KR101906768B1 - Process for producing aqueous cross-linking agent for surface treatment of polyester fabric - Google Patents

Abstract

The present invention provides a method of preparing an aqueous cross-linking agent for treating a surface of polyester fabric. The method comprises: a first step of mixing polyalcohol with a first organic solvent at the temperature of 80 to 100°C; a second step of carrying out a reaction by adding Lewis acid catalysts and epichlorohydrin to a mixture prepared in the first step at the temperature of 60 to 90°C; a third step of adjusting the pH of the reaction mixture obtained in the second step to neutral and carrying out a reaction on the reaction mixture at the temperature of 70 to 80°C; a fourth step of adding a strongly alkaline aqueous solution to a reaction product obtained in the third step and carrying out a condensation reaction on the reaction product; a fifth step of adding a second organic solvent and washing water to a reaction product obtained according to the fourth step to separate a salt layer from a resin layer; and a sixth step of recovering and removing the second organic solvent from a resultant product obtained according to the fifth step. The fourth step of carrying out the condensation reaction comprises: a step A of carrying out a reaction after adding two-thirds of the strongly alkaline aqueous solution necessary for reaction with halohydrin ether to the reaction product obtained according to the third step; and a step B of carrying out a reaction after adding the second organic solvent to a reaction product obtained according to the step A and then adding one-third of the strongly alkaline aqueous solution necessary for reaction with the halohydrin ether to the mixture of the second organic solvent and the reaction product. A reaction temperature in the step B is controlled to be lower than a reaction temperature in the step A. According to the present invention, by using the method of preparing an aqueous cross-linking agent for treating a surface of polyester fabric, it is possible to obtain an aqueous cross-linking agent for treating a surface of polyester fabric, with high a solubilization rate while the probability of formation of an unreacted intermediate can be significantly lowered.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing an aqueous cross-linking agent for surface treatment of polyester fibers,

The present invention relates to a method for producing an aqueous crosslinking agent for surface treatment of polyester fibers.

Typical examples of fibers used as rubber reinforcements in rubber composites such as tires include nylon, rayon, and polyester.

Among them, the polyester fiber has a benzene ring in its molecular structure and a rigid molecular chain, and thus the tire cord made of the polyester fiber has good elasticity and fatigue resistance, less occurrence of flat spot, creep resistance and durability Is excellent. Due to these properties, polyester is widely used as a tire reinforcing fiber material.

However, despite these advantages, polyester fibers are difficult to adhere to elastomers such as rubber, which is an adhesive material, as an adhesive material, so that primer treatment is applied to the surface of polyester fibers to increase initial adhesion, Can be increased. An isocyanate-based water-dispersible resin and an aqueous cross-linking agent are mainly used as an adhesive substrate used for an adhesive primer.

However, the water-based cross-linking agent known so far has a problem in that when mixed with an isocyanate resin which is a water-dispersible resin in the surface treatment of polyester fiber, the mixing tank is washed from time to time or the residue is discarded due to sedimentation of agglomerates in a continuous process such as viscosity increase and coagulation phenomenon Problems occur, and workability, defects, and economic losses are very large. This is because the water-soluble crosslinking agent of the water-based crosslinking agent has a low water-solubility or compatibility with other resins. In order to achieve a high water-solubility during the production of a high-temperature reaction and solvent polymerization, However, this method can not prevent the loss of resin and the generation of a large amount of malicious wastewater. Therefore, there is no known method for producing a wastewater having a high yield, a high permeability and minimizing the generation of wastewater.

Accordingly, an object of the present invention is to provide a method for producing a water-based crosslinking agent having excellent affinity for water-dispersible resin and water at a high yield and minimizing the generation of waste water.

According to an aspect of the present invention, there is provided a process for preparing polyhydric alcohol, comprising the steps of: mixing polyhydric alcohol and a first organic solvent at 80 to 100 ° C; A second step of adding Lewis acid catalyst and epichlorohydrin to the mixture of the first step and dropwise adding the mixture at 60 to 90 캜; A third step of adjusting the pH of the reaction mixture obtained according to the second step to neutral and conducting the reaction at 70 to 80 ° C; And a fourth step of adding a strong alkaline aqueous solution to the reaction product of the third step and performing a condensation reaction, wherein a second organic solvent and wash water are added to the reaction product obtained in the fourth step, A fifth step of separating the liquid from the liquid. And a sixth step of recovering and removing the second organic solvent from the resultant product obtained in the fifth step, wherein the fourth step of performing the condensation reaction comprises adding halohydrin to the reaction product obtained by the third step, Adding a strong alkaline aqueous solution corresponding to 2/3 of the strong alkaline aqueous solution required for the reaction with the ether and reacting it with the aqueous solution of the strong alkaline aqueous solution required for the reaction with the ether; adding a second organic solvent to the reaction product obtained in the step A and then adding halohydrin ether And a step B for adding a strong alkaline aqueous solution corresponding to 1/3 of the strong alkaline aqueous solution required for the reaction and reacting the strong alkaline aqueous solution, wherein the reaction temperature of the step B is controlled to be smaller than the reaction temperature of the step A, A process for preparing a waterborne crosslinking agent for processing is provided.

By using the method for producing an aqueous crosslinking agent for surface treatment of polyester fibers of the present invention, it is possible to obtain a water-based crosslinking agent for surface treatment of polyester fibers having a remarkably low generation of unreacted intermediate product and a high rate of water-solubility. By minimizing the hydrolyzable chlorine content of the product, it is possible to minimize the generation of the wastewater by reducing the generation of the intermediate product, and thus the high yield and the separated liquid phase in the washing process can be clearly distinguished, minimizing the amount of process water used.

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The water-based crosslinking agent for surface treatment of polyester fibers according to the present invention has a remarkably low viscosity (coarse phenomenon) and coagulation phenomenon when mixed with an aqueous dispersion isocyanate resin and a water-based crosslinking agent, which are resins for surface treatment of polyester fibers, The resin loss can be prevented smoothly, and defects such as adhesion failure and partial discoloration due to agglomerates can be minimized.

Hereinafter, the method for producing an aqueous crosslinking agent for surface treatment of a polyester fiber of the present invention will be described in more detail.

A first step of mixing the polyhydric alcohol and the first organic solvent at 80 to 100 캜; A second step of adding Lewis acid catalyst and epichlorohydrin to the mixture of the first step and dropwise adding the mixture at 60 to 90 캜; And a third step of adjusting the pH of the reaction mixture obtained in the second step to neutrality and performing the reaction at 70 to 80 ° C. And a fourth step of adding a strong alkaline aqueous solution to the reaction product of the third step and performing a condensation reaction, wherein a second organic solvent and wash water are added to the reaction product obtained in the fourth step, A fifth step of separating the liquid from the liquid. And a sixth step of recovering and removing the second organic solvent from the resultant obtained in the fifth step, wherein the fourth step of carrying out the condensation reaction comprises reacting the reaction product obtained by the third step with a halohydrin ether Adding a strong alkaline aqueous solution corresponding to 2/3 of the strong alkaline aqueous solution required for the reaction and reacting it; adding a second organic solvent to the reaction product obtained in the step A and then reacting with a halohydrin ether And a step B for adding a strong alkaline aqueous solution corresponding to 1/3 of the strong alkaline aqueous solution required for the step A to react with the strong alkaline aqueous solution, wherein the reaction temperature of the step B is controlled to be smaller than the reaction temperature of the step A, A method for producing a water-based cross-linking agent is provided.

The reaction temperature in step A is 50 to 60 DEG C, and the reaction temperature in step B is 30 to 40 DEG C. When the reaction temperature of the step A and the step B is controlled to the above-mentioned range, the effect of suppressing the hydrolyzable chlorine content such as isomer formation due to the increase of the reaction temperature upon addition of the aqueous strong alkaline solution can be obtained.

According to the method for producing an aqueous crosslinking agent for surface treatment of polyester fibers according to the present invention, first, a first organic solvent is added to a polyhydric alcohol and mixed at 80 to 100 ° C. If the addition of the polyhydric alcohol and the first organic solvent is carried out at a temperature lower than 80 ° C, the dissolution state is poor. If the temperature is higher than 100 ° C, coloration such as discoloration may be caused.

In the epoxidation reaction with general polyhydric alcohols, an explosive exothermic reaction occurs when the reactivity of the Lewis acid catalyst is added in the presence of epichlorohydrin in comparison with the production process of the general glycidyl ether, so that the temperature control is very difficult and the side reaction If the amount of the catalyst is excessively increased, it is difficult to produce the desired product due to the adverse reaction, and the introduction of the catalyst at a low temperature has a problem that it is difficult to reach the reaction time and the heat generation process to the final target reaction temperature.

In order to solve the above-described problems, the present inventors conducted a reaction in which a polyhydric alcohol is dissolved in a first organic solvent and then epichlorohydrin is added at 60 to 90 ° C in the range of 2 to 8 hours in the presence of a Lewis acid catalyst. Since the polyhydric alcohol is dissolved in the first organic solvent and the reaction of epichlorohydrin proceeds in the first organic solvent solution state of the polyhydric alcohol, the temperature is easily controlled and discoloration and side reactions are significantly reduced. The polyhydric alcohol is at least one selected from compounds represented by the following general formulas (1a), (1b) and (1c), and is preferably a polyhydric alcohol having two or more valences.

[Formula 1a]

Wherein R < ₅ > is -H.

[Chemical Formula 1b]

Wherein R ₃ is -H, R ₄ is -OH,

[Chemical Formula 1c]

Wherein R < ₅ > is H and R < ₆ > is OH.

The epichlorohydrin may be represented by the following formula (2).

[Formula 2]

Wherein R ₇ is -OH or Cl.

The first organic solvent used for dissolving the polyhydric alcohol is preferably at least one selected from the group consisting of dioxane, benzene, and toluene, and more preferably, dioxane is used. The content of the first organic solvent is 80 to 90 parts by weight based on 100 parts by weight of the polyhydric alcohol. When the content of the first organic solvent is within the above range, the dissolution state is good and stable reaction is carried out without epoxidized state when epichlorohydrin is added.

BF ₃ and its complex salts such as BF ₃ .Et ₂ O, BF ₃ .H ₂ O, Sn (BF ₄ ), and the like can be used as non-limiting examples of the Lewis acid catalyst used in the reaction of the polyhydric alcohol and epichlorohydrin. _{2, Fe (BF 4) 2} , Ca (BF 4) 2, Zn (BF 4) 2, Mg (BF 4) 2, Cu (BF 4) 2, and the like of tin chloride, particularly Sn (BF _{4) 2, Fe (BF 4) 2} , Ca (BF 4) 2, Zn (BF 4) 2, Mg (BF 4) 2, it is more preferable from the reactivity to use a Cu (BF _{4) 2.} the Lewis acid The content of the catalyst is preferably 1000 to 1500 ppm based on 100 parts by weight of epichlorohydrin.

The content of epichlorohydrin is 4.0 to 6.5 mol based on 1 mol of sorbitol for sorbitol, 2.5 to 4.0 mol based on 1 mol of glycerin for glycerin, 1 mol of isobaride for isobaride To 2.0 moles to 3.5 moles. If the content of epichlorohydrin is lower than the lower limit of the reaction molar amount of the polyhydric alcohol, it takes a long time to reach an appropriate reaction temperature and the yield of the final product is lowered. When the content of epichlorohydrin exceeds the upper limit value on the basis of the reaction mole of the polyhydric alcohol The loss of residual epichlorohydrin in the unreacted state is large and the rate of hydrolysis is extremely reduced.

The reaction temperature of the polyhydric alcohol and epichlorohydrin is 60 to 90 ° C, more preferably 70 to 80 ° C, as described above. If the reaction temperature is less than 60 ° C, there is a large amount of unreacted products of epichlorohydrin and polyhydric alcohol, resulting in poor reactivity. As a result, the yield of the final product is low and the generation of the intermediate product is low. If it exceeds 90 DEG C, there is a risk of discoloration, and formation of an isomer is large, which is undesirable because the intermediate reaction is formed in a secondary reaction by a strong alkali catalyst. The reaction time is somewhat variable depending on the reaction temperature, and the reaction time is about 2 to 8 hours, preferably about 4 to 6 hours.

Since the reaction between the polyhydric alcohol and epichlorohydrin is influenced by moisture remaining in the polyhydric alcohol or epichlorohydrin, it is preferable to adjust the moisture content of the reactant to within a predetermined range. This can be controlled by the content of water contained in the organic solvent recovered in the first organic solvent recovery process after completion of the epichlorohydrin addition reaction.

The content of water contained in the polyhydric alcohol and epichlorohydrin is 1% by weight or less, particularly preferably 0.1 to 0.5% by weight, from the viewpoint of reactivity.

The pH of the reaction mixture obtained in the second step is adjusted to neutral, and the reaction is carried out at 70 to 80 ° C for the third step of aging to remove unreacted epichlorohydrin, thereby minimizing the formation of intermediates .

According to the second step, the strong alkaline aqueous solution may be additionally neutralized to the halohydrin ether within a range of 70 wt% with respect to the amount of the Lewis acid catalyst, so that the epoxidation reaction can be stably performed.

Subsequently, a strong alkali aqueous solution is added to the halohydrin ether obtained in the third step to carry out the condensation reaction thereof. The reaction of the halohydrin ether with the strong alkali aqueous solution is carried out in accordance with the two steps A and B. [

In Step A, a strong alkaline aqueous solution corresponding to 2/3 of the strong alkaline aqueous solution required for the reaction with the halohydrin ether and the halohydrin ether is added and reacted at 50 to 60 ° C. Step B is a step of adding a second organic solvent to the reaction product, adding thereto a strong alkaline aqueous solution corresponding to 1/3 of the strong alkaline aqueous solution required for reaction with the halohydrin ether, and reacting at 30 to 40 ° C. As described above, when the content of the strong alkaline aqueous solution is divided into two stages and the temperature of each step is controlled, an effect of suppressing the hydrolyzable chlorine content such as isomer formation due to the increase of the reaction temperature upon addition of the strong alkaline aqueous solution can be obtained. If the halohydrin ether and the strong alkali aqueous solution are added and reacted in one step all at once, it is difficult to control the reaction temperature and the yield of the intermediate product due to the side reaction is so high that the production yield of the coagulated residue due to the hydrolyzable chlorine, .

The second organic solvent is preferably at least one selected from the group consisting of methyl isobutyl ketone, methyl ethyl ketone, methyl butyl ketone, methyl n-amyl ketone, benzene and toluene.

As the strong alkali, sodium carbonate, potassium carbonate, sodium hydroxide, calcium hydroxide, potassium hydroxide or a mixture thereof is used, and a strong alkaline aqueous solution can be prepared by dissolving the above-mentioned strong alkali in water. The strong alkali aqueous solution is, for example, 25 to 100% by weight of sodium hydroxide, for example a 50% by weight aqueous solution of sodium hydroxide. At this time, the content of the strong alkali is preferably 0.8 to 1.3 mol based on 1 mol of epichlorohydrin based on 100% of the solid content.

A fifth step of separating the resin layer and the salt layer by adding a second organic solvent and wash water to the reaction product obtained in the fourth step; And a sixth step of recovering and removing methyl isobutyl ketone from the resultant product obtained in the fifth step. And then a seventh step of adding a phosphoric acid-based substance to the resultant product obtained in the sixth step.

The phosphoric acid-based material is added and reacted at 60 to 80 ° C, for example, at 75 ° C and filled with a 5 to 10 micron filter to obtain an aqueous crosslinking agent for surface treatment of polyester fibers. Phosphate-based material, for example, phosphoric acid, trisodium phosphate (Na3PO4), the second is a sodium phosphate (Na ₂ HPO _4), sodium hexametaphosphate [(NaPO _{3) 6]} at least one selected from the third in that phosphoric acid It is more advantageous in terms of stability and the like to use sodium (Na ₃ PO ₄ ), dibasic sodium phosphate (Na ₂ HPO ₄ ), and sodium hexametaphosphate [(NaPO 3) 6]. The phosphoric acid-based material controls its content so that the pH of the reaction product can be adjusted to a neutral state.

The concentration of the phosphoric acid material is, for example, 50 to 85% by weight. The reaction time after the addition of the phosphoric acid-based material is, for example, in the range of 0.5 to 1.0 hour.

The method for producing an aqueous crosslinking agent for surface treatment of a polyester fiber according to the present invention is characterized in that a halohydrin ether is obtained at a low temperature using an organic solvent and subjected to a step of aging in the third step, , The generation of glycerolized unreacted intermediate product by the side reaction in the secondary reaction is markedly lowered, and an aqueous crosslinking agent for surface treatment of polyester fibers having a high water-solubility can be obtained.

The water-based crosslinking agent for surface treatment of polyester fibers according to the present invention is characterized in that the epoxidation reaction of the halohydrin ether and the strong alkali aqueous solution in the secondary reaction is divided into two stages of A and B stages to carry out a condensation reaction to obtain the hydrolyzable chlorine content It is possible to obtain a water-based crosslinking agent for surface treatment of polyester fibers that minimizes the generation of wastewater by minimizing the generation of intermediates, thereby achieving a high yield and minimizing the amount of process water used by dividing the liquid surface in the washing process.

Due to the high water-solubility characteristics of the present invention, viscosity increase (rumen phenomenon) and flocculation phenomenon are remarkably low during mixing of the water-dispersed isocyanate resin and the water-based cross-linking agent, which is a resin for surface treatment of polyester fibers, workability is smooth, resin loss can be prevented, It is possible to minimize defects such as adhesion failure and partial discoloration due to the above-described problems. As described above, the water-based crosslinking agent obtained according to the present invention can be used in applications such as a curing accelerator such as a urethane resin and an acrylic resin, an adhesion imparting agent, a viscosity adjusting agent, a water-solubility improving agent, Lt; / RTI >

According to another aspect of the present invention, the water-based crosslinking agent for surface treatment of polyester fibers obtained by the above production method has a total chlorine content of 10 wt% or less, for example, 5 wt% or less, for example, 0.1 to 3 wt% The content of hydrolyzable chlorine is 5700 to 9100 ppm, and the content of total chlorine is 65,000 to 92,000 ppm. The solubility (water-solubilization ratio) of the water-based crosslinking agent in water is 110% to 180%, and the yield of the object is 95% or more, for example, 95 to 98%.

According to still another aspect of the present invention, there is provided a surface-treated polyester fiber using an aqueous cross-linking agent obtained by the above-mentioned production method.

The surface-treated polyester fiber includes a polyester fiber, and a surface treatment film comprising a cross-linking reaction product of an aqueous cross-linking agent and a water-dispersible resin obtained by the above production method on the polyester fiber. Such a surface-treated polyester fiber can be produced according to a method described later.

The water-based crosslinking agent, the water-dispersible resin and the solvent of the present invention are mixed to obtain a surface treatment film composition. As the water-dispersible resin, an isocyanate-based resin can be used. The isocyanate resin means a compound having at least two isocyanate groups in the molecular structure. The isocyanate group in the isocyanate resin reacts with a hydroxyl group in the modified polyester polyol resin to form a urethane bond (-NHCOO-), thereby forming a polymer network, thereby imparting durability Can be given.

The isocyanate resin may be at least one selected from the group consisting of 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), diphenylmethane- Diisocyanate (2,4-MDI), diphenylmethane-2,2'-diisocyanate (2,2'-MDI), 1,6-hexamethylene diisocyanate (1,6-HDI), 2,2,4 (2,4,4) -trimethylhexamethylene diisocyanate (2,2,4 (2,4,4) -TMDI), * j phenylenediisocyanate (PPDI ), 4,4'-dicyclohexylmethane diisocyanate (HMDI), m-xylene diisocyanate (XDI), isophorone diisocyanate (IPDI), 1,5-naphthalene diisocyanate (NDI) -Cyclohexyl diisocyanate (CHDI), isocyanurate-modified hexamethylene diisocyanate, and polyether-modified hexamethylene diisocyanate. For example, MDI (methylene di-isocyanate) resin or HDI (hexamethylene di-isocyanate) resin can be used.

The isocyanate resin is a mixture of hexamethylene diisocyanate trimer (Burnock DN955, DIC, NCO%: 5-8%) available from DIC, Desmodur N3300 available from Bayer MaterialScience and polyhydride modified hexamethylene diisocyanate (Bayhydur 3100 ). ≪ / RTI > The isocyanate resin may have an isocyanate group content (NCO%) of 5 to 23% by weight. As the isocyanate resin of the present invention, for example, a blocked methylene diisocyanate resin (Degussa Corporation, VESTAGON EP BF 9030) may be used.

The content of the crosslinking agent is 10 parts by weight or less, for example, 8 to 10 parts by weight, based on 100 parts by weight of the total amount of the surface treatment film composition. The surface treatment film composition may further contain a curing accelerator. As such a curing accelerator, tertiary amines such as trialkylamines such as triethylamine, triethanolamine, and tri-alcoholamine can be used.

The surface-treated polyester fiber of the present invention has the above-mentioned surface treatment film, so that the crosslinking density in the surface treatment film is high, and the adhesion to other substrates is greatly improved.

The surface-treated polyester fiber is not limited in its application field. For example, the polyester fiber for rubber reinforcement can be produced by treating with a composition for reinforcing rubber.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but it should be understood that the present invention is not limited to the following examples.

Example  One

182 g of sorbitol and 146 g of a dioxane solution were added to a 2 L four-necked flask equipped with a reflux condenser and the reaction flask was heated to 90 DEG C to completely dissolve it. Then, 1500 ppm of Sn (BF ₄ ) ₂ was added to the reaction flask, and the mixture was stirred for 1 hour. Subsequently, 510 g of ECH (epichlorohydrin) was added at a reaction temperature of 75 ° C for 5 hours. After completion of the reaction, the reaction mixture was aged for 1 hour. Then, 0.55 g of a 50% by weight aqueous solution of sodium hydroxide was added to the reaction mixture and reacted for 30 minutes. Subsequently, evaporation under reduced pressure was carried out for 2 hours to remove and recover the dioxane.

Then, the condensation reaction of the resultant product (glycidylation reaction of halohydrin ether) according to the above procedure was carried out in the following steps A and B. 189 g of a 50% by weight sodium hydroxide aqueous solution was added to the obtained halohydrin ether at 55 캜 for 1.5 minutes while being added with 1.5 to 1.6 g per minute for 120 minutes.

Subsequently, 407 g of methyl isobutyl ketone was added to the reaction product, 95 g of a 50 wt% aqueous sodium hydroxide solution was added, and the epoxidation reaction was carried out while adding 3.1 to 3.2 g per minute at 35 DEG C for 30 minutes.

After completion of the reaction, 715 g of methyl isobutyl ketone and 405 g of water were added to the reaction mixture, and the mixture was stirred and allowed to stand for separation of the resin layer and the brine layer to remove the brine layer to obtain a resin layer. Subsequently, methyl isobutyl ketone as a second organic solvent in the reaction mixture was recovered by reducing the pressure for 3 hours, 0.1 g of 98 wt% phosphoric acid was added thereto, stirred at 75 ° C for 1 hour, 481 g of an aqueous crosslinking agent for surface treatment of polyester fibers was obtained.

Comparative Example  One

466 g of an aqueous crosslinking agent for surface treatment of polyester fibers was obtained in the same manner as in Example 1, except that 0.55 g of a 50 wt% strong alkali aqueous solution was not added after completion of aging with epichlorohydrin in Example 1.

Comparative Example  2

Except that the glycidylation reaction of the halohydrin ether was carried out in the same manner as in Example 1 except that 284 g of a 50% by weight aqueous solution of sodium hydroxide was added without carrying out the glycidylation reaction of the halohydrin ether in the two steps (Step A and Step B) , And the procedure of Example 1 was repeated to obtain 402 g of an aqueous crosslinking agent for surface treatment of polyester fibers.

Practice 2

184.2 g of glycerin and 147 g of dioxane were added to a 2 L four-necked flask equipped with a reflux condenser, and the reaction flask was heated to 90 DEG C to completely dissolve it. Then, 1500 ppm of Sn (BF4) 2 was added to the reaction flask, and the mixture was stirred for 1 hour. Subsequently, 555 g of ECH (epichlorohydrin) was added at a reaction temperature of 75 ° C for 5 hours. After completion of the reaction, aging was performed for 1 hour. Then, 0.57 g of a 50% by weight aqueous solution of sodium hydroxide was added to the reaction mixture and reacted for 30 minutes. Subsequently, evaporation under reduced pressure was carried out for 2 hours to remove and recover the dioxane,

Subsequently, the condensation reaction of the resultant product (the epoxidation reaction of the halohydrin ether) obtained in the above procedure was carried out sequentially in steps A and B. Subsequently, 188 g of a 50 wt% aqueous solution of sodium hydroxide was added to the obtained halohydrin ether at 55 ° C for 1.5 minutes while being added with 1.5 to 1.6 g per minute for 120 minutes.

Next, 434 g of methyl isobutyl ketone was added to the reaction product, 94 g of a 50 wt% aqueous solution of sodium hydroxide was added, and the epoxidation reaction was performed while adding 3.1 to 3.2 g per minute at 35 캜 for 30 minutes.

After completion of the reaction, 763 g of methyl isobutyl ketone and 432 g of water were added to the reaction mixture, and the mixture was stirred and allowed to stand for separation of the resin layer and the brine layer to remove the brine layer to obtain a resin layer. Subsequently, methyl isobutyl ketone as a second organic solvent in the reaction mixture was recovered by reducing the pressure for 3 hours, 0.1 g of 98 wt% phosphoric acid was added thereto, and the mixture was stirred at 75 캜 for 1 hour. 511 g of an aqueous crosslinking agent for fiber surface treatment was obtained.

Comparative Example  3

485 g of an aqueous crosslinking agent for surface treatment of polyester fibers was obtained in the same manner as in Example 2, except that 0.55 g of a 50 wt% strong alkali aqueous solution was not added after completion of epichlorohydrin dropping in Example 2.

Comparative Example  4

The procedure of Example 2 was repeated except that 282 g of a 50 wt% aqueous solution of sodium hydroxide was added in the glycidylation reaction of the halohydrin ether in Example 2, regardless of the two stages, to obtain 383 g of an aqueous crosslinking agent for surface treatment of polyester fibers ≪ / RTI >

Example  3

146 g of isobaride and 117 g of a dioxane solution were added to a 2 L four-necked flask equipped with a reflux condenser and the reaction flask was heated to 90 DEG C to completely dissolve it. Then, 1500 ppm of Sn (BF4) 2 was added to the reaction flask, and the mixture was stirred for 1 hour. Subsequently, 220 g of ECH (epichlorohydrin) was added at a reaction temperature of 75 캜 for 5 hours. After completion of aging for 1 hour, 0.25 g of a 50% by weight aqueous sodium hydroxide solution was added to the reaction mixture and reacted for 30 minutes. Subsequently, evaporation under reduced pressure was carried out for 2 hours to remove and recover the dioxane. Then, the epoxidation reaction of the halohydrin ether obtained in accordance with the above procedure was sequentially carried out in steps A and B.

125 g of a 50 wt% aqueous solution of sodium hydroxide was added to the obtained halohydrin ether at 55 ° C for 120 minutes while being added with 1.0 to 1.1 g per minute.

Subsequently, 378 g of methyl isobutyl ketone was added to the reaction product, 95 g of a 50 wt% aqueous solution of sodium hydroxide was added, and the glycidylation reaction was performed while adding 3.0 to 3.1 g per minute at 35 DEG C for 30 minutes.

When the reaction was completed, 403 g of methyl isobutyl ketone and 228 g of water were added to the reaction mixture, and the mixture was stirred and allowed to stand for separation of the resin layer and the brine layer to remove the brine layer to obtain a resin layer. Subsequently, methyl isobutyl ketone as a second organic solvent in the reaction mixture was recovered by reducing the pressure for 3 hours, 0.1 g of 98 wt% phosphoric acid was added thereto, and the mixture was stirred at 75 캜 for 1 hour. 238 g of an aqueous crosslinking agent for fiber surface treatment was obtained.

Comparative Example  5

230 g of an aqueous crosslinking agent for surface treatment of polyester fibers was obtained in the same manner as in Example 3, except that 0.25 g of a 50 wt% strong alkali aqueous solution was not added after completion of epichlorohydrin drop-wise addition in Example 3.

Comparative Example  6

Example 3 was carried out in the same manner as in Example 3, except that 220 g of a 50 wt% aqueous solution of sodium hydroxide was added in the glycidylation reaction of halohydrin ether in two steps, 181 g of an aqueous crosslinking agent for surface treatment of polyester fibers was obtained.

Example  4

153.7 g of sorbitol and 38.4 g of glycerin and 153 g of dioxane were added to a 2 L four-necked flask equipped with a reflux condenser, and the reaction flask was heated to 90 캜 to completely dissolve it. Then, 1500 ppm of Sn (BF4) 2 was added to the reaction flask, and the mixture was stirred for 1 hour. Subsequently, 545 g of ECH (epichlorohydrin) was added at a reaction temperature of 75 캜 for 5 hours. After completion of aging for 1 hour, 0.58 g of a 50% by weight aqueous solution of sodium hydroxide was added to the reaction mixture and reacted for 30 minutes. Subsequently, evaporation under reduced pressure was carried out for 2 hours to remove and recover the dioxane. Then, the epoxidation reaction of the halohydrin ether obtained in the above procedure was sequentially carried out in steps A and B. Subsequently, 202 g of a 50 wt% aqueous solution of sodium hydroxide was added to halohydrin ether obtained by the above process while being added with 1.6 to 1.7 g per minute at 55 캜 for 120 minutes.

Subsequently, 435 g of methyl isobutyl ketone was added to the reaction product, 101 g of a 50 wt% aqueous solution of sodium hydroxide was added, and the epoxidation reaction was carried out while 3.3 to 3.4 g / minute was added at 35 캜 for 30 minutes.

After completion of the reaction, 815 g of methyl isobutyl ketone and 461 g of water were added to the reaction mixture, and the mixture was stirred and allowed to stand for separation of the resin layer and the brine layer to remove the brine layer to obtain a resin layer. Subsequently, methyl isobutyl ketone as a second organic solvent in the reaction mixture was recovered by reducing the pressure for 3 hours, 0.1 g of 98 wt% phosphoric acid was added thereto, and the mixture was stirred at 75 캜 for 1 hour. 505 g of an aqueous crosslinking agent for fiber surface treatment was obtained.

Comparative Example  7

494 g of an aqueous crosslinking agent for surface treatment of polyester fibers was obtained in the same manner as in Example 4, except that 0.58 g of a 50% by weight strong alkali aqueous solution was not added after completion of epichlorohydrin dropping in Example 4.

Comparative Example  8

In the epoxidation reaction of the halohydrin ether in Example 1, the same procedure as in Example 4 was carried out except that 303 g of a 50 wt% aqueous solution of sodium hydroxide was added in two stages, 375 g of an aqueous crosslinking agent for ester fiber surface treatment was obtained (yield: 72%, water-solubility of 160%).

Example  5: Surface treatment of polyester fiber

Polyethylene terephthalate as a polyester fiber was mixed with an aqueous crosslinking agent obtained in Example 1 and an isocyanate resin (blocked methylene diisocyanate resin (Degussa Corporation, VESTAGON EP BF 9030) which is a water dispersion resin having a solid content of 60 wt% A composition for 1-Dip surface treatment containing soft water as a solvent is applied, followed by drying and then applying resorcinol formaldehyde latex, which is a composition for a second dip surface treatment, The surface-treated polyester fibers were prepared. The compositions of the surface treatment compositions used in the first and second dip processes are shown in Tables 1 and 2, respectively.

Ingredients Formulation (g) Water-based crosslinking agent 2.7 Blocked Isocyanate solution 6.35 NBR LaTeX 7.45 Soft water 83.5 Total 100

The polyester fiber was impregnated with the composition of the primary dip process of Table 1 and then dried at 250 캜 for 100 seconds to prepare a polyester fiber having a primary surface treatment film.

Ingredients Formulation (g) Resorcinol 1.88 Formalin 37% 2.76 Vinyl pyridine-SBR latex (40.5%) 42.1 Caustic soda (10%) 0.51 Ammonium Hydroxude (28%) 3.32 Soft water 49.43 Total 100

The composition of the second dip process in Table 2 was impregnated with the polyester fiber treated with the primary surface treatment film and then dried at 250 캜 for 100 seconds to obtain a surface treated polyester fiber having a secondary surface treatment film and a non- 1PLY laminated surface-treated polyester fibers as shown in Table 1 and Table 2 were laminated on a sulfurized NBR compound rubber sheet and vulcanized at 175 ° C under a pressure of 50 N for 10 minutes to prepare a vulcanized rubber sheet for reinforcing polyester fiber.

Example  6 to 8

A vulcanized rubber sheet for reinforcing a polyester fiber was prepared in the same manner as in Example 5, except that the aqueous crosslinking agent obtained in Example 2 was used instead of the aqueous crosslinking agent obtained in Example 1.

Comparative Example  9-1 and 9-2

A surface-treated polyester fiber reinforcing vulcanized rubber sheet was prepared in the same manner as in Example 5 except that the crosslinking agent obtained in Comparative Example 1 and Comparative Example 2 was used in place of the aqueous crosslinking agent obtained in Example 1, .

Comparative Example  10-1 and 10-2

A surface-treated polyester fiber reinforcing vulcanized rubber sheet was prepared in the same manner as in Example 5 except that the crosslinking agent obtained in Comparative Example 3 and Comparative Example 4 was used in place of the aqueous crosslinking agent obtained in Example 2, .

Comparative Example  11-1 and 11-2

A surface-treated polyester fiber reinforcing vulcanized rubber sheet was produced in the same manner as in Example 5 except that the crosslinking agent obtained in Comparative Example 5 and Comparative Example 6 was used in place of the aqueous crosslinking agent obtained in Example 3, .

Comparative Example  12-1 and 12-2

A surface-treated polyester fiber reinforcing vulcanized rubber sheet was prepared in the same manner as in Example 5 except that the crosslinking agent obtained in Comparative Example 7 and Comparative Example 8 was used in place of the aqueous crosslinking agent obtained in Example 4, .

Evaluation example  One

The epoxy equivalent, the hydrolyzable chlorine content, the chlorine content, the water content, the viscosity, the yield and the water-solubility of the water-based crosslinking agent for surface treatment of polyester fibers obtained in Example 1-4 and Comparative Example 1-8 were measured, Table 3 shows the results.

The epoxy equivalent was determined by titrating 0.1 N aqueous NaOH solution and the hydrolyzable chlorine content, chlorine content and moisture content were measured using the Karl-Fusher method and the viscosity was measured with a Brookfield viscometer , And the degree of hydrolysis was expressed as a percentage based on 100% solubility when 10 g of an aqueous crosslinking agent for surface treatment of polyester fibers was dissolved in 100 g of water (25 ° C).

The viscosity was measured using a Brookfield viscometer. The gelation time was measured by mixing 6 g of water-dispersed isocyanate and 1 of water-based crosslinking agent 1 for polyester fiber surface treatment, Plate was used and expressed as sec. The residue was obtained by mixing 500 ml of glass beaker with 400 ml of water, 12 g of magnesium stearate at 200 rpm, stirring for 30 minutes, and allowing to stand for 30 minutes. Respectively.

The epoxy equivalent, hydrolyzable chlorine content, total chlorine content, water content, viscosity, yield and rate of water-solubility of the aqueous crosslinking agent for surface treatment of the polyester fiber are shown in Table 3 below.

division Epoxy
equivalent weight
(g / eq) Hydrolyzable chlorine (ppm) Subdivision fraction
(ppm) Moisture content
(wt%) Viscosity
(cps @ 25) Yield
(%) Acceptance rate
(%) Example 1 170.6 9,050 91,350 0.1 18,500 97 160 Example 2 139.3 8,153 89,570 0.1 165 98 175 Example 3 228.2 5,794 69,544 0.1 850 96 180 Example 4 181.5 8,048 85,740 0.1 4,950 97 170 Comparative Example 1 171.9 9,127 93,535 0.1 18,150 94 95 Comparative Example 2 183.4 11,531 120,450 0.2 20,120 81 148 Comparative Example 3 140.8 8,275 90,054 0.1 165 95 105 Comparative Example 4 147.3 10,978 115,490 0.2 212 75 153 Comparative Example 5 230.1 5,996 70,135 0.1 890 93 100 Comparative Example 6 243.8 9,548 99,574 0.15 1,330 73 170 Comparative Example 7 181.9 8,150 86,050 0.1 4,950 95 98 Comparative Example 8 186.3 11,493 121,274 0.15 6,050 72 160

As shown in Table 3, