KR100616180B1 - Polyester fiber having enhanced adhesive property with rubber - Google Patents

Abstract

The present invention relates to a polyester fiber for rubber reinforcement, characterized in that the epoxy compound and the tertiary amine compound having two or more epoxy groups in the spinning or stretching process is given, the polyester fiber promotes the reaction between the epoxy and the fiber It shows stable heat-resistant adhesive strength.

Description

Polyester fiber having enhanced adhesive property with rubber             

The present invention relates to the production of polyester fibers having good adhesion to rubber, in particular heat resistance.

Polyester fiber, which is widely used as a reinforcing material for rubber structures such as tires, belts and hoses, has poor adhesion to rubber. Therefore, the surface of the fiber is used by using an adhesive comprising an epoxy compound, an isocyanate compound, and a halogenated phenol compound as an adhesive matrix component. Various methods have been conventionally proposed to improve the adhesion to rubber by coating.

For example, typical adhesive agents for polyester fibers include reaction products of halogenated phenols such as 2,6-bis (2 ', 4'-dihydroxyphenylmethyl) -4-chlorophenyl and resorcinol / formaldehyde. Is mixed with a liquid consisting of an initial condensate of resorcinol / formaldehyde and rubber latex (hereinafter referred to as 'RFL') (JP-A-46-11251). However, when using this adhesive agent, it is necessary to considerably increase the adhesion amount of the adhesive agent to the polyester fiber in order to obtain sufficient adhesive force (pulling force), and 2,6-bis (2,4-dihydroxyphenylmethyl)- Halogenated phenols, such as 4-chlorophenyl (commonly abbreviated as capsules), use ammonia water to enhance the adhesion effect, so that a large amount of these alkalis remain in the fiber, so that hydrolysis of polyester fibers by these alkalis is inevitable, and hydrolysis is not possible. Since there is a problem that the adhesion strength after thermal aging of the resulting polyester fiber for rubber reinforcement is promoted by heat significantly.

Alternatively, the polyester fibers are first treated with a first treatment liquid consisting of a mixture of epoxy compounds and caprolactam or diisocyanate blocked with phenol, followed by a second treatment liquid consisting of RFL. US Pat. No. 3,234,067. This method has a problem that the polyester fiber material obtained with the trouble of requiring two steps of the adhesive treatment process (hereinafter referred to as the 'dipping process') is hard and has poor moldability.

Accordingly, an object of the present invention is to provide a polyester fiber capable of maintaining excellent adhesive strength even after thermal aging in view of the above-mentioned problems of the prior art.

In the present inventor's research for solving the above problems, when the epoxy compound and the tertiary amine compound having two or more epoxy groups are given in the stretching step of the polyester fiber manufacturing process, the obtained polyester fiber is adhered to the rubber compound. It has been found that the properties are improved, and in particular, it maintains excellent adhesion even at high temperatures for a long time in the state of entering the reinforcement in the rubber compound.

Therefore, according to the present invention, there is provided a heat-resistant adhesive polyester fiber characterized in that an epoxy compound having two or more epoxy groups and a tertiary amine compound are provided.

Hereinafter, the present invention will be described in more detail.

According to a preferred embodiment of the present invention can be prepared by imparting an epoxy compound and tersia liamine compound in the spinning or stretching process. Tercyariamine is given to promote the reaction of the polyester fiber with an epoxy compound having two or more epoxy groups.

Although not intended to be limiting, it is desirable to produce the polyester fibers in a process where spinning and stretching are separate for uniform adhesion of the epoxy. In particular, it is advantageous to treat the epoxy and tersia liamine compounds in a stretching process in which the fiber is running slowly.

Polyester fiber in the present invention means a fiber made of ethylene terephthalate of at least 90% by weight, preferably at least 95% by weight of the repeating unit of the polymer.

In the manufacturing process, spinning and stretching are separated, but it is preferable that the four-speed running speed (hereinafter referred to as yarn speed) in the stretching air is not more than 1,000 m / min. Here, the process of spinning and stretching separated means that the polyester chip is melt-spun to stretch the undrawn yarn (UDY) and the partially drawn yarn. When the stretching yarn speed exceeds 1,000 m / min, not only the uniform adhesion of the epoxy compound due to the overspeed is impaired, but also there is a problem in that the work of the slope is difficult. In particular, it is preferable to apply the stretching yarn speed to 100 to 500 m / min.

