KR101086454B1 - Adhesive composition and rubber enhancing fiber treated using its - Google Patents

Abstract

The present invention relates to an adhesive composition for rubber reinforcing fiber treatment and a rubber reinforcing fiber treated with the composition, to provide an adhesive composition comprising an epoxy compound comprising two or more epoxy groups and an aromatic compound containing a hydroxyl group in a specific range. do. The present invention also provides a rubber reinforcing fiber obtained by treating the fiber during the spinning or stretching process using the adhesive composition.

Since the adhesive composition of the present invention has excellent solution stability and reactivity, it is easy to process rubber reinforcing fibers, and the obtained rubber reinforcing fibers have excellent adhesion with natural or synthetic rubbers, and thus are applied to rubber products such as tires, belts, and hoses. Effectively increase the physical properties.

Rubber reinforcing fiber, epoxy, aromatic compound, adhesion

Description

Adhesive composition and rubber reinforcing fiber treated with the composition TECHNICAL FIELD

The present invention is to improve the adhesion between the rubber reinforcing fibers and the rubber composition by treating the rubber reinforcing fibers with an adhesive composition containing an epoxy compound and an aromatic compound containing a hydroxyl group in a specific range, the rubber and the compatibility is increased An adhesive composition for reinforcing fiber treatment and a rubber reinforcing fiber treated with the composition.

Rubber is largely divided into natural rubber and synthetic rubber. Since rubber has excellent physical properties such as elasticity, rubber is widely used in modern industrial fields such as tires, belts, and hoses. However, while rubber has excellent elasticity, low mechanical properties such as strength and rigidity are added to supplement the reinforcing material.

The rubber reinforcing material is mainly reinforcing fibers (reinforcing fibers, or reinforcing fibers) of twisted yarn cord, polyester fibers represented by polyethylene terephthalate (polyester), nylon (Nylon) Polyamide fibers (polyamide fibers), poly (vinylalcohol) fibers and the like are used. However, the reinforcing fibers have poor adhesiveness with the rubber to be applied, and require separate adhesives.

According to Japanese Patent Application No. 46-11251, 2,6-bis (2 ', 4'-dihydroxyphenylmethyl) -4-chlorophenyl (2,6-bis (2', 4'-dihydroxyphenylmethyl)- Reaction products of halogenated phenols such as 4-chlorophenyl and resorcinol / formaldehyde (resocinol formaldehyde latex, hereinafter referred to as 'RFL') Is referred to as.

When using the RFL treatment liquid, the components of the RFL must be present to some extent on the surface of the reinforcing fibers so that the reinforcing fibers obtain sufficient adhesion (pulling force, adhesion) over a predetermined range after treatment.

In addition, halogenated phenols such as 2,6-bis (2,4-dihydroxyphenylmethyl) -4-chlorophenyl (commonly abbreviated as "packs") use ammonia water to enhance the adhesion effect. Alkali component of the ammonia water remains in the reinforcing fibers in a large amount to cause hydrolysis of the reinforcing fibers. Moreover, in view of the fact that the hydrolysis phenomenon is promoted by heat, the reinforcing fibers treated with the treatment liquid have a problem that the adhesive strength is greatly lowered after heat aging.

In addition, U.S. Patent No. 3,234,067 improves the adhesion of reinforcing fibers to rubber by coating the surface of the reinforcing fibers with an adhesive based on epoxy, isocyanates, and halogenated phenol compounds. It says it can. Specifically, the polyester fiber, which is a reinforcing fiber, is treated with a first treatment liquid consisting of a mixture of an epoxy compound and a diisocyanate blocked with caprolactam or phenol, followed by a second treatment liquid consisting of RFL. A double dipping system is proposed.

However, RFL used as the second treatment liquid has poor compatibility with the diisocyanate of the first treatment liquid, so that the dispersion stability is lowered, and when heat is applied during coating of the reinforcing fibers obtained after the treatment, phenol or capro as the blocking compound It is not preferable because a problem harmful to the environment such as lactam or the like generates harmful gases occurs.

As described above, in the double-dipping system, it is necessary to make the first treatment liquid highly reactive with the RFL used as the second treatment liquid. In addition, it is urgent to develop a treatment liquid that can solve the above problems.

