment temperature during adhesive treatment, and that they cause little damage to the polyester after dissociation. I think that the. In the case of ethyleneimine, this is probably because an adhesive structure with excellent heat resistance is formed due to a complex reaction accompanying the linkage of the ethyleneimine ring. Examples of epoxy resins used in the present invention include:
Reaction of aliphatic polyhydric alcohols such as glycerin, propylene glycol, ethylene glycol, hexanetriol, sorbitol, trimethylolpropane, 3-methylbentanetriol, polyethylene glycol, and polypropylene glycol with halohydrins such as epichlorohydrin. products, resorcinol, catechol, hydroquinone, 1,3,5-trihydroxybenzene, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)dimethylmethane, 4,4'-bihydroxyphenyl, etc. Reaction products of aromatic polyhydric alcohols and halohydrins such as epichlorohydrin, /borac-type phenolic resins, novolac-type cresol resins, /borac-type resorcinol resins, etc. /borac-type phenolic resins and epichlor Epoxy compounds obtained by oxidizing unsaturated bonds with peracetic acid, such as reaction products with halohydrins such as hydrin, diglycidyl ether, vinylcyclohexene diepoxide, and 3,4-epoxy-6-methylcyclohexenecarboxylate. Particularly preferred are reaction products of novolak-type phenolic resins such as novolac-type phenolic resins, novolac-type cresol resins, and novolak-type resorcinol resins, and halohydrins such as epichlorohydrin. The reason why this epoxy resin is particularly preferable is not clear, but it has excellent heat resistance due to the formation of a three-dimensional network structure due to the presence of the polyfunctional epoxy resin having three or more functionalities and the high cohesive force between the many aromatic rings connected to each other. It is thought that an adhesive layer is formed. R which is the third treatment liquid of the present invention
FL liquid 'C} is an initial condensate obtained by reacting resorcin and formalin under an acid or alkali catalyst,
One or two types of latex such as styrene-butadiene latex, carboxyl group-containing styrene-butadiene latex, styrene-butadiene-vinylpyridine latex, acrylonitrile-butadiene latex, polychloroprene latex, polybutadiene latex, natural rubber latex, etc. The molar ratio of resorcin and formalin is preferably in the range of 1:0.5, but preferably 1:4, and the solid content ratio of resorcin-formalin initial condensate and latex is by weight. A ratio of 5:95 to 5:50 is preferred. In addition, the second aspect of the present invention,
Blocked disocyanate and/or the third treatment liquid
Or an aqueous dispersion of epoxy resin [B' and RFL liquid'
The adhesion rate of C' to the polyester fiber material is not particularly limited, but it is preferably 2 to 15% based on the total solid content of the legs and feet. In the polyester fiber material treated according to the present invention, the block disocyanate and/or epoxy resin and/or RFL, which are the main components of the adhesive, sufficiently penetrate into the inside of the polyester fiber due to the action of the carrier. It is thought that this and the adhesive form a strong bond. The result is a polyester delicate material which has very good adhesion to rubber, particularly its ability to retain adhesion when exposed to high temperatures for long periods in rubber.
The thus obtained polyester fiber material of the present invention has significantly improved adhesive strength reduction when exposed to high temperature for a long time in rubber compared to conventional polyester fiber materials. This is an epoch-making product that can also be applied to reinforcing materials for rubber products such as large tires and belts used under harsh conditions. The present invention will be explained in more detail below using examples, but the present invention is not limited thereto. Note that parts in the examples mean parts by weight. Example 1 An o-phenylphenol carrier (Yamakawa Pharmaceutical Co., Ltd. A carrier-containing suture removal oil treatment solution was prepared by adding Tetrosin OE) 3 (manufactured by Co., Ltd.). On the other hand, a polyethylene terephthalate tube with an intrinsic viscosity of 1.03 (measured at 30°C in a mixed solvent of phenol:tetrachloroethane=3:2) was heated at a shark thread temperature of 305°C with a pore size of 0.
．． The undrawn yarn thus obtained was cooled to a temperature below the secondary transition point of the polymer, and then oiled in the usual manner. The above-mentioned carrier-containing paper thread oil treatment solution was applied using a roller, and the paper thread was wound at a total speed of 0/min. Adhesion rate of carrier is 0.2% based on yarn weight
Met. Next, the film was stretched in two stages to a total of 6 times using heated stretching pins of 9 and 0 and a slit heater of 20 mm, and then fixed-length heat setting was performed using a slit heater at 250°C. The residence time in the slit heater was 2.5 seconds for both stretching and heat setting. The carboxyl terminal group content of the polyethylene terephthalate drawn yarn of 100 plates/192 filaments obtained here was 1.
