JP2024039122A - Polyester fiber cord for rubber reinforcement - Google Patents

Abstract

[Problem] A polyester fiber cord for rubber reinforcement, which is made of a new adhesive treatment agent that does not contain resorcin-formaldehyde resin and uses alternative raw materials that are advantageous in reducing environmental impact, exhibits initial adhesive strength equal to or greater than that of conventional RFL adhesives, and has significantly improved heat-resistant adhesive strength when exposed to high temperatures for a long period of time in rubber during the rubber vulcanization process or product use, and has improved fatigue resistance, making it suitable as a tire reinforcement material. Also provided is a polyester fiber cord for rubber reinforcement, which can suppress the accumulation of resin residue in the dipping process and has good productivity. [Solution] A polyester fiber cord for rubber reinforcement, in which polyester fibers are coated with a first treatment agent containing at least four types of compounds: (A) a compound containing an oxazoline group, (B) a blocked isocyanate compound, (C) a rubber latex, and (D) an epoxy compound, and further coated with an outer layer of a second treatment agent containing at least three types of compounds: (a) a lignin derivative, (b) a blocked isocyanate compound, and (c) a rubber latex, and the first treatment agent is, based on a total solid content of 100% by weight, A polyester fiber cord for rubber reinforcement, comprising (A) 10 to 50% by weight of a compound containing an oxazoline group, (B) 3 to 13% by weight of a blocked isocyanate compound, (C) 20 to 60% by weight of a rubber latex, and (D) 20 to 60% by weight of an epoxy compound, wherein the (a) lignin derivative contained in the second treatment agent has a number average molecular weight of 10,000 to 60,000 and a weight average molecular weight of 80,000 to 130,000, and does not contain a resorcinol-formaldehyde resin. [Selected Figure] None

Description

The present invention relates to a rubber-reinforcing polyester fiber cord that is made of a new adhesive treatment agent that is advantageous in reducing environmental impact and has significantly improved heat-resistant adhesive strength.

Synthetic fibers such as nylon fibers, polyester fibers, and aromatic polyamide fibers are widely used as reinforcing materials in rubber products such as tires, hoses, and belts. As a means for adhering these synthetic fibers and rubber compositions of rubber products, RFL (resorcinol formalin latex) adhesives containing resorcinol, formaldehyde resin consisting of resorcinol and formalin, and rubber latex have been widely used. However, both resorcinol and formalin are deleterious substances, have a high environmental impact, and are harmful to health, so in recent years there has been a demand to suppress their release into the atmosphere during use and to reduce their usage.

In addition, as mentioned above, synthetic fibers are widely used as reinforcing materials in rubber products, but polyester fibers have excellent strength, elastic modulus, and thermal dimensional stability, so they are particularly suitable for use in tire applications. has been done. When polyester fibers are embedded in rubber products and used as reinforcing materials, they undergo thermal deterioration in high-temperature environments. Its chemical thermal deterioration is affected by the rubber itself and various additives blended into the rubber. Polyester fibers that have been subjected to high temperature treatment in rubber containing amine-based anti-aging agents mainly contain these amine-based compounds, low molecular weight compounds and water molecules generated by oxidative deterioration of the rubber itself, and water molecules contained in the rubber. It is decomposed into amines and hydrolyzed by moisture, etc. Such amine-decomposed or hydrolyzed polyester fibers have a problem in that their initial properties such as adhesiveness and strength are significantly reduced, making them unusable.

When polyester fibers undergo amine decomposition or hydrolysis, the strength decreases due to molecular chain scission, and the adhesion between the rubber and the fiber layer decreases. However, although polyester fibers have these drawbacks when used as rubber reinforcing fibers, they have high strength, high modulus of elasticity, excellent thermal dimensional stability, and progress has been made in improving fatigue resistance and adhesion. Coupled with technological improvements, in recent years it has been used as the carcass material for most passenger car radial tires. However, because it has the above-mentioned essential drawbacks, it is used only for carcass materials for passenger cars with relatively small tire sizes, as it is difficult to trap the heat generated when tires run at high speeds and is resistant to chemical deterioration. is the current situation. It is only used in a small number of large tires for trucks, buses, etc. Generally, polyester fiber cords are not used for cap ply materials of truck, bus tires, aircraft tires, run-flat tires, radial tires, etc.

Cap ply materials and run-flat tire reinforcement materials generate more heat and reach higher temperatures than carcass materials, so conventional polyester fiber cords cannot withstand their use, and nylon 66 and rayon fibers, which have excellent heat-resistant adhesive strength, are generally used. has been done. Polyester fibers are preferred as the fiber material for tire reinforcing materials in terms of cost, supply stability, and elastic modulus, but in order to apply them to these uses, it is necessary to significantly improve the heat-resistant adhesive strength of polyester fiber cords.

In addition, in order to make the fibers have adhesive properties with rubber, it is essential to treat the fiber surface with an adhesive represented by the above-mentioned RFL, but in the adhesive treatment process, the adhesive composition applied Resin scum may adhere to processing equipment such as the rolls of dipping machines, making continuous production difficult due to cleaning, resulting in decreased productivity, and resin scum accumulated on the rolls may be transferred to the surface layer of the dip cord, resulting in quality abnormalities. There was a problem with connecting.

As techniques for solving the above problem, there are, for example, the prior art disclosed in Patent Documents 1 to 6.

Patent Document 1 discloses a method of treating polyester fibers with an aqueous adhesive composition containing a thermosetting resin having a specific functional group and an unsaturated elastomer latex.

Patent Document 2 describes at least one component selected from the group consisting of polyphenols, chlorophenol resins, and lignin resins, and at least one component selected from water-soluble polymers other than the above-mentioned components or water-dispersible polymers other than the above-mentioned components. A method for treating polyester fibers with an organic fiber adhesive containing one component is disclosed.

Patent Document 3 discloses a method of treating polyester fibers with an aqueous adhesive composition containing a specific trifunctional or higher functional blocked isocyanate oligomer, latex, polyacrylate or lignin compound, and additives.

Patent Document 4 discloses a method in which polyester fibers are treated with a treatment liquid containing a carrier and a blocked isocyanate aqueous solution, and then treated with RFL containing an epoxy compound.

Patent Document 5 discloses a method in which polyester fibers are treated with a treatment liquid containing a thermoplastic polymer, a heat-reactive water-based urethane, and an epoxy compound, and then treated with RFL.

Patent Document 6 discloses a method in which polyester fibers are treated with a treatment agent containing three types: a compound containing an oxazoline group, an epoxy compound, and rubber latex, and then treated with RFL.

Special table 2019-518087 publication WO2018/003572 US Publication No. 2020/0024416 Japanese Patent Application Publication No. 2006-2327 Japanese Patent Application Publication No. 2001-19927 Japanese Patent Application Publication No. 2013-10909

However, although Patent Documents 1 to 3 do not use resorcinol/formaldehyde resin and exhibit adhesive strength comparable to conventional RFL adhesives, they do not require further improvement in heat-resistant adhesive strength, improved fatigue resistance in rubber, and The contribution to performance improvement was not sufficient. Although Patent Documents 4 to 6 show improvement in heat-resistant adhesive strength, they all use conventional RFL adhesives and have the problem of a large environmental burden. Furthermore, in all of Patent Documents 1 to 6, the production problem of accumulation of resin residue during the dipping process remained.

The present invention was developed as a result of research aimed at solving the problems in the prior art described above.

The object of the present invention is to provide a polyester fiber cord for rubber reinforcement made of a new adhesive treatment agent that does not contain resorcinol/formaldehyde resin and uses alternative raw materials that are advantageous in reducing environmental impact, and which is equivalent to or superior to conventional RFL adhesives. It exhibits an initial adhesion strength of This invention relates to polyester fiber cord for rubber reinforcement. Furthermore, the present invention provides a polyester fiber cord for rubber reinforcement that can suppress resin scum accumulation in a dipping process and has good productivity.

In order to solve this problem, the present invention employs the following means.

That is,
(1) The polyester fiber is coated with a first treatment agent containing at least four types: (A) a compound containing an oxazoline group, (B) a blocked isocyanate compound, (C) rubber latex, and (D) an epoxy compound, and A polyester fiber cord for rubber reinforcement, the outer layer of which is coated with a second treatment agent containing at least three types: (a) a lignin derivative, (b) a blocked isocyanate compound, and (c) rubber latex; The total solid content of the agent is 100% by weight, (A) 10 to 50% by weight of a compound containing an oxazoline group, (B) 3 to 13% by weight of a blocked isocyanate compound, and (C) 20 to 60% by weight of rubber latex. % by weight, (D) contains 20 to 60% by weight of the epoxy compound, and the number average molecular weight of (a) lignin derivative contained in the second treatment agent is 10,000 to 60,000 and the weight average molecular weight is 80,000. ~130,000, and is characterized by not containing resorcinol or formaldehyde resin.

(2) The polyester fiber cord for rubber reinforcement as described in (1) above, wherein the blocked isocyanate compound (B) contained in the first treatment agent is a bifunctional MDI-based blocked isocyanate.

(3) The polyester fiber cord for rubber reinforcement as described in (1) above, wherein the blocked isocyanate compound (b) contained in the second treatment agent is a bifunctional MDI-based blocked isocyanate.

(4) The blocked isocyanate compound (B) contained in the first treatment agent is a bifunctional MDI-based blocked isocyanate, and the blocked isocyanate compound (b) contained in the second treatment agent is The polyester fiber cord for rubber reinforcement as described in (1) above, which is a bifunctional MDI-based blocked isocyanate.

(5) The rubber latex (C) contained in the first treatment agent includes VP latex having a Mooney viscosity (ML1+4 100°C) of 20 to 100 and a Tg of -70°C to -30°C. The polyester fiber cord for rubber reinforcement as described in (1) above.

(6) The rubber latex (c) contained in the second treatment agent includes VP latex having a Mooney viscosity (ML1+4 100°C) of 20 to 100 and a Tg of -70°C to -30°C. The polyester fiber cord for rubber reinforcement as described in (1) above.

(7) The blocked isocyanate compound (B) contained in the first processing agent is a bifunctional MDI-based blocked isocyanate, and the blocked isocyanate compound (b) contained in the second processing agent is , is a bifunctional MDI-based blocked isocyanate, and furthermore, the rubber latex (C) contained in the first processing agent has a Mooney viscosity (ML1+4 100°C) of 20 to 100 and a Tg of -70°C to -30. ℃, and the (c) rubber latex contained in the second treatment agent is a VP latex with a Mooney viscosity (ML1+4 100℃) of 20 to 100 and a Tg of -70℃ to -30℃. The polyester fiber cord for rubber reinforcement as described in (1) above, characterized in that it contains latex.

(8) The oxazoline group-containing compound (A) contained in the first treatment agent has a Tg of 0 to 80°C and an oxazoline group content of 1.0 to 5.0 mmol/g, solid. The polyester fiber cord for rubber reinforcement according to any one of (1) to (7) above.

(9) The polyester fiber cord for rubber reinforcement as described in any one of (1) to (7) above, wherein the cord surface layer has a tackiness of 2.0 to 10.0 N/cm ² .

(10) Second processing agent When the total solid content is 100% by dry weight of the processing agent, the content of (a) lignin derivative is 5 to 50% by weight, and (a) the lignin derivative and ( b) The solid content weight ratio of the blocked isocyanate compound is (solid content of a):(solid content of b) = 10:1 to 10:20. The polyester fiber cord for rubber reinforcement according to any one of the above.

(11) The amount of resin deposited in the film formed by the first treatment agent is 1 to 4% by weight, and the amount of resin deposited in the film formed by the second treatment agent is 1 to 4% by weight, and the amount of resin deposited in the film formed by the first treatment agent is 1 to 4% by weight. The polyester fiber cord for rubber reinforcement as described in any one of (1) to (7) above, characterized in that the total amount of resin deposited in the coating by the second treatment agent is 2 to 6% by weight.

(12) A tire made using the rubber-reinforcing polyester fiber cord according to any one of (1) to (11) above.

According to the present invention, a polyester fiber cord for rubber reinforcement is made of a new adhesive treatment agent that does not contain resorcinol/formaldehyde resin and uses alternative raw materials that are advantageous in reducing environmental impact, and is equivalent to or better than conventional RFL adhesives. It exhibits an initial adhesion strength of This invention relates to polyester fiber cord for rubber reinforcement. Further, it is possible to provide a polyester fiber cord for rubber reinforcement that can suppress resin residue accumulation in the dipping process and has good productivity.

The present invention will be explained in detail below.

The polyester fiber cord for rubber reinforcement of the present invention is characterized in that the polyester fiber contains at least four types: (A) a compound containing an oxazoline group, (B) a blocked isocyanate compound, (C) rubber latex, and (D) an epoxy compound. The outer layer is further coated with a second treatment agent containing at least three types: (a) a lignin derivative, (b) a blocked isocyanate compound, and (c) rubber latex.

The polyester fiber used in the present invention is preferably a fiber made by melt-spinning and drawing a polyester containing terephthalic acid as the main difunctional carboxylic acid and ethylene glycol as the main glycol component. , 6-naphthalene dicarboxylic acid, 4,4-dicarboxyphenoxyethane, isocyanate groups, etc., and fibers made of polyester in which ethylene glycol is partially or completely replaced with diethylene glycol, propylene glycol, butanediol, etc. can also be used.

Further, the polyester may be a copolymer of a trifunctional compound such as trimesic acid, trimellitic acid, boric acid, phosphoric acid, glycerin, and trimethylolpropane, as long as the amount is small.

The polyester fiber cord for rubber reinforcement of the present invention has excellent mechanical properties such as high strength, high toughness, high modulus of elasticity, low shrinkage, and high fatigue resistance, and can be exposed to high temperatures for a long time in rubber. In order to suppress adhesive deterioration and strength deterioration, the polyester fiber used in the present invention preferably has the following properties.
(1) Intrinsic viscosity (IV) = 0.7 to 1.2, more preferably 0.8 to 1.1
(2) Carboxyl terminal group (COOH) = 10 to 30 eq/t, more preferably 12 to 25 eq/t
(3) Content of diethylene glycol (DEG) = 0.5 to 1.5% by weight, more preferably 0.5 to 1.2% by weight
(4) Strength (T) = 6.0 to 10.0 cN/dtex, more preferably 7.0 to 9.0 cN/dtex
(5) Elongation (E) = 8-20%, more preferably 10-16%
(6) Intermediate elongation (ME) = 4.0 to 6.5%, more preferably 4.5 to 6.0%
(7) Dry heat shrinkage rate (ΔS150°C) = 2.0 to 12.0%, more preferably 3.0 to 10.0%.

In order for the polyester fiber used in the rubber-reinforcing polyester fiber cord of the present invention to have particularly chemical durability, it is advantageous that the polyester fiber has a high viscosity, a low amount of carboxyl terminal groups, and a low content of diethylene glycol.

The polyester fiber used in the present invention may be modified with a terminal carboxyl group capping agent such as a carbodiimide compound, an epoxy compound, an isocyanate compound, and an oxazoline compound in order to reduce the number of carboxyl terminal groups.

Moreover, the polyester fiber of the present invention may be one to which a polyepoxide compound has been added in advance in the spinning process. Examples of the polyepoxide compound that can be used in the present invention include compounds containing at least two or more epoxy groups in one molecule in an equivalent amount of 0.1 g or more per 100 g of the compound. Specifically, these include reaction products of polyhydric alcohols such as pentaerythritol, ethylene glycol, polyethylene glycol, propylene glycol, glycerol, and sorbitol with halogen-containing epoxides such as epichlorohydrin, and unsaturated products such as peroxide or hydrogen peroxide. Polyepoxide compounds obtained by oxidizing compounds, namely 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexenecarboxylate, bis(3,4-epoxy-6-methyl-cyclohexylmethyl)adipate, phenol novolak type , hydroquinone type, biphenyl type, bisphenol S type, brominated novolac type, xylene-modified novolak type, phenolglyoxal type, trisoxyphenylmethane type, trisphenol PA type, and bisphenol type polyepoxides. Particularly preferred are sorbitol glycidyl ether type and cresol novolac type polyepoxides.

These compounds are usually used in the form of emulsions, but in order to make emulsions or solutions, the compounds may be used as they are, or if necessary, dissolved in a small amount of solvent and added with known emulsifiers, such as It is used by emulsifying or dissolving it using sodium alkylbenzene sulfonate, dioctyl sulfosuccinate sodium salt, nonylphenol ethylene oxide adduct, etc.

The polyepoxide compound is applied together with a spinning oil in the polyester fiber spinning process. The amount of the polyepoxide compound deposited at this time is in the range of 0.1 to 5% by weight. If the amount of the polyepoxide compound attached is less than 0.1% by weight, the effect of the polyepoxide compound may not be sufficiently exhibited, and there is a possibility that satisfactory adhesion between the polyester fiber and the rubber may not be obtained. On the other hand, if the amount of the polyepoxide compound exceeds 5% by weight, the fiber becomes extremely hard, making it difficult to apply it during the spinning process, and also reducing the permeability of the treatment agent used in the next process. As a result, adhesive performance deteriorates, which is not preferable.

The polyester fiber used in the present invention is not subject to restrictions on fineness, number of filaments, cross-sectional shape, etc., but usually, a total fineness of 200 to 5000 dtex, 30 to 1000 filaments, circular cross-section yarn is used, and a total fineness of 250 to 3000 dtex, 50 ~500 filaments, circular cross-section yarns are more preferred. If the total fineness is less than 200 dtex, the strength of the cord may be insufficient, and if it exceeds 5000 dtex, the cord may become thick and the handleability may deteriorate. Further, if the number is less than 30 filaments, the cord may become hard and the handling properties may deteriorate, and if it exceeds 500 filaments, there may be a lot of fuzz and the quality may deteriorate.

The polyester fiber cord for rubber reinforcement of the present invention can be obtained by twisting the above-mentioned polyester fibers into a twisted cord, and then treating the twisted cord as it is or by weaving it into a raw blind and then treating it with an adhesive. The raw cord used for normal carcass tire cord is first twisted in the S or Z direction, then two or three first twisted cords are put together and the same number of final twists are usually applied in the opposite direction to the first twisted cord to form a plied cord. That is. This twisted cord is treated with an adhesive to obtain a dipped cord. On the other hand, after weaving a twisted cord as a warp and a cotton thread as a weft, or covering a synthetic fiber with a cotton thread as a weft into a raw blind fabric, the raw blind fabric is treated with an adhesive to obtain a dipped fabric.

The polyester fiber cord for rubber reinforcement of the present invention refers to both the above-mentioned dipped cord and dipped fabric.

The polyester fiber cord for rubber reinforcement of the present invention is characterized in that the polyester fiber contains at least four types: (A) a compound containing an oxazoline group, (B) a blocked isocyanate compound, (C) rubber latex, and (D) an epoxy compound. The outer layer is further coated with a second treatment agent containing at least three types: (a) a lignin derivative, (b) a blocked isocyanate compound, and (c) rubber latex.

The compound containing an oxazoline group (A) used in the first treatment agent of the present invention refers to a compound containing an oxazoline group (preferably 2-oxazoline refers to a compound containing Although the skeleton can have one or more oxazoline groups, it is more preferable to have a large number of oxazoline groups, which are reactive functional groups, in order to improve adhesive performance. Hydrocarbon chains, ethylene glycol chains, bisphenols such as bisphenol A, and initial polymers such as phenol resins, novolak resins, and resol resins are used as the main chain skeletons of oxazoline group-containing compounds, and their molecular skeletons contain Substances containing aromatic rings or heterocycles are also used. Furthermore, substances containing an oxazoline group at the end or side chain of the main component monomer and/or a polymer or oligomer made thereof are also useful. These monomers include styrene, styrene derivatives, acrylonitrile, methacrylic esters, methacrylic acid, ethylene, butadiene, acrylamide, etc., and these are used as individual polymers and/or oligomers, and also as copolymerized substances. . It can also be used as a mixture of these.