In order to solve the problems of the prior art as described above, the present invention can not only suppress the deterioration of the adhesive force when mixing the rubber composition and rubber reinforcing fibers, but also shorten the standing time after weaving to increase spinning operation and post-processing properties. It is an object to provide an adhesive composition for rubber reinforcing fiber treatment.

In addition, the adhesive composition of the present invention is characterized in that it can be suitably applied to a double-dipping system due to its high reactivity with the RFL adhesive composition.

In addition, another object of the present invention is to provide a rubber reinforcing fiber treated using the adhesive composition.

In order to achieve the above object, the present invention

Epoxy compounds containing two or more epoxy groups in one molecule; And

Provided is an adhesive composition for treating rubber reinforcing fibers containing an aromatic compound containing a hydroxyl group.

Preferably, the adhesive composition comprises 1 to 50 parts by weight of an aromatic compound containing a hydroxyl group based on 100 parts by weight of an epoxy compound.

The present invention also provides a rubber reinforcing fiber surface-treated using the adhesive composition.

The rubber reinforcing fibers are preferably polyester resins of polyethylene terephthalate and polybutylene terephthalate, polyimide resins, polyamide resins and polyvinyl alcohol resins.

The present invention is described in more detail below.

The present invention provides an adhesive composition for treating rubber reinforcing fibers for increasing the adhesion between the rubber reinforcing fibers and the rubber compositions used to increase the physical properties of rubber compositions such as tires, belts and hoses.

을 포함하는 물질로서, 경화 후 반응 수축이 매우 작고 기계적 성질 및 내마모성, 치수 안정성이 매우 우수하다. 상기 에폭시 화합물은 가교 반 응을 수행하기 위하여 1 분자 중에 2 개 이상의 에폭시기를 함유하는 것이 바람직하며, 고온에서 가공 시 상기 화합물 자체가 휘발하는 경우가 있는 바, 그 분자량은 100 이상으로 하는 것이 바람직하다.First, the epoxy compound that is a component of the adhesive composition according to the present invention is an epoxy bond in the molecular structure

As a material containing, the reaction shrinkage after curing is very small, mechanical properties and wear resistance, dimensional stability is very excellent. In order to carry out the crosslinking reaction, the epoxy compound preferably contains two or more epoxy groups in one molecule, and the compound itself may volatilize when processed at high temperature, and the molecular weight thereof is preferably 100 or more. .

The epoxy compound can be suitably used within the range of the epoxy group and the molecular weight as long as it is commonly used in this field. For example, the usable epoxy compound may be a general bisphenol A type epoxy (Bisphenol A Type Epoxy); Bisphenol F Type Epoxy; Novolac type epoxy; Flame retardant epoxy; Cyclic aliphatic epoxy (Cycloaliphatic Epoxy); Rubber modified epoxy (Rubber Modified Epoxy); Aliphatic Polyglycidyl Type Epoxy; And glycidyl amine type epoxy (Glycidylamine Type Epoxy).

The epoxy compound may be glycerol, pentaerythritol, sorbitol, ethylene glycol, ethylene glycol, propylene glycol, and polypropylene glycol. obtained by reacting a polyhydric alcohol such as propyleneglycol) with a halogen-containing epoxide compound such as epichlorohydrin, resorcinol, bis (4-hydroxyphenyl) diethylethane (bis ( 4-hydroxyphenyldiethylethane), phenol-formaldehyde resin and resorcinol-formaldehyde resin, cresol resin, novolac resin, bisphenol A It is obtained by making polyhydric phenols, such as a bisphenol A type resin, react with the said halogen containing epoxide compound.

Preferably, the epoxy compound of the present invention should take into account the degree of crosslinking reaction closely related to the adhesion ability, so as to be 0.1 to 2.0% by weight of the rubber reinforcing fiber to be treated. In this case, when the content of the epoxy compound is less than the above range, even if the crosslinking reaction of the epoxy compound is ideally performed, the content is small, resulting in a problem that the adhesion between the final fiber and rubber is lowered. In addition, if the above range is exceeded, excessive crosslinking may cause a drop in the process of the epoxy compound, and even if the spinning workability is greatly reduced, a defect such as foreign matters may occur during post-processing such as weaving.