The weight was q/1 piyu, and the intrinsic viscosity was 0.85 (measured using the method described above). Three of these yarns were twisted together to obtain one cord (uneven twist number x 41. revision/1 rune). The cord thus obtained was made of polyethylene polyphenylysocyanate (Millionate MR manufactured by Nippon Polyurethane Industries).
) 20% aqueous dispersion of caprolactam block (7 parts of water, 1 part of methyl cellulose, 0.6 parts of sodium alkyl sulfonate, 0.1 part of polyethylene glycol monolaurylate, and 1 part of caprolactam block) Polymethylene polyphenyl isocyanate 2
30 parts (30 parts of the mixture was prepared by adding porridge and pulverizing and dispersing for 2 hours in a pole mill) were immersed in the first stage treatment solution diluted with 10 parts of water for 5 seconds, and then placed in heated air at 220 qo. The specimens were heat-treated in a 9-meat sand bath. The processing code thus obtained was then mixed with 5.7 parts of solcin, 6.3 parts of a 37% formalin aqueous solution, and 3 parts of a 10% caustic soda aqueous solution in 185.5 parts of water. 7 parts and aged at 3000 for 6 hours, then added Nippol 251 Spot S [butadiene-styrene-vinylpyridine copolymer latex manufactured by Nippon Zeon ■ (solid content 41
%)] 175.7 parts and 23.6 parts of water added}
immersed in water for 5 seconds, then heated in air at 220 pm for 9 s.
Machi Sunama heat treated. The adhesive adhesion rate of the cord treated with a two-stage adhesive in this way is 3.0% for the first stage adhesive and 2.1% for the second stage adhesive based on the weight of the polyester cord. %Met. The two-stage adhesive treated cord thus obtained was heated at 140°C for 40 minutes with the following rubber compound.
Table 1 shows the results of measuring the H-adhesion strength after 60 minutes of vulcanization and adhesion at 17 and 0 minutes. Rubber compound composition used in the adhesion test Smoked sheet No. 3 70. Kuo SBR-1712
42.0 Zinc white 5
0 Sulfur Yellow 2.5
Stearic acid 2.5〃N-
Cyclohexy-2-penzothiazole sulfenamide (accelerator) 1.0 / Intal 5.
0〃N-Phenyl-N'-isopropyl-P-phenylenediamine (anti-aging agent) 1.5〃FEF carbon black 50〃For comparison, Table 1 shows the presence of a carrier (tetrosin O) in the spinning oil.
Comparative Example 1 shows the H-adhesion strength obtained when processing was carried out under the same conditions as in Example 1 except that E) was not added. As is clear from Table 1, the cord treated according to the present invention (Example 1) has superior adhesion performance compared to Comparative Example 1, which does not use a carrier, especially at 60°C at 170°C.
Extremely high absolute value of adhesive strength and retention of initial adhesive strength (adhesive strength after 40 minutes of vulcanization at 140°C) during high-temperature and long-term vulcanization, i.e. heat resistance of adhesive strength. It had excellent characteristics. Table 1 Example 2 Epon 812 (manufactured by Shell Chemical Co., Ltd.) was added to an aqueous emulsion obtained by dissolving European yarn oil agent 7 base for polyester fibers containing fatty acid esters and nonionic surfactants as main components in 900 parts of water. A paper thread oil treatment solution containing an epoxy compound was prepared by dispersing the 3 base parts (reaction product of glycerin and epichlorohydrin). Polyester fibers were stretched and heat-set under the same conditions as in Example 1, except that this treatment liquid was used in place of the carrier-containing paper yarn oil treatment liquid of Example 1. The amount of carboxyl terminal groups in the polyethylene terephthalate drawn yarn of 100 dishes/192 filaments obtained here was 1 q/1 day, and the solid content deposition rate of the epoxy compound-containing yarn oil treatment liquid was 0 relative to the yarn weight. It was .9%. Three of these drawn yarns were twisted together to obtain one cord (total number of twists x 41.0/10 arcs). The code obtained in this way was added to a 2% aqueous solution of a reaction product of resorcinol, p-chlorophenol, and formaldehyde (Valkabond E manufactured by VALNATUX) {this is VALKABOND E (solid content concentration 2
0%) diluted with 9 parts of water] for 5 seconds, and then heat-treated in heated air at 150°C for 9 days. Next, the treated cord was mixed with a 20% aqueous dispersion of gocaprolactam blocked borimethylene phenyl isocyanate 7 prepared in the same manner as in Example 1, and a phenol novolac type epoxy resin (EPNI1 manufactured by Ciba Geigy).
38) 30 parts of a 20% aqueous dispersion {this was prepared by using EPNII Satoshi in place of the caprolactam-floxed polymethylene polyphenylisocyanate of Example 1} and the same procedure as in Example 1. Adjusted RFL liquid 2
00 parts for 5 seconds in a three-way adhesive treatment solution, and then heat treated in heated air at 220 oo for 2 minutes. The carrier and adhesive adhesion rates of the cord thus obtained by carrier treatment followed by adhesive treatment are 0.4 and 5.0, respectively, based on the weight of the original cord. It was mother weight percent. The H-adhesion strength when this treated cord was hot-adhesed with the rubber compound of Example 1 at 140 qo, 4 powders or 170 qo for 120 minutes is as shown in Table 2. For comparison, Table 2 shows Comparative Example 2 where the treatment was carried out under the same conditions as Example 2 except that the carrier (VALKABOND E) treatment was not applied, and the treatment order of the carrier treatment and adhesive treatment is shown in Table 2. Comparative Example 3 shows a case where the treatment was carried out under the same conditions as in Example 2 except that the conditions were reversed. As is clear from Table 2, the code (
Example 2) was particularly effective at 170°C and
The adhesive strength after 20 minutes of vulcanization was extremely excellent. Table 2 Example 3 All Example 1 except for using a spinning oil treatment solution that does not contain Tetrosin OE, which is a carrier for polyester fibers.
The yarn was woven, stretched, and heat-set under the same conditions as above to obtain 100 plate No. 92 filaments with a carboxyl end group content of 1 stage q/1 night, and an intrinsic viscosity of 0.85 class yarn liquid solid content adhesion rate of 0.8%. A polythelene terephthalate fiber yarn was obtained. Three of these yarns are twisted together to form one cord (number of twists: 39 x 4)
0T/10 enemies). The cord is medium 140, length l
OW, I made a sudare fabric with 25 ends/inch. The thus obtained Sudare fabric was treated with Tetrosin SP (manufactured by Yamakawa Pharmaceutical Co., Ltd.), which is a chlorobenzene carrier.
5 parts were immersed in a treatment liquid mixed in 95 parts of water for 5 seconds, and then heat treated in heated air at 220°C for 2 minutes. Next, a 20% aqueous dispersion of a cresol novolac type epoxy resin (ECN1273 manufactured by Ciba-Geigi Co., Ltd.) (this was prepared by using ECN1273 in place of the caprolactam blocked polymethylene polyphenylisocyanate of Example 1). Soak for 5 seconds, then soak for 2
Heat treatment was performed for 2 minutes in heated air at 2,000 °C. Then, it was immersed in the RFL solution prepared in the same manner as in Example 1 for 5 seconds,
Then, heat treatment was performed for 2 minutes in heated air at 0°C. The solid content adhesion rates of the chlorobenzene carrier, epoxy resin, and RFL in the Sudare fabric treated in these three stages were each 0.54.6 with respect to the original Sudare fabric.
and 1.9%. One cord was extracted from the center of the adhesive-treated sudare fabric thus obtained, and Example 1 was prepared.
140 pm, 40 min or 170 q with rubber compound of
○, H-adhesion strength when vulcanized for 60 minutes is 13
．． 1k9/arc and 9.8k9/ground, and the corresponding H-adhesion force 8.8k9/ground obtained in the case of a sudare fabric treated under the same conditions as in Example 3, except that it was not treated with Tetrosin SP for comparison. It showed extremely high adhesive strength compared to 4.2k9/node. Also, the first stage processing in this example (
carrier treatment) and second stage treatment (eboxy resin treatment)
The daily adhesion strength when the process was performed under the same conditions as in this example except that the order of was changed was 9.
0ko/, 170℃, 60 minutes vulcanization is 4.3k9
It was an arc. Furthermore, when all the processing orders in this example were changed, and RFL treatment was performed in the first stage, carrier treatment was performed in the second stage, and epoxy resin treatment was performed in the third stage, the H-adhesion strength was 140 qo and 40 minutes was applied. In the case of sulfur, it was 3.8k9/press, 170qo, and in the case of 60 minutes vulcanization, it was 35k9/arc. Example 4 The same untreated sudare fabric as in Example 3 was treated with Vulcabond E (
20% aqueous dispersion of ethyleneimine block of diphenylmethane diisocyanate (solids content 20%) and ethyleneimine block of diphenylmethane diisocyanate (this is the same as in Example 1). After being immersed for 5 seconds in a treatment solution prepared by mixing 4 parts of water and 4 parts of water (prepared using a block body), it was heat-treated for 9 times in heated air at 20 pi. Next, a 20% aqueous dispersion of methyl ethyl ketone oxime blocked polymethylene polyphenylisocyanate prepared in the same manner as in Example 1 (this is a 20% aqueous dispersion of methyl ethyl ketone oxime blocked polyphenylsocyanate in place of the do-caprolactam blocked disocyanate compound in Example 1). (prepared using methylene polyphenylysocyanate)
and RFL liquid for 5 seconds in a 20:80 (weight ratio) mixture, and then treated in heated air at 23,000 for 2 minutes. The total adhesion rate of VALKABOND E and the ethyleneimine block of diphenylmethane diisocyanate was 3. The total deposition of methyl ethyl ketone oxime blocked polymethylene polyphenyl isocyanate and RFL was 2.2 weight percent on the untreated sdale fabric. When one cord was extracted from the center of the thus obtained adhesive-treated sudare fabric and vulcanized and bonded with the rubber compound of Example 1 for 40 minutes at 14,000 o0 or 60 minutes at 170 o0, the H-adhesion strength was 14, respectively. .8kg/Togato 11
．． 4 kg/cm, showing extremely high initial acid adhesion strength and heat-resistant adhesive strength. For comparison, we investigated the H-adhesive strength when treated under the same conditions as in Example 4 except that Vulcan Bond E was not added. The value is 9.0 for each
kg/skin and 44 kg/skin, which was a much lower value than in Example 4. As another comparative example, ethyleneimine block 2 of diphenylmethane diisocyanate was added to the first treatment liquid.
Adding 5 parts of water instead of 5 parts of 0% aqueous dispersion and adding 2 parts of methyl ethyl ketone oxime blocked polymethylene polyphenylisocyanate in the second treatment solution.
When treated under the same conditions as in Example 4 except for using an RFL solution that does not contain 0% moisture, the H-adhesion strength was 8.3X9/2, 17 when vulcanized at 140°C for 40 minutes.
In the case of 0qo, 6-shot vulcanization, the arc was 4.5k9', and only a very low adhesive strength was obtained compared to Example 4, which contained blocked disocyanate in the first and second treatment liquids. Ta. Furthermore, in this example, the order of the first stage treatment and the second stage treatment was changed, and the other conditions were the same as in this example, and the H-adhesion strength was as follows: 9.1
k9/en, 17pi0, 60 minutes vulcanization is 4.4X9/
It was. Example 5 The same cord used in Example 2 was mixed with 1 part of Vulkabond E (solid content 20%) and the same caprolactam blocked polymethylene polyphenylisocyanate/phenol novolac type epoxy resin used in Example 2. RF
L = 70/30/200 (solid content weight ratio) 75 parts of a three-way mixed adhesive processing solution (total solid content concentration 20%) and immersed for 5 seconds in a carrier-containing adhesive processing solution diluted with 15 parts of water. , and then heat treated in heated air at 220° C. for 9 inspections. The treatment code was further applied to the same methyl ethyl ketone oxime as used in Example 4. Polymethylene polyphenylisocyanate/RFL=20/80 (solid content weight ratio) mixed adhesive treatment solution (total solid content concentration 20%) for 5 seconds, then in heated air at 23,000 °C for 90 seconds Heat treated. The solid content adhesion rates of the first-stage and second-stage treatment agents to the untreated cord were 5.0 and 2.4% by weight, respectively. The treatment cord thus obtained was treated with the same rubber compound as in Example 1 at 140q0, 40 minutes and 17pi0,
When the H-adhesion strength was measured after 12 minutes of vulcanization and adhesion, they were 19.0k9/arc and 11.0k9/arc, respectively, and the cords were treated under the same conditions as Example 5 except that Vulkabond E was not added. High adhesion compared to the corresponding H-adhesion of 17.6k9/arc and 5.9kg, especially 170oo
A cord with significantly improved adhesive strength after 120 minutes of vulcanization was obtained. Example 6 The same untreated cord used in Example 2 was mixed with 2 parts of Vulkabond E (20% solids) and a 20% water dispersion of caprolactam blocked 4,4',4''-triphenylmethane triisocyanate. Liquid (prepared in the same manner as the blocked disocyanate aqueous dispersion in Example 1) 20
The specimen was immersed for 5 seconds in a treatment solution in which a portion of the specimen was mixed with an RFL solution (prepared in the same manner as in Example 1) and 6 foundations, and then heat-treated in heated air at 0° C. for 120 seconds. The dry weight increase rate of the cord before and after the treatment was 6.4%. The thus obtained treated cord was vulcanized and bonded with the same rubber compound as in Example 1 at 14 pi, 4 powders, and 170 qC for 120 minutes, and the H-adhesion strength was measured.