The epoxy compound contains two or more epoxy groups in one molecule, and particularly preferably a compound having a molecular weight of 100 or more and an epoxy equivalent of 100 or more. When the epoxy group per molecule is 1 or less, crosslinking is not formed, so it is not used. If the molecular weight is 100 or less, the boiling point is close to the processing temperature at the time of coating and there is a problem that volatilization at the time of processing is not used. Specific examples of the epoxy compound include reaction products of polyhydric alcohols such as glycerol, pentaerythritol, sorbitol, ethylene glycol, polyethylene glycol, propylene glycol and polypropylene glycol with halogen-containing epoxides such as epichlorohydrin, resorcinol, Reaction products of polyhydric phenols, such as bis (4-hydroxyphenyl) diethyl ethane, phenol formaldehyde resin, resorcinol formaldehyde resin, cresol novolak resin, bisphenol A resin, and the said halogen-containing epoxides, etc. are mentioned. have.

The tertiary amine (trivalent amine) is preferably one in which all of the hydrogen in ammonia is substituted with an alkyl group, an allyl group, a phenol group and the like. Specific examples thereof include trimethylamine, triethylamine, trimethanolamine, triethanolamine, dimethylethanolamine, and the like.

The amount of epoxy and tertiary amine is appropriately adjusted according to the type of the compound, and it is preferable to give 0.1 to 1.0% of epoxy to the weight of fiber and 0.1 to 5.0% of the weight of epoxy to the weight of epoxy. If the amount of epoxy is too small, the adhesiveness between the fiber and the fiber of the fiber produced by the absolute lack of the required amount of crosslinking is low. If the amount of epoxy is too high, the spinning workability due to the epoxy drop becomes worse due to the excessive epoxy application and the weaving process is required. It acts as a foreign body and impairs workability.

Tersiatriamine promotes the reaction between polyester and epoxy. If the content of tersiariamine is too small compared to epoxy, the tertiary amine hardly functions to promote the reaction of epoxy due to the absolute shortage of the amount necessary for the role of catalyst. The reaction rate of istiaricamine itself is rapidly increased, and the reaction between the fiber and epoxy necessary for improving the adhesion is insufficient. In particular, when the content of teriatriamine is 0.2 to 2%, a better effect can be obtained, which is preferable.

Features and other advantages of the present invention as described above will become more apparent from the embodiments described below. It should be understood, however, that the present invention is not limited to the following examples.

Example 1

A polyester chip with an ultimate viscosity of 1.03 (measured at 30 ° C in a mixed solvent of phenol: tetrachloroneethane = 3: 2) was spun at a spinning temperature of 305 ° C with a hole diameter of 0.4 mm and a hole count of 192. For non-drawn yarn obtained by spinning at a discharge rate of 360 g / min at a temperature below the secondary transition point of the polymer, and using a conventional oiling roller, which is mainly composed of fatty acid esters and nonionic surfactants. An aqueous emulsifying solution in which 12 Kg of oil was dissolved in 80 Kg of water was added to the spinning emulsion treatment solution, and the unstretched yarn was obtained through the spinning machine of the one-stage Godetrol system. The temperature and line speed of the spinner gothetola were 50 ° C. and 600 m / min. Obtained undrawn yarn physical properties were 550% elongation and 5,400 denier of fineness.

The resulting undrawn yarn was drawn in a transverse stretching machine of a two stage oven-roller system. The speed and temperature of each roller set of the transverse stretching machine is 1 stage roller-40m / min, 80 ℃, 2 stage roller-160m / min, 100 ℃, 3 stage roller-240m / min, 100 ℃, 4 stage roller-220m / min, 80 degreeC, and the oven temperature between a 2nd stage and a 3rd stage roller was 240 degreeC, and the oven temperature between 3rd stage and a 4th stage roller was 250 degreeC.

Epoxy emulsifier was applied before the two-stage oven, and 8 Kg and 0.1 Kg of nonionic surfactant, trimethanolamine 0.08 as EPON812 (reaction product of glycerin and epichlorohydrin manufactured and sold by SHELL) Kg dissolved in 92 Kg of water was used.

The drawn yarn was evaluated for the initial adhesive strength and the heat resistant adhesive strength through 1), 2), 3) below. Adhesion results over time, spinning operation and post-processing properties are shown in Table 1.

1) Resorcinol / Formalin / Rubber Lataxe Adhesive (referred to as RFL for convenience)-A conventional adhesive composition for tire cords (concentration 20%) is prepared by the following method.

RFL adhesive

Raw material name Addition amount (part) Resorcinol 8.8 Formalin (37%) 4.76 Sodium hydroxide (10%) 10 Styrene / butadiene-1,3 / vinylpyridine, 15/70/15 rubber (41%) 56 water 17.6

2) Pass the 1000-denier / 2-ply polyester cord for tire reinforcement through the adhesive bath of 1) at a speed of 15-30 meters per minute to attach 3-8% solids, and dry at 150 ° C for 2 minutes and then 220 It is coated by heat treatment for 2 minutes at ℃.

3) The treated cords were evaluated by the initial H-test (H-Test) below the initial heat adhesion and heat resistance (measured after heat aging 76 hours in 150 ℃ oven).

<H-Test>

The following rubber composition was used to prepare according to ASTMD-2138-72 and vulcanized at 150 ° C. for 30 minutes at a pressure of 60 Kg / cm 2. The adhesive force was evaluated by drawing by Instron at 300 ° C./min at 25 ° C.

Rubber composition

Raw material name Addition amount (part) SBR 100 Zinc oxide 5 Carbon black 50 Stearic acid One Nectron 60 25 Tetramethylthiuram monosulfide 1.5 2-mertoptobenzothiazole 0.5 Yiwu 1.5

Example 2

20 Kg and 0.1 Kg of nonionic surfactant, trimethanolamine, ECN1400 (creation product of cresol novolak resin with epichlorohydrin as a product of CIBAGEIGY, concentration 40%). Dissolving 0.08 Kg in 80 Kg of water was used, and the results of the adhesion of the drawn yarn over time, spinning operation and post-processability are shown in Table 1.

Example 3

The same process as in Example 1 was carried out, but 8 kg and 0.1 kg of nonionic surfactant and 0.08 kg of triethanolamine were dissolved in 92 Kg of EPON812 (reaction product of glycerin and epichlorohydrin, manufactured by SHELL) with an epoxy emulsion. It was used, and the results of the adhesion of the drawn yarn over time, spinning operation and post-processing properties are shown in Table 1.

Example 4

The same process as in Example 1 was carried out, but 8 Kg and 0.1 K g of nonionic surfactant and 0.32 Kg of triethanolamine were dissolved in 92 Kg of water using EPON812 (reaction product of glycerin and epichlorohydrin manufactured by SHELL) as an epoxy emulsion solution. It was used, and the results of the adhesion of the drawn yarn over time, spinning operation and post-processing properties are shown in Table 1.

Example 5

The same process as in Example 1 was carried out, but 8Kg and 0.1Kg of nonionic surfactant and triethylamine (0.084Kg) were added to 92Kg of water using EPON812 (reaction product of glycerin and epichlorohydrin manufactured by SHELL) as an epoxy emulsion. The dissolved ones were used, and the results of the adhesion of the drawn yarns over time, spinning operation and post-processing properties are shown in Table 1.

Example 6

The same process as in Example 1 was carried out, but 8 Kg, 0.1 K g of nonionic surfactant and 0.08 Kg of trimethanolamine were dissolved in 92 Kg of EPON812 (reaction product of glycerin and epichlorohydrin manufactured by SHELL) with an epoxy emulsion. Table 1 shows the results of adhesive strength, spinning operation and post-processing of the obtained stretched yarn over time.

Example 7

Through the same process as in Example 1, 8Kg and 0.1Kg of nonionic surfactant, trimethanolamine 0.08Kg of EX-313 (reaction product of glycerin and epichlorohydrin, manufactured by NAGASE) as an epoxy emulsion solution, 92Kg of water Dissolved in was used, and the results of the adhesion strength, spinning operation and post-processing of the resulting stretched yarn is shown in Table 1.