In particular, an aromatic compound containing a hydroxyl group, which is another component of the adhesive composition according to the present invention, includes at least one hydroxyl group (OH) in a molecular structure to increase adhesion through a condensation reaction with an epoxy compound as a first component, and In the case of the subsequent process also reacts with RFL (Resorcinol Formaldehyde Latex) to further increase the adhesion.

The aromatic compound containing a hydroxyl group is preferably a material exhibiting acidity in order to facilitate compatibility with other materials, for example, dispersion, and to suppress hydrolysis of rubber reinforcing fibers. In the present invention, it is selected from the group consisting of phenol, resorcinol, salicylic acid, p-chlorophenol and resorcinol formaldehyde condensation product alone or a mixture thereof. .

Preferably, the aromatic compound containing a hydroxyl group of the present invention is 0.01 to 50.0 parts by weight based on 100 parts by weight of the epoxy compound in consideration of the adhesion and dispersibility. At this time, if the content of the component is less than the above range can not be expected to improve the adhesion according to the addition of the compound at all, if it exceeds the above range condensation of the epoxy compound capable of reacting with the aromatic compound and the RFL compound of the subsequent process The reaction proceeds excessively, so that the solubility in water used as a diluent is very low, so that the dispersibility is lowered, resulting in a decrease in the solution stability of the final adhesive treatment liquid obtained.

In particular, by employing an aromatic compound containing a hydroxyl group as in the present invention, it can be suitably applied to a double-dipping system used in rubber reinforcing fiber treatment due to the excellent reactivity with the epoxy compound as well as RFL.

As described above, the adhesive composition for treating the rubber reinforcing fiber of the present invention includes an epoxy compound and an aromatic compound containing a hydroxyl group having excellent reactivity with the compound, thereby performing surface treatment of the rubber reinforcing fiber.

The rubber reinforcing fiber is used to increase the physical properties of the rubber product, and is treated with the adhesive composition according to the present invention to include a functional group having an adhesive ability such as an epoxy group on the surface of the rubber reinforcing fiber, thereby excellent adhesion when mixed with the rubber composition It can significantly increase the mechanical properties of the rubber composition.

Such rubber reinforcing fibers may be all fibers commonly used to increase the physical properties of the rubber composition, for example, poly (ethyleneterephthalate) and polybutylene terephthalate (poly (buthyleneterephthalate)) Polyester resins; Polyimide resins; Polyamide resins; And it is selected from the group consisting of poly (vinylalcohol) resins, preferably using a polyester resin.

At this time, the molecular weight of the rubber reinforcing fibers, denia, the number of filaments, the cross-sectional shape, the yarn properties, the fine structure, the presence or absence of additives, polymer properties such as terminal carboxyl concentration, etc. are not particularly limited in the present invention.

In order to process the rubber reinforcing fibers using the adhesive composition according to the present invention, after the spinning oil is dispersed, the adhesive composition is added thereto to form an adhesive treatment liquid. Manufacture.

The spinning emulsion is not particularly limited in the present invention, and may be appropriately selected depending on the rubber reinforcing fiber to be used. The spinning oil may be emulsified with natural oils such as palm oil and castor oil, ester oils of higher alcohols or polyhydric alcohols with higher fatty acids, synthetic oils such as alkyl polyethers, lubricants of such synthetic oils, and smoothing agents. Surfactant to be dispersed and antistatic agents, heat-resistant and / or colorants, etc. may be used in combination.

In this case, as the surfactant, a compound in which an alkylene oxide is added to castor oil or a higher alcohol, or an ester oil of polyethylene (or polypropylene) oxide or polyethylene glycol and a higher fatty acid may be used.

As described above, the method for treating rubber reinforcing fibers using the adhesive treatment agent containing the adhesive composition is not particularly limited in the present invention, and is known in the art.

For example, the treatment of rubber reinforcing fibers using the adhesive treatment agent according to the present invention alone; After treatment of the adhesion treatment agent, treatment in two steps using a post treatment agent such as RFL; Various methods such as pretreatment after mixing the adhesion treatment agent and RFL, followed by two steps of posttreatment with RFL solution may be used.