The oxazoline group-containing compound may be used in the form of a liquid, molten, solid, or a solution in water or an organic solvent capable of dissolving these, or in the form of a suspension dispersed in water (emulsion particles, latex particles, etc.). For example, such a compound may be used as is, or dissolved in a small amount of solvent as necessary, and emulsified or dissolved using a known emulsifier, such as sodium alkylbenzenesulfonate, sodium dioctyl sulfosuccinate, or nonylphenol ethylene oxide adduct.

The oxazoline group-containing compound preferably has a Tg (glass transition temperature) of 0 to 80°C and an oxazoline group content of 1.0 to 5.0 mmol/g, solid, more preferably Tg (glass transition temperature) It is preferable that the temperature is 10 to 70°C and the amount of oxazoline group is 1.2 to 3.0 mmol/g, solid. Outside this range, heat-resistant adhesive strength may decrease.

The blocked isocyanate compound (B) used as the first treatment agent in the present invention is a compound whose blocking agent is released by heating to generate an active isocyanate compound. Blocked isocyanate compounds include polyisocyanate compounds having skeletons such as diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), and triphenylmethane triisocyanate, and phenols such as phenol, cresol, and resorcinol. Examples include reaction products with blocking agents such as lactams such as ε-caprolactam and valerolactam, and oximes such as acetoxime, methyl ethyl ketoxime, and cyclohexane oxime.

Among these blocked isocyanate compounds, bifunctional MDI-based blocked isocyanates in which diphenylmethane diisocyanate is blocked with a blocking agent are particularly preferred in terms of obtaining good adhesive strength and fatigue resistance. More preferred are bifunctional MDI-based blocked isocyanates blocked with oximes. Note that polymeric MDI having three or more functional isocyanate groups is not preferable because fatigue resistance may decrease.

The rubber latex (C) that can be used in the first treatment agent of the present invention is, for example, natural rubber latex, butadiene rubber latex, styrene-butadiene rubber latex, vinylpyridine-styrene-butadiene rubber latex, nitrile rubber latex, hydrogenated nitrile Examples include rubber latex, chloroprene rubber latex, chlorosulfonated rubber latex, ethylene propylene diene rubber latex, and these can be used alone or in combination. Among these, VP latex with a Mooney viscosity (ML1+4 100°C) of 20 to 100 and a Tg of -70°C to -30°C, more preferably a Mooney viscosity (ML1+4 100°C) of 30 to 80 and a Tg of -60°C. It is preferable from the viewpoint of adhesive strength and fatigue resistance that it contains VP latex at a temperature of -40°C.

The epoxy compound (D) that can be used in the first treatment agent of the present invention has two or more epoxy groups in one molecule.

Compounds having two or more epoxy groups in the molecule include, for example, glycidyl ether type epoxy resin obtained from a compound having a hydroxyl group in the molecule, glycidyl amine type epoxy resin obtained from a compound having an amino group in the molecule, Glycidyl ester type epoxy resin obtained from a compound having a carboxyl group in the molecule, a cycloaliphatic epoxy resin obtained from a compound having an unsaturated bond in the molecule, a heterocyclic epoxy resin such as triglycidyl isocyanate, or selected from these. These include epoxy resins in which two or more types coexist within the molecule.

Specific examples of glycidyl ether type epoxy resins include bisphenol A type epoxy resins obtained by the reaction of bisphenol A and halogen-containing epoxides such as epichlorohydrin, and bisphenol A type epoxy resins obtained by the reaction of bisphenol F and the halogen-containing epoxides. biphenyl-type epoxy resin obtained by the reaction of biphenyl with the halogen-containing epoxide, resorcinol-type epoxy resin obtained by the reaction of resorcinol with the halogen-containing epoxide, bisphenol S and the halogen-containing epoxide. Bisphenol S-type epoxy resin obtained by reaction with polyhydric alcohols and the above-mentioned halogen-containing epoxides, polyethylene glycol-type epoxy resin, polypropylene glycol-type epoxy resin, bis-(3,4-epoxy -6-methyl-dicyclohexylmethyl) adipate, 3,4-epoxycyclohexene epoxide, etc. Epoxy resins obtained by oxidizing unsaturated bond parts, other naphthalene type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, And halogen or alkyl substituted products of these can be used.

The polyester fiber cord for rubber reinforcement of the present invention is coated with a first treatment agent containing (A) a compound containing an oxazoline group, (B) a blocked isocyanate compound, (C) rubber latex, and (D) an epoxy compound. However, based on the total solid content (dry weight) of the first treatment agent, (A) the compound containing an oxazoline group is 10 to 50% by weight, (B) the blocked isocyanate compound is 3 to 13% by weight, and (C) It is necessary that the rubber latex contains 20 to 60% by weight and the (D) epoxy compound contains 20 to 60% by weight, preferably containing (A) an oxazoline group based on the total solid content of the first processing agent. The compound contains 12 to 45% by weight, (B) the blocked isocyanate compound 4 to 12% by weight, (C) the rubber latex 25 to 55% by weight, and (D) the epoxy compound 25 to 55% by weight. Preferably, based on the total solid content of the first treatment agent, (A) the compound containing an oxazoline group is 15 to 40% by weight, (B) the blocked isocyanate compound is 5 to 11% by weight, and (C) the rubber latex is It is preferable that the epoxy compound (D) is contained in an amount of 30 to 50% by weight. (A) If the proportion of the compound containing an oxazoline group is out of this range, heat-resistant adhesive strength and fatigue resistance may deteriorate. If the proportion of the blocked isocyanate compound (B) is out of this range, the initial adhesive strength may decrease. If the ratio of (C) rubber latex is out of this range, the initial adhesive strength may decrease and the fatigue resistance may deteriorate. (D) If the ratio of the epoxy compound is out of this range, the initial adhesive strength and fatigue resistance may deteriorate.

In addition to the above (A), (B), (C), and (D), the first treatment agent used in the present invention may include, as necessary, within a range that does not impede the purpose and effect of the present invention. A surfactant, an antifoaming agent, a vulcanization regulator, an antioxidant, and a pH regulator may be added.

The lignin derivative (a) used in the second treatment agent of the present invention is a chemically treated lignin that exists in trees, which are biomass. Examples of such substances include, for example, kraft lignin obtained from kraft pulp waste liquid and lignin sulfonic acid obtained from sulfite pulp waste liquid in the paper manufacturing process using wood as a raw material. Lignosulfonic acid has a sulfonic group introduced into the side chain of the phenylpropane structure of lignin, and examples of the lignin sulfonate include sodium lignosulfonate, magnesium lignosulfonate, calcium lignosulfonate, and the like. In the present invention, these can be used alone or in combination, and among them, sodium ligninsulfonate is most preferably used from the viewpoint of adhesive strength.

The lignin derivative (a) used in the present invention needs to have a number average molecular weight of 10,000 to 60,000 and a weight average molecular weight of 80,000 to 130,000, preferably a number average molecular weight of 20,000 to 50,000 and a weight average molecular weight of 80,000 to 130,000. It is preferable that the molecular weight is 90,000 to 120,000. If the number average molecular weight and weight average molecular weight exceed the upper limit of this range, fatigue resistance may be insufficient, storage stability of the adhesive treatment agent may deteriorate, resin residue may accumulate during the dipping process, and continuous production may become difficult. It can be difficult. If the number average molecular weight and weight average molecular weight are less than the lower limit of this range, the initial adhesive strength with rubber and fatigue resistance will deteriorate, which is undesirable. Further, the weight average molecular weight (Mw)/number average molecular weight (Mn) is preferably 2.5 to 5.0, more preferably 2.8 to 4.7. Outside this range, adhesive strength and fatigue resistance may be insufficient. Note that the number average molecular weight and weight average molecular weight in the present invention refer to values measured by the method described in the Examples section.

The blocked isocyanate compound (b) used in the second treatment agent in the present invention is the same as the blocked isocyanate compound (B) used in the first treatment agent, and the blocked isocyanate compound preferably used is also the same.

The rubber latex (c) that can be used in the second treatment agent of the present invention is the same as the rubber latex (C) used in the first treatment agent, and the preferred Mooney viscosity is also the same. For example, natural rubber latex, butadiene rubber latex, styrene-butadiene rubber latex, vinylpyridine-styrene-butadiene rubber latex, nitrile rubber latex, hydrogenated nitrile rubber latex, chloroprene rubber latex, chlorosulfonated rubber latex, ethylene-propylene rubber latex, Examples include diene rubber latex, and these can be used alone or in combination. Among these, VP latex with a Mooney viscosity (ML1+4 100°C) of 20 to 100 and a Tg of -70°C to -30°C, more preferably a Mooney viscosity (ML1+4 100°C) of 30 to 80 and a Tg of -60°C. It is preferable from the viewpoint of adhesive strength and fatigue resistance that it contains VP latex at a temperature of -40°C.

In the second treatment agent of the present invention, when the total solid content contained in the adhesive treatment agent is 100% by weight, the content of (a) lignin derivative is preferably 5 to 50% by weight, more preferably The amount is 7 to 45% by weight, more preferably 10 to 40% by weight. If it is less than 5% by weight or more than 50% by weight, adhesive strength and fatigue resistance may be insufficient.

Further, the solid content weight ratio of (a) lignin derivative and (b) blocked isocyanate compound is preferably (solid content of a):(solid content of b) = 10:1 to 10:20, More preferably, the ratio is 10:5 to 10:20. If the amount of (b) is small in a range exceeding this weight ratio, the adhesive strength may be insufficient, and if the amount of (b) is large in a range exceeding this weight ratio, the cord will become hard and the adhesive force will be insufficient. Fatigue resistance may deteriorate, and if the cord is used to reinforce rubber products such as tires, belts, and hoses, the durability of the product may deteriorate, which is not preferable.

In addition, the solid content weight ratio of (a) lignin derivative, (B) blocked isocyanate compound, and (c) rubber latex is ((solid content of a) + (solid content of b)): (solid content of c) )=10:90 to 60:40, more preferably 20:80 to 50:50. Outside this range, adhesive strength may be insufficient or fatigue resistance may deteriorate.

In addition to the above-mentioned (a), (b), and (c), the second processing agent used in the present invention may also include surfactants as necessary, within a range that does not impede the purpose and effect of the present invention. , an antifoaming agent, a vulcanization regulator, an antioxidant, a pH regulator, carbon black, a coloring agent, etc. may be added.

The first treatment agent of the present invention has a solid content dissolved or dispersed in water, and the total solid content concentration is preferably 1 to 15% by weight, more preferably 2 to 13% by weight, and even more preferably The content is preferably 3 to 10% by weight. Outside this range, the initial adhesive strength and heat-resistant adhesive strength may deteriorate.

The second treatment agent of the present invention has a solid content dissolved or dispersed in water, and the total solid content concentration is preferably 5 to 25% by weight, more preferably 10 to 20% by weight, and even more preferably The content is preferably 12 to 18% by weight. Outside this range, the initial adhesive strength may decrease.

The amount of resin deposited in the film by the first treatment agent of the present invention is 1 to 4% by weight based on 100% by weight of polyester fiber, and the amount of resin deposited in the film by the second treatment agent is 1 to 4% by weight based on 100% by weight of polyester fiber. and the total amount of resin deposited by the first treatment agent and the second treatment agent is 2 to 6% by weight based on 100% by weight of the polyester fiber, but preferably, The amount of resin deposited in the film by the first treatment agent is 1.5 to 3.0% by weight based on 100% by weight of polyester fiber, and the amount of resin deposited in the film by the second treatment agent is 1.5 to 3.0% by weight based on 100% by weight of polyester fiber. 1.5 to 3.0% by weight, and the total resin adhesion amount of the film by the first treatment agent and the film by the second treatment agent is 2 to 5% by weight based on 100% by weight of the polyester fiber. Good. Outside this range, adhesive strength may deteriorate.

Further, the tackiness of the surface layer of the polyester fiber cord for rubber reinforcement of the present invention is preferably 2.0 to 10.0 N/cm ² , more preferably 3.0 to 9.0 N/cm ² . good. The tackiness of the surface layer of the cord can be measured by the method described below. If the tackiness of the cord surface layer is less than 2.0, the adhesive force with the rubber may decrease, and if it exceeds 10.0, resin scum will accumulate during the dipping process, worsening the cord's process passability. There are things to do. The tackiness of the cord can be adjusted within a preferable range, especially by optimizing the type and content of latex in the second bath treatment agent, and the ratio of the latex to other compounded chemicals.

Next, a method for manufacturing the polyester fiber cord for rubber reinforcement of the present invention will be described.

As an example of the method for manufacturing the rubber-reinforcing polyester fiber cord of the present invention, polyester fibers are treated with at least (A) a compound containing an oxazoline group, (B) a blocked isocyanate compound, (C) rubber latex, and (D) an epoxy compound. The resulting cord is adhered to a first treatment agent containing four types, heat-treated, and then treated with a first treatment agent containing at least three types: (a) a lignin derivative, (b) a blocked isocyanate compound, and (c) rubber latex. 2. This method involves attaching it to a processing agent and heat-treating it. The polyester fibers may be in the form of twisted cords or raw blinds. The heat treatment after adhesion of the first treatment agent and the second treatment agent is preferably performed by drying moisture at a temperature of 100 to 150°C, followed by heat treatment at 200 to 255°C.

A method for attaching the first treatment agent or the second treatment agent to the polyester fibers includes, for example, dipping treatment, in which a twisted yarn cord is placed in a dip tank in which a roller is installed and filled with an adhesive treatment agent. Alternatively, it refers to applying a treatment agent to the twisted cord or raw blind fabric by running the raw blind fabric. Heat treatment refers to heating the twisted cord or raw blind fabric by running the twisted cord or raw blind fabric in an oven equipped with rollers and which can be set at a predetermined temperature. A dipping machine for performing such dipping and heat treatment is commercially available from, for example, Ritzler. Note that as another method for attaching the treatment agent to the polyester fibers, in addition to dipping treatment, any method such as application by spraying the adhesive treatment agent from a nozzle can be employed.

In addition, in order to control the amount of solid content of the adhesive treatment agent attached to the polyester fibers, means such as squeezing with a pressure roller, scraping with a scraper, blowing off with air, and suction may be used.

Furthermore, during the mechanical softening process after the drying and heat treatment described above, a softening process can be performed to obtain a desired cord stiffness by sliding the polyester fiber cord on the edge.

The rubber-reinforcing polyester fiber cord of the present invention thus obtained is a rubber-reinforcing polyester fiber cord made of a new adhesive treatment agent that does not contain resorcinol/formaldehyde resin and uses alternative raw materials that are advantageous in reducing environmental impact. As a result, it exhibits an initial adhesion strength that is equal to or better than conventional RFL, and has significantly improved heat-resistant adhesive strength when exposed to high temperatures for long periods in rubber during the rubber vulcanization process or product use, and has improved fatigue resistance. , relates to a rubber reinforcing polyester fiber cord suitable as a tire reinforcing material. Further, it is possible to provide a polyester fiber cord for rubber reinforcement that can suppress resin residue accumulation in the dipping process and has good productivity.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. In addition, in the Examples specifically described below, each measured value was determined by the following method.

(1) Amount of Adhesive Treatment Agent Adhered The amount of adhesive applied was determined according to the dip pickup mass method of JIS L1017 (2002).

(2) Initial adhesive strength and heat-resistant adhesive strength Indicates the adhesive strength between the polyester fiber cord and rubber. The initial adhesive strength was measured in accordance with the 3.1T test (Method A) of JIS L1017 (2002) Annex 1, by embedding a polyester fiber cord in unvulcanized rubber and applying 50 kg/cm ² at 150°C for 30 minutes. After performing press vulcanization and cooling, the polyester fiber cord is pulled out from the rubber block at a speed of 300 mm/min, the load required for pulling it out is determined for each sample, and the initial adhesion is determined as the arithmetic average value of 10 samples. I used it as power. In addition, the heat-resistant adhesive strength was measured in accordance with the 3.1T test (Method A) of JIS L1017 (2002) Annex 1, by embedding a polyester fiber cord in unvulcanized rubber and applying 50 kg/kg at 150°C for 180 minutes. After performing press vulcanization, the synthetic fiber cord is pulled out from the rubber block at a speed of 300 mm/min, the load required for pulling it out is determined for each sample, and the arithmetic average value of ¹⁰ samples is calculated. Heat-resistant adhesive strength.

(3) Fatigue resistance in rubber (retention rate)
Evaluation was made in accordance with JIS L1017 (2002) Annex 1, 2.2.2 Disc fatigue strength (Goodrich method). Two polyester fiber cords are embedded in unvulcanized rubber and press vulcanized at 150° C. for 30 minutes at 50 kg/cm ² to create a rubber composite. This test piece was deformed at 2600 cycles/min with one cycle of compression 6.3% and elongation 12.6% in an atmosphere of 100°C for 12 hours, and then the polyester fiber cord was removed from the rubber and fractured after fatigue. The strength was measured, and the retention rate of breaking strength before and after the fatigue test was determined for each sample, and the arithmetic mean value of the eight samples was taken as the fatigue resistance in rubber (retention rate).

The composition of the unvulcanized rubber compound used to measure the initial adhesive strength, heat-resistant adhesive strength, and fatigue resistance in rubber is as follows.
Natural rubber (RSS#1): 70 (parts by weight)
SBR (#1502, manufactured by JSR Corporation): 30 (parts by weight)
HAF carbon black: 40 (parts by weight)
Stearic acid: 2 (parts by weight)
Sulfur: 2 (parts by weight)
Zinc white: 5 (parts by weight)
2,2'-dithiobenzothiazole: 3 (parts by weight)
Naphthenic acid process oil: 3 (parts by weight).

(4) Passability through dipping process Two 1670 dtex polyester multifilament yarns (manufactured by Toray Industries, Inc., "Tetron" 1670T-360-705M) are twisted with a number of twists of 40 twists/10cm for the first twist and 40 times/10cm for the final twist. and obtain a twisted cord. The twisted yarn cord is immersed in the first treatment agent using a computer processor (manufactured by Ritzler Co., Ltd.), then dried at 120°C for 2 minutes, and then heat-treated at 245°C for 1 minute. Subsequently, after being immersed in the second treatment agent, it is dried at 120°C for 2 minutes, and then heat-treated at 240°C for 1 minute to obtain a polyester fiber cord. After the heat treatment process using the second treatment agent ran for 3000 m, the amount of resin sludge accumulated on the heat treatment furnace turn roll (roll that the cord comes into contact with) of the computer processor was confirmed, and (resin sludge: many = B>A> S=none). In the present invention, S and A are considered as passing scores for process passability that can withstand practical use, but S is more excellent in practical use.

(5) Measurement of number average molecular weight and weight average molecular weight of lignin derivative The number average molecular weight and weight average molecular weight of the lignin derivative were measured by GPC method (gel permeation chromatography). A solvent (ammonia buffer/methanol) was added to the lignin derivative sample, stirred at room temperature to dissolve it, and filtered through a 0.5 μm filter. Thereafter, measurement was performed using GPC, a peak was detected using a UV detector, and the molecular weight was measured using relative values based on polyethylene oxide and polyethylene glycol standards. The measurement results are described in Examples described later. Details of the measurement conditions are described below.
Measuring device: Shimadzu Co., Ltd. Columns used: 1 TSKgel GMPW _XL , 1 G3000PW _XL (φ7.8 mm x 30 cm, manufactured by Tosoh)
Solvent: 0.1M ammonia buffer (pH 11)/methanol (4/1, v/v)
Standard material: monodisperse polyethylene oxide, polyethylene glycol manufactured by Tosoh and Agilent Detector: UV detector (Shimadzu SPD-M20A).

(6) Tackiness of cord surface layer Unvulcanized rubber (thickness 0.4 mm) was attached with double-sided tape to the contact part (1 x 1.5 cm) of "Tackiness Checker" HTC-1 manufactured by Toyo Seiki Co., Ltd. On the other hand, a polyester fiber cord was wrapped around a flat aluminum plate so that there were no gaps. The tackiness of the polyester fiber cord on the aluminum plate was measured using a "tackiness checker" under the measurement conditions of a crimping force of 10 N and a crimping time of 6 seconds (unit: N/1.5 cm ² ). The arithmetic mean value of the six measurements was calculated, and the value converted to the unit N/cm ² was taken as the tackiness of the cord surface layer. The composition of the unvulcanized rubber compound used was the same as in (3) above.

(7) Tire high-speed durability A radial tire with a tire size of 165-SR13 was produced using the above-mentioned polyester fiber cord as a carcass ply in the same manner as in a normal tire manufacturing process. After completing the high-speed durability test specified in JIS D4230 using a drum testing machine, the speed was further increased in 10 km/h units every 30 minutes to measure the travel distance until the tire broke. The evaluation was expressed using an index in which 100 was the evaluation result of a tire whose carcass ply was made of a polyester fiber cord using an RFL adhesive (conventional example), which will be described later. The larger the index, the better the high-speed durability.

(Examples 1 to 12, Comparative Examples 1 to 7)
(A) a compound containing an oxazoline group, (B) a blocked isocyanate compound, (C) rubber latex, and (D) an epoxy compound are mixed so that the solid content ratio is as shown in Table 1, and diluted with water. A first treatment agent having a total solid content concentration of 6% by weight was obtained. In addition, only in Example 2, the total solid content concentration was 2% by weight.

In addition, (a) lignin derivative, (b) blocked isocyanate compound, and (c) rubber latex were mixed so that the solid content ratio was as shown in Table 1, and diluted with water to give a total solid content concentration of 15% by weight. % of the second treatment agent was obtained. In addition, only in Example 2, the total solid content concentration was 20% by weight.

Two 1670 dtex polyester multifilament yarns (manufactured by Toray Industries, Inc., "Tetron" 1670T-360-705M) were twisted with a number of twists of 40 times/10 cm for first twist and 40 times/10 cm for final twist to obtain a twisted yarn cord. .

The twisted cord was immersed in the first treatment agent using a computer processor (manufactured by Ritzler Co., Ltd.), dried at 120°C for 2 minutes, and then heat-treated at 245°C for 1 minute. Subsequently, after being immersed in the second treatment agent, it was dried at 120°C for 2 minutes, and then heat-treated at 240°C for 1 minute to obtain a polyester fiber cord.

Table 1 shows the amount of resin deposited in the film coated with the first treatment agent and the resin deposited amount of the coat coated with the second treatment agent on the obtained polyester fiber cord.

The components of the first bath treatment agent shown in Table 1 are as follows.
(A)-1: Compound containing an oxazoline group (“Epocross” K-2035E manufactured by Nippon Shokubai Co., Ltd., acrylic-styrene copolymer containing an oxazoline group, Tg 50°C, oxazoline group amount 1.8 mmol/g, solid)
(A)-2: Compound containing oxazoline group (“Epocross” WS-700 manufactured by Nippon Shokubai Co., Ltd., acrylic copolymer containing oxazoline group, Tg 50°C, oxazoline group amount 4.5 mmol/g, solid)
(A)-3: Compound containing oxazoline group (“Epocross” K-2010E manufactured by Nippon Shokubai Co., Ltd., acrylic-styrene copolymer containing oxazoline group, Tg -50°C, oxazoline group amount 1.8 mmol/g, solid )
(A)-4: Compound containing oxazoline group (“Epocross” WS-300 manufactured by Nippon Shokubai Co., Ltd., acrylic-styrene copolymer containing oxazoline group, Tg 90°C, oxazoline group amount 7.7 mmol/g, solid)
(B)-1: Blocked isocyanate (Meisei Chemical DM-6400, oxime block MDI, number of functional groups: 2)
(B)-2: Blocked isocyanate (DM-3031CONC manufactured by Meisei Chemical, lactam block MDI, number of functional groups: 2)
(B)-3: Blocked isocyanate (“Elastron” BN-27 manufactured by Daiichi Kogyo Seiyaku, lactam block polymeric MDI, number of functional groups: 5)
(B)-4: Blocked isocyanate (Meikanate TP-10 manufactured by Meisei Chemical, oxime block TDI, number of functional groups: 6)
(C)-1: Rubber latex (“PYRATEX” manufactured by Japan A&L Co., Ltd., VP latex, Mooney viscosity (ML1+4 100°C) 35, Tg-55°C).
(C)-2: Rubber latex (“PYRATEX-HM” manufactured by Japan A&L Co., Ltd., VP latex, Mooney viscosity (ML1+4 100°C) 90, Tg-55°C).
(C)-3: Rubber latex (“PYRATEX-LB” manufactured by Japan A&L Co., Ltd., VP latex, Mooney viscosity (ML1+4 100°C) 120, Tg-25°C).
(D)-1: Epoxy compound (“Denacol” EX614B, manufactured by Nagase ChemteX Corporation).

The components of the second bath treatment agent shown in Table 1 are as follows.
(a)-1: Lignin derivative (“Vanilex” N manufactured by Nippon Paper Industries Co., Ltd., sodium lignin sulfonate, number average molecular weight 29,000, weight average molecular weight 105,000)
(a)-2: Lignan derivative (“Vanilex” RN manufactured by Nippon Paper Industries Co., Ltd., sodium lignin sulfonate, number average molecular weight 34,000, weight average molecular weight 112,000)
(a)-3: Lignin derivative (Pearlex” NP manufactured by Nippon Paper Industries Co., Ltd., sodium lignin sulfonate, number average molecular weight 97,000, weight average molecular weight 146,000)
(a)-4: Lignin derivative (Nippon Paper Industries Co., Ltd. "Sun Extract" P252, sodium lignin sulfonate, number average molecular weight 66,000, weight average molecular weight 135,000)
(b)-1: Blocked isocyanate (Meisei Chemical DM-6400, oxime block MDI, number of functional groups: 2)
(b)-2: Blocked isocyanate (DM-3031CONC manufactured by Meisei Chemical, lactam block MDI, number of functional groups is 2)
(b)-3: Blocked isocyanate (“Elastron” BN-27 manufactured by Daiichi Kogyo Seiyaku, lactam block polymeric MDI, number of functional groups: 5)
(c)-1: Rubber latex (“PYRATEX” manufactured by Japan A&L Co., Ltd., VP latex, Mooney viscosity (ML1+4 100°C) 35, Tg-55°C).
(c)-2: Rubber latex (“PYRATEX-HM” manufactured by Japan A&L Co., Ltd., VP latex, Mooney viscosity (ML1+4 100°C) 90, Tg-55°C).
(c)-3: Rubber latex (“PYRATEX-LB” manufactured by Japan A&L Co., Ltd., VP latex, Mooney viscosity (ML1+4 100°C) 120, Tg-25°C).

(Comparative example 8)
The same treatment as in Example 1 was performed except that the immersion with the first treatment agent and the heat treatment in Example 1 were not performed.

(Conventional example)
The same immersion and heat treatment as in Example 1 was performed using a treatment agent having the composition shown in Table 1 as the first treatment agent and a conventional RFL adhesive as the second treatment agent. RFL is made by mixing resorcin/formalin at a molar ratio of 1/1.5 in the presence of caustic soda, adjusting the solid content concentration to 10%, and aging for 2 hours. An initial condensate (RF (resorcinol formaldehyde resin)) was obtained. Next, this initial condensate (RF) and rubber latex (Piratex, manufactured by Japan A&L Co., Ltd.) were mixed at a ratio of RF/L=1/5 (solid content weight ratio) and aged for 24 hours. This mixture was diluted with water to give a solid content of 15% by weight.

After the polyester fiber cord obtained as described above was embedded in unvulcanized rubber and vulcanized, initial adhesive strength, heat-resistant adhesive strength, and fatigue resistance in rubber were measured. Furthermore, a radial tire was made using this polyester fiber tire cord as a carcass ply, and a high-speed durability test was conducted. The results are shown in Tables 1 and 2.

As shown in the results in Tables 1 and 2, in the case of the examples according to the present invention, the adhesive treatment agent does not contain resorcinol/formaldehyde resin, which is advantageous in reducing the environmental impact compared to the conventional RFL adhesive, and is more effective than rubber. It can be seen that the adhesiveness is as good as that of RFL adhesive, the heat-resistant adhesive strength is significantly better, and the fatigue resistance is improved. Furthermore, it can be seen that the accumulation of resin scum in the dipping process is suppressed and productivity is good. It can also be seen that tire performance with high-speed durability performance superior to tire cords made with conventional RFL adhesives can be obtained.

Claims (12)

The polyester fiber is coated with a first treatment agent containing at least four types: (A) a compound containing an oxazoline group, (B) a blocked isocyanate compound, (C) rubber latex, and (D) an epoxy compound, and further as an outer layer thereof. , a polyester fiber cord for rubber reinforcement coated with a second treatment agent containing at least three types: (a) a lignin derivative, (b) a blocked isocyanate compound, and (c) rubber latex, the first treatment agent comprising: When the total solid content is 100% by weight, (A) the compound containing an oxazoline group is 10 to 50% by weight, (B) the blocked isocyanate compound is 3 to 13% by weight, (C) the rubber latex is 20 to 60% by weight, (D) contains 20 to 60% by weight of an epoxy compound, and (a) the lignin derivative contained in the second treatment agent has a number average molecular weight of 10,000 to 60,000 and a weight average molecular weight of 80,000 to 130,000; A polyester fiber cord for rubber reinforcement that does not contain resorcinol or formaldehyde resin. The polyester fiber cord for rubber reinforcement according to claim 1, wherein the blocked isocyanate compound (B) contained in the first processing agent is a bifunctional MDI-based blocked isocyanate. The polyester fiber cord for rubber reinforcement according to claim 1, wherein the blocked isocyanate compound (b) contained in the second processing agent is a bifunctional MDI-based blocked isocyanate. The blocked isocyanate compound (B) contained in the first treatment agent is a difunctional MDI-based blocked isocyanate, and the blocked isocyanate compound (b) contained in the second treatment agent is a difunctional MDI-based blocked isocyanate. The polyester fiber cord for rubber reinforcement according to claim 1, characterized in that it is an MDI type blocked isocyanate. Claim 1, wherein the rubber latex (C) contained in the first treatment agent includes VP latex having a Mooney viscosity (ML1+4 100°C) of 20 to 100 and a Tg of -70°C to -30°C. Polyester fiber cord for rubber reinforcement described in . Claim 1, wherein the rubber latex (c) contained in the second processing agent includes VP latex having a Mooney viscosity (ML1+4 100°C) of 20 to 100 and a Tg of -70°C to -30°C. Polyester fiber cord for rubber reinforcement described in . The blocked isocyanate compound (B) contained in the first treatment agent is a difunctional MDI-based blocked isocyanate, and the blocked isocyanate compound (b) contained in the second treatment agent is a difunctional MDI-based blocked isocyanate. It is an MDI-type blocked isocyanate, and further,
The rubber latex (C) contained in the first processing agent contains VP latex having a Mooney viscosity (ML1+4 100°C) of 20 to 100 and a Tg of -70°C to -30°C, and The rubber latex (c) contained in the processing agent includes VP latex having a Mooney viscosity (ML1+4 100°C) of 20 to 100 and a Tg of -70°C to -30°C. Polyester fiber cord for rubber reinforcement. Claim 1, wherein the oxazoline group-containing compound (A) contained in the first treatment agent has a Tg of 0 to 80°C and an oxazoline group content of 1.0 to 5.0 mmol/g, solid. 7. The polyester fiber cord for rubber reinforcement according to any one of items 7 to 7. The polyester fiber cord for rubber reinforcement according to any one of claims 1 to 7, characterized in that the tackiness of the cord surface layer is 2.0 to 10.0 N/cm2. When the total solid content is 100% by dry weight of the second processing agent processing agent, the content of (a) lignin derivative is 5 to 50% by weight, (a) lignin derivative, and (b) block. The rubber according to any one of claims 1 to 7, wherein the solid content weight ratio of the doisocyanate compound is (solid content of a):(solid content of b) = 10:1 to 10:20. Polyester fiber cord for reinforcement. The amount of resin attached to the film formed by the first treatment agent is 1 to 4% by weight, and the amount of resin adhered to the film formed by the second treatment agent is 1 to 4% by weight, and the amount of resin adhered to the film formed by the first treatment agent and the second treatment are The polyester fiber cord for rubber reinforcement according to any one of claims 1 to 7, characterized in that the total amount of resin deposited in the coating by the agent is 2 to 6% by weight. A tire comprising the rubber-reinforcing polyester fiber cord according to any one of claims 1 to 7.