0k9/arc and 9.0k9/arc, and the corresponding adhesive strength of the cord treated under the same conditions as Example 6 except that water was used instead of Vulkabond B was 168 kg/arc and 4.8k9/arc. A cord with extremely high adhesion strength, especially when cured at 170°C for 120 minutes, was obtained.

[Brief explanation of drawings]

Figure 1 shows the relationship between the adhesion rate and adhesive strength of the reaction product of resorcinol, p-chlorophenol, and formaldehyde, which is a carrier, when treated with an RFL solution containing blocked isocyanate after carrier treatment. This is a graph showing.

Claims (1)

[Scope of Claims] 1. When imparting adhesion to rubber to a polyester fiber material, (A) a treatment liquid containing a carrier, (B) a dispersion of blocked isocyanate and/or epoxy resin, and (C) a treatment liquid containing a carrier. ) The polyester fiber material is treated in one or more multi-stage treatments using a combination of the three resorcinol-formaldehyde-rubber latex mixed liquids, and the first-stage treatment bath contains at least the above-mentioned treatment liquid ( A method for producing a polyester fiber material with improved adhesion to rubber, characterized in that the final treatment bath of A) contains at least the mixed liquid (C). 2. The method for producing a polyester fiber material according to claim 1, wherein the number of processing stages is two or more stages. 3 The number of treatment stages is two, and the first stage treatment bath contains the treatment liquid (A) and the mixed liquid (C), and the second stage treatment bath contains the aqueous dispersion (B) and the mixed liquid (C). A method for producing a polyester fiber material according to claim 1 or 2. 4. Claim 1, wherein the number of treatment stages is two, and the first stage treatment bath contains the treatment liquid (A), and the second stage treatment bath contains the aqueous dispersion (B) and the mixed liquid (C). A method for producing a polyester fiber material according to item 1 or 2. 5 The number of treatment stages is three, and the first stage treatment bath contains the treatment liquid (A), the second stage treatment bath contains the aqueous dispersion (B), and the third stage treatment bath contains the mixed liquid (C). A method for producing a polyester fiber material according to claim 1 or 2. 6 The number of treatment stages is two, and the first stage treatment bath contains the treatment liquid (A) and the aqueous dispersion (B), and the second stage treatment bath contains the aqueous dispersion (B) and the mixed liquid (C). A method for producing a polyester fiber material according to claim 1 or 2. 7 The polyester fiber material undergoes two steps in the spinning or drawing process.
Claims 1 to 2 are a yarn obtained by treating with an epoxy compound having at least 3 epoxy groups and then heat-treating at 150 to 260°C, a cord made by twisting the yarn, or a fabric woven from the yarn. A method for producing a polyester fiber material according to any one of Item 6. 8. The carrier is selected from phenol derivatives such as o-phenylphenol and p-chlorophenol, halogenated benzenes such as monochlorobenzene and trichlorobenzene, and reaction products of resorcinol, p-chlorophenol, and formaldehyde. A method for producing a polyester fiber material according to any one of claims 1 to 7. 9. The polyester fiber material according to any one of claims 1 to 8, wherein the isocyanate component of the blocked isocyanate is a polyisocyanate that at least partially contains molecules having three or more isocyanate groups. Manufacturing method. 10 The blocking agent component of blocked isocyanate is
A method for producing a polyester fiber material according to any one of claims 1 to 9, wherein the polyester fiber material is a lactam, oxime or ethyleneimine. 11. Any one of claims 1 to 10, wherein the epoxy resin is a reaction product of a novolak-type phenolic resin or/and a novolak-type cresol resin or/and a novolak-type resorcinol resin with a halohydrin such as epichlorohydrin. Method of manufacturing the polyester fiber material described.