As a treatment method using such an adhesive treatment agent, conventional methods such as immersing, applying, or spraying a rubber reinforcing fiber to increase the adhesive ability to the adhesive treatment agent are employed.

Following the above process, the obtained rubber reinforcing fibers are dried in an oven or the like and then heat treated. At this time, the drying and heat treatment is carried out drying for 70 to 200 seconds at 70 to 100 ℃, and then heat treatment for 30 to 120 seconds at a temperature of 210 to 250 ℃.

As a result, rubber reinforcing fibers coated with the adhesive composition according to the present invention on the surface can be obtained, and the obtained rubber reinforcing fibers are mixed with the rubber composition in a subsequent process to increase the physical properties of the rubber composition.

On the other hand, the surface treatment of the rubber reinforcing fibers can be treated in two steps using a separate adhesive composition, such as RFL.                     

This treatment method is simplified, and is made by surface treatment with an adhesive composition according to the present invention, followed by heat treatment, followed by coating the RFL treatment solution and heat treatment similarly to the above-described process. However, at this time, the treatment time using the treatment solution should be appropriately adjusted so that the content of the adhesive solids present on the surface of the rubber reinforcing fiber is in the range of 3 to 8% (weight ratio).

As described above, the rubber reinforcing fibers according to the present invention can be used in the production of rubber products such as tires, belts and hoses to exhibit excellent adhesion with the rubber composition, resulting in effectively increasing the physical properties of the final rubber product.

According to a preferred embodiment of the present invention, an epoxy compound is used, and an adhesive composition including resorcinol, salicylic acid and RFL condensate is prepared as an aromatic compound containing a hydroxyl group.

Surface treatment of the polyester cord (cord) as a rubber reinforcing fiber using the obtained adhesive composition, after measuring the adhesive force after 3 weeks was confirmed that the adhesion between the rubber reinforcing fibers and the rubber composition according to the present invention is excellent. (See Table 3). In addition, as a result of checking the processability such as spinning operation through the process, in the case of the comparative example deviated from the composition of the present invention, the long-term spinning operation such as the epoxy compound is accumulated on the Godt Roller, which is very poor, the present invention In the case of the embodiment according to the above-described problems rarely occur or appeared to be insignificant.

Thus, the rubber reinforcing fibers treated with the adhesive composition according to the present invention increases the adhesiveness with the rubber composition, it is possible to obtain sufficient adhesion even in a small amount can effectively increase the mechanical properties of the rubber composition. .

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the following examples are only examples of the present invention, and the present invention is not limited to these examples.

Example 1 Preparation of Polyester Rubber Reinforcement Fiber

A polyester chip having an intrinsic viscosity of 1.03 (measured at 30 ° C. in a mixed solvent of phenol: tetrachloroethane = 3: 2) was subjected to a spinning temperature of 305 ° C. at a hole diameter of 0.4 mm and a hole count of 220 g in a spinneret of 192. The undrawn yarn was obtained by spinning at a discharge amount of / min, and the obtained undrawn yarn was cooled to a temperature below the secondary transition point of the polymer, and a spinning emulsion treatment liquid was applied by using an ordinary oiling roller.

As the spinning emulsion treatment liquid, one obtained by dissolving 12 kg of an oil for polyester having a fatty acid ester and a nonionic surfactant as a main component in 80 kg of water was used.

Next, it was introduced into a direct spinning machine of a five-stage goth roller in order to draw the unstretched polyester fiber, and using an oil jet between the five-stage goth roller and the winder The adhesive composition according to the invention was sprayed onto the polyester fibers. At this time, the degree of spraying was sufficiently buried so that the epoxy emulsifier liquid fell in the polyester cord so that the adhesive liquid of 3 to 8% (solid content) was attached.

The adhesive composition of Example 1 used above was dissolved in 92 kg of water by dissolving 8 kg of EPON812 ^TM , 0.4 kg of resorcinol, and 0.1 kg of nonionic surfactant, which are epoxy compounds obtained by reacting glycerin with epichlorohydrin. Was prepared.

In the drawing process, the temperature and line speed of the direct spinning stretching machine Godet roller are 80 ° C-400 m / min for the first step roller, 100 ° C-410 m / min for the second step roller, 110 ° C-1600 m / min for the three step roller, respectively. Four-stage roller 200 ° C.-2000 m / min, and five-stage roller room temperature-1980 m / min.

Subsequently, the polyester fibers obtained after the stretching step were heat treated at 150 ° C. for 2 minutes and at 220 ° C. for 2 minutes to prepare polyester fibers for rubber reinforcement.

Example 2 Preparation of Polyester Rubber Reinforcement Fiber

Polyester rubber reinforcing fibers were prepared in the same manner as in Example 1, except that 20 kg of ECN1400 ^™ , 0.4 kg of resorcinol, and 0.1 kg of nonionic surfactant were dissolved in 80 kg of water as an adhesive composition. . At this time, the ECN1400 ^TM is a compound (concentration 40%) obtained by reacting with a cresol novolak resin and epichlorohydrin manufactured by CIBAGEIGY.

Example 3 Preparation of Polyester Rubber Reinforcement Fiber

Polyester rubber reinforcing fibers were prepared in the same manner as in Example 1, except that 8 kg of EPON812 ^™ , 2.0 kg of salicylic acid, and 0.1 kg of nonionic surfactant were dissolved in 92 kg of water as the adhesive composition.

Example 4 Preparation of Polyester Rubber Reinforcing Fibers

Polyester rubber reinforcing fibers were prepared in the same manner as in Example 1, except that 8 kg of EPON812 ^™ , 1.6 kg of salicylic acid, and 0.1 kg of nonionic surfactant were dissolved in 92 kg of water as an adhesive composition.

Example 5 Preparation of Polyester Rubber Reinforcement Fibers

A polyester rubber reinforcing fiber was prepared in the same manner as in Example 1, except that 4 kg of EPON812 ^™ , 0.4 kg of salicylic acid, and 0.1 kg of nonionic surfactant were dissolved in 96 kg of water as an adhesive composition.

Example 6 Preparation of Polyester Rubber Reinforcement Fiber

A polyester rubber reinforcing fiber was prepared in the same manner as in Example 1 except that 12 kg of EPON812 ^™ , 2.4 kg of 50% RF condensate, and 0.1 kg of nonionic surfactant were dissolved in 88 kg of water as an adhesive composition. Prepared.

Example 7 Preparation of Polyester Rubber Reinforcing Fibers

A polyester rubber reinforcing fiber was prepared in the same manner as in Example 1, except that 8 kg of EX-614 ^TM , 0.8 kg of salicylic acid, and 0.1 kg of a nonionic surfactant were dissolved in 92 kg of water as an adhesive composition. . At this time, the EX-614 ^TM is a compound obtained by reacting glycerin and epichlorohydrin manufactured by NAGASE.

Comparative Example 1: Preparation of Polyester Cord Treated with RFL Adhesive

In order to compare the adhesion with the RFL used as a conventional adhesive composition was carried out as follows.

First, as a spinning emulsion treatment liquid, one obtained by dissolving 12 kg of an oil for polyester and 8 kg of an epoxy compound EPON812 mainly composed of a fatty acid ester and a nonionic surfactant was dissolved in 80 kg of water.

Next, it was carried out in the same manner as described above in Example 1, wherein the composition as shown in Table 1 as the adhesive composition, resorcinol, formaldehyde and sodium hydroxide and styrene / 1,3-butadiene / vinylpyridine (15:70:15) was dispersed in water to prepare a RFL adhesive composition for a tire cord at 20% concentration.

Raw material name weight% Resocinol 8.8 Formaldehyde (37%) 4.76 NaOH (10%) 10 Styrene / 1.3-butadiene / vinyl pyridine rubber (41%) 56 water 17.6

Comparative Example 2: Preparation of Polyester Rubber Reinforcement Fiber

As the adhesive composition, except that 8 kg of an epoxy compound EPON812 ^TM and 0.1 kg of a nonionic surfactant were dissolved in 92 kg of water, the same procedure as in Example 1 was performed to prepare a polyester fiber for rubber reinforcement.

Comparative Example 3: Preparation of Polyester Rubber Reinforcement Fiber

Polyester rubber reinforcement was carried out in the same manner as in Example 1, except that 8 kg of EPON812 ^™ , 6.0 kg of salicylic acid, and 0.1 kg of nonionic surfactant were dissolved in 86 kg of water so as not to include an amine compound as the adhesive composition. Fibers were prepared.

Comparative Example 4: Preparation of Polyester Rubber Reinforcement Fiber

Polyester was carried out in the same manner as in Example 1, except that 8 kg of EPON812 ^™ , 0.04 kg of resorcinol, and 0.1 kg of nonionic surfactant were dissolved in 92 kg of water to contain an excessive amount of the amine compound as the adhesive composition. Rubber reinforcing fibers were made.

The composition of Example 1 to Comparative Example 4 as described above is as shown in Table 2 below.

division Epoxy adhesive treatment agent Epoxy compound Hydroxyl-containing aromatic compounds Nonionic
Surfactants water Kinds content Kinds content content content Example 1 EPON812 ¹⁾ 8 kg Resorcinol 0.4 kg 0.1 kg 92 kg Example 2 ECN1400 ²⁾ 20 kg Resorcinol 0.4 kg 0.1 kg 80 kg Example 3 EPON812 8 kg Resorcinol 2.0 kg 0.1 kg 92 kg Example 4 EPON812 8 kg Salicylic acid 1.6 kg 0.1 kg 92 kg Example 5 EPON812 4 kg Salicylic acid 0.4 kg 0.1 kg 96 kg Example 6 EPON812 12 kg RF condensate 2.4 kg 0.1 kg 88 kg Example 7 EX-614 ³⁾ 8 kg Salicylic acid 0.8 kg 0.1 kg 91 kg Comparative Example 1 EPON812 8 kg - - 0.1 kg 80 kg Comparative Example 2 EPON812 8 kg - - 0.1 kg 92 kg Comparative Example 3 EPON812 8 kg Salicylic acid 6.0 kg 0.1 kg 86 kg Comparative Example 4 EPON812 8 kg Resorcinol 0.04 kg 0.1 kg 86 kg 1) SHELL Corporation; Reaction product of glycerin with epichlorohydrin
2) CIBAGEIGY company; Reaction of Cresol Novolac Resin with Epichlorohydrin
(40% concentration)
3) NAGASE Corporation; Reaction product of glycerin with epichlorohydrin

Test Example

A: Adhesion Test (H-test)

In order to measure the adhesion of the impregnated polyester cords obtained in the above examples and comparative examples, a rubber composition having a composition as shown in Table 3 below was treated in accordance with the provisions of ASTM D-2138-72 and a pressure of 60 kg / cm 2. It was vulcanized at 150 ° C. for 30 minutes.

 Subsequently, the vulcanized polyester cord was heat-aged and cut in an oven at 150 ° C. for 76 hours to prepare a specimen, and then drawn out at 25 ° C. at 300 ° C./min with an Intron to obtain adhesion (kgf / 25 mm). ) Was evaluated. The obtained results are as shown in Table 4 below.

Raw material name Addition amount (part) Styrene-Butadiene Rubber
(Styrene-Butadiene Rubber, SBR) 100 Zinc oxide 5 Carbon black 50 Stearic acid One Nectron 60 ^TM 25 Tetramethyl Thiuram Monosulfide
(tetra methyl thiurammonosulfide) 1.5 2-Mercapto benzothiazole 0.5 Yiwu 1.5

B: radiation operation

In order to determine the spinning operation in manufacturing the impregnated polyester cords obtained in Examples and Comparative Examples, the degree of foreign matter deposition on the Godette roller was examined, and the obtained results are shown in Table 4 below.

C: Post Processing

In order to determine the post-processability at the time of manufacturing the impregnated polyester cords obtained in Examples and Comparative Examples, the degree of foreign body sedimentation during weaving was examined, and the obtained results are shown in Table 4 below.

division In the drawing company
Epoxy compound
(weight%) Hydroxyl-containing aromatic compounds
(% By weight) ^* Adhesion of 3 Weeks
(kg / cm) Foreign body presence Godet roller during spinning Body when weaving Example 1 0.41 5 10.0 radish radish Example 2 0.39 5 9.5 radish radish Example 3 0.37 25 11.0 radish radish Example 4 0.41 20 10.0 radish radish Example 5 0.21 10 11.0 radish radish Example 6 0.62 10 10.5 YOU ^*** YOU ^*** Example 7 0.41 10 11.5 radish radish Comparative Example 1 0.38 - 12.0 plenty radish Comparative Example 2 0.39 - 8.0 radish radish Comparative Example 3 0.40 75 7.0 plenty radish Comparative Example 4 0.38 10 8.5 radish plenty *, ** Reference amount of epoxy compound
*** error range

According to Table 4, in the case of the polyester cord obtained by treatment with the adhesive composition according to the present invention showed an adhesive force in the range of 9.5 to 11.5 kg / cm, in the comparative example it is not only low adhesion but also foreign matter accumulated on the roller during the process It can be seen that workability is low due to side reactions and unreacted reactions.

Specifically, in the case of Comparative Example 1, as a large amount of the epoxy compound to be processed during processing is laminated on the Godet roller, there is a problem in the long-term operability, such as difficult to proceed properly.

In addition, in the case of Comparative Example 2 it was found that by omission of both the heat treatment and the catalyst after the treatment of the epoxy compound, as the reaction between the initial epoxy compound and the polyester end group proceeded slowly, the adhesive strength was seriously insufficient as 8 kg / cm.                     

Moreover, the applied aromatic compound content of Comparative Example 3 was too high, so that the dispersion of the treatment liquid was very nonuniform, resulting in poor workability and very low adhesion of 7 kg / cm.

In addition, in the case of Comparative Example 4, the content of the added resorcinol was too small to obtain the effect of the addition of the aromatic compound, there was a problem such as foreign matter laminated on the body when weaving.

As described above, according to the present invention, the rubber composition and the rubber reinforcing fiber excellent in adhesion performance were obtained, and in order to increase the adhesion performance, an adhesive composition including an aromatic compound containing a hydroxyl group in the epoxy compound was prepared.

By the adhesive composition of the present invention, the present invention can not only suppress the deterioration of the adhesive strength when mixing the rubber composition and the rubber reinforcing fibers, but also shorten the leaving time after weaving to obtain the effect of increasing the spinning operation and post-processability. Could.

In addition, the obtained rubber reinforcing fibers can increase the adhesiveness with the rubber composition, can obtain a sufficient adhesion even in a small amount can effectively increase the mechanical properties of the rubber composition.

In addition, the hydroxyl group-containing aromatic compound contained above has excellent reactivity with RFL which is conventionally used as an adhesive treatment agent, thereby facilitating the adoption of a double-dipping system in treating rubber reinforcing fibers.

Thus, as the adhesion of the rubber reinforcing fibers is increased, the processability with the rubber composition is increased, and as a result, it is effective to increase the physical properties of the final processed rubber product.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention as defined by the following claims It can be understood that

Claims (6)

Epoxy compounds containing two or more epoxy groups in one molecule; And Group consisting of phenol, resorcinol, salicylic acid, p-chlorophenol and resorcinol formaldehyde condensation product alone and mixtures thereof Contains an aromatic compound containing at least one hydroxyl group selected from, Adhesive composition for rubber reinforcing fiber treatment, containing 1 to 50 parts by weight of an aromatic compound containing a hydroxyl group, based on 100 parts by weight of the epoxy compound. The adhesive composition according to claim 1, wherein the adhesive composition comprises 5 to 25 parts by weight of an aromatic compound containing a hydroxyl group based on 100 parts by weight of an epoxy compound. The adhesive composition of claim 1, wherein the epoxy compound has a molecular weight of 100 daltons or more. delete Epoxy compounds containing two or more epoxy groups in one molecule; And Group consisting of phenol, resorcinol, salicylic acid, p-chlorophenol and resorcinol formaldehyde condensation product alone and mixtures thereof Contains an aromatic compound containing at least one hydroxyl group selected from, Rubber reinforcing fibers treated with an adhesive composition for rubber reinforcing fiber treatment, containing 1 to 50 parts by weight of an aromatic compound containing a hydroxyl group, based on 100 parts by weight of the epoxy compound. The rubber reinforcing fiber according to claim 5, wherein the adhesive composition is treated with a composition containing 5 to 25 parts by weight of an aromatic compound containing a hydroxyl group based on 100 parts by weight of an epoxy compound containing two or more epoxy groups in one molecule.