Example 8

The same process as in Example 1 was carried out, but 8Kg and 0.1Kg of nonionic surfactant and trimethanolamine 0.16Kg of EPON812 (reaction product of glycerin and epichlorohydrin as a product of SHELL) were added to 92Kg of water as an epoxy emulsion. The dissolved ones were used, and the results of the adhesion of the drawn yarns over time, spinning operation and post-processing properties are shown in Table 1.

Example 9

The same process as in Example 1 was carried out, but 8Kg and 0.1Kg of nonionic surfactant and 0.04Kg of trimethanolamine were dissolved in 92Kg of water using EPON812 (reaction product of glycerin and epichlorohydrin manufactured by SHELL) as an epoxy emulsion. Table 1 shows the results of adhesive strength, spinning operation and post-processing of the obtained stretched yarn over time.

Comparative Example 1

The same process as in Example 1 was carried out, but 8 Kg, 0.1 Kg of nonionic surfactant and 0.008 Kg of trimethanolamine were dissolved in 92 Kg of EPON812 (reaction product of glycerin and epichlorohydrin, manufactured by SHELL) with an epoxy emulsion. Table 1 shows the results of adhesive strength, spinning operation and post-processing of the obtained stretched yarn over time.

Comparative Example 2

The same process as in Example 1 was carried out, but EPON812 8Kg and 0.1Kg of nonionic surfactant and 0.8Mg of trimethanolamine were dissolved in 92Kg of water as the epoxy emulsion solution. And post-processing properties are shown in Table 1.

Comparative Example 3

The same process as in Example 1 was carried out, but the epoxy emulsifier solution EPON812 50Kg and 0.1Kg of non-ionic surfactant, trimethanolamine 1.0Kg dissolved in 50Kg of water, the resulting stretched adhesive over time results and spinning operation And post-processing properties are shown in Table 1.

[Comparative Example 4]

Epoxy compound-containing spinning emulsion treatment solution was prepared by dispersing 8 kg of EPON812 in an aqueous emulsifier solution in which 12 Kg of polyester oil having a fatty acid ester and a nonionic crab lubricant were dissolved in 80 Kg of water. On the other hand, a polyester chip having an ultimate 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 an odd number of spinnerets of 220 g / The unstretched yarn obtained by spinning with the discharge amount of min is cooled to a temperature below the secondary transition point of the polymer, and the above-mentioned oil-forming roller is used to impart the emulsion treatment solution containing the epoxy compound. After drawing, I got a drawing company. The temperature and flux of the direct spinning stretcher Godetrola are 1 stage-80 ℃, 400m / min, 2 stage-100 ℃, 410m / min, 3 stage -110 ℃, 1600m / min, 4 stage-200 ℃, 2000m / min, 5-stage-room temperature, 1980m / min% and winding speed was 1980m / min.

Initial adhesive force and heat-resistant adhesive force of the obtained stretched yarn were evaluated by the method mentioned above. Adhesion results over time and spinning operation and post-processing are shown in Table 1.

[Comparative Example 5]

The same process as in Comparative Example 4 was carried out, but an aqueous emulsifying solution prepared by dissolving 80 Kg of water in 12 Kg of polyester oil having a fatty acid ester and a nonionic surfactant as a main component was prepared as a spinning emulsion treatment solution and was not smoked through an oil roller. Epoxy emulsion solution was prepared by dissolving EPON812 (reaction product of SHELL glycerin and epichlorohydrin) in the presence of 8 Kg and 0.1 Kg of nonionic surfactant in 92 Kg of water. The oil yarn was used to give the drawn yarn (the amount of filling was sufficiently buried so that a small amount of liquid dropped from the yarn). The resulting adhesive strength over time of the drawn yarn, spinning operation and post-processing properties are shown in Table 1.

Comparative Example 6

The same procedure as in Comparative Example 5 was carried out, but 8 parts of EPON812 (reaction product of SHELL glycerin and epichlorohydrin), 0.1 Kg of nonionic surfactant and 0.08 Kg of trimethanolamine were dissolved in 92 Kg of water. The result of the adhesion of the drawn yarn over time and the spinning operation and post-processability are shown in Table 1.

division EPOXY amount in drawn yarn (wt%) Amount of catalyst based on EPOXY (wt%) Initial adhesive strength after 2 weeks (Kg / cm) 2 Weeks Heat-resistant Adhesive Luck (Kg / cm) Presence of foreign body during spinning Body foreign body when weaving Example 1 0.40 1.0 13.5 10.5 radish radish Example 2 0.41 1.0 12.5 11.0 radish radish Example 3 0.39 1.0 14.0 12.0 radish radish Example 4 0.40 4.0 13.0 10.5 radish radish Example 5 0.38 1.0 12.0 10.0 radish radish Example 6 0.41 1.0 13.5 11.0 radish radish Example 7 0.40 1.0 12.0 10.0 radish radish Example 8 0.40 2.0 12.5 10.5 radish radish Example 9 0.41 0.5 12.5 10.0 radish radish Comparative Example 1 0.39 0.1 8.5 6.0 radish radish Comparative Example 2 0.38 10 7.0 5.0 radish radish Comparative Example 3 1.7 2.0 8.5 5.0 radish plenty Comparative Example 4 0.40 0 12 10 plenty radish Comparative Example 5 0.39 0 5 2 radish radish Comparative Example 6 0.35 1.0 10.0 8.0 radish radish

As is apparent from the experimental results of the above-described examples and comparative examples, in the case of Comparative Example 4 there was a problem in the long-term operability as the epoxy compound is accumulated in the godetrola, and in the case of Comparative Example 5 both the heat treatment and the catalyst after the epoxy application By omission, the reaction of the initial epoxy with the polyester terminal group progressed slowly, and the initial adhesive strength was insufficient after 2 weeks. Comparative Example 6 obtained a relatively high initial adhesive strength but did not obtain sufficient adhesive strength due to the nonuniformity of the epoxy compound imparted according to the high yarn speed. In Comparative Example 1, the reaction promotion was limited due to the small content of the applied catalyst, and thus the adhesion was low after 2 weeks. In Comparative Example 2, the content of the catalyst was too much compared to that of the epoxy, so that the side reaction of the epoxy was promoted and the adhesion was low. In Comparative Example 3, the imparting amount of epoxy was excessively excessive, so that weaving was lowered due to the dropping of the epoxy layer during weaving and the loss of adhesive force was excessive due to the excess of the epoxy layer.                     

On the other hand, the embodiment according to the present invention was able to obtain a stable heat-resistant adhesion by promoting the reaction between the epoxy and the fiber according to the uniform adhesion of the epoxy according to the stable yarn flux and the addition of a catalyst.

Claims (3)

In the polyester fiber, an epoxy compound having two or more epoxy groups and a tertiary amine compound are given, the amount of epoxy is 0.1-1.0% based on the weight of the fiber, and the amount of the tertiary amine is 0.1 to 5.0% by weight of the epoxy. Heat-resistant adhesive polyester fiber characterized in that the. delete The method according to claim 1, wherein 8.8 parts by weight of resorcinol, 4.76 parts by weight of formalin (37%), 10 parts by weight of sodium hydroxide (10%), styrene / butadiene-1,3 / vinylpyridine 15/70/15 rubber ( 41%) 15 to 30 per minute so that 3 to 8% solids is attached to the 1000 denier / 2-ply cord made of the polyester fibers in a resorcinol / formalin / rubber Latax adhesive bath comprising 56 parts by weight and 17.6 parts by weight of water. After passing through the meter at a speed of 2 minutes and drying at 150 ° C. for 2 minutes, it is coated by heat treatment at 220 ° C. for 2 minutes to make a treatment cord. The treated cord is 100 parts by weight of SBR, 5 parts by weight of zinc oxide, 50 parts by weight of carbon black, ASTMD-2138 using a rubber composition containing 1 part by weight of stearic acid, 25 parts by weight of nectron-60, 1.5 parts by weight of tetramethylthiuram monosulfide, 0.5 parts by weight of 2-mertoptobenzothiazole, and 1.5 parts by weight of io Prepared according to -72 and vulcanized at 150 DEG C for 30 minutes at a pressure of 60 Kg / ㎠, for 2 weeks After 2 weeks, the initial adhesive strength of the two-week fruit was measured by instron at 300mm / min at 25 ℃, and the initial adhesive strength was 12 kg / cm or more, and the two-week fruit heat adhesive strength was measured after thermal aging in the oven at 150 ° C. for 76 hours. The heat-resistant adhesive polyester fiber, characterized in that 10 kg / cm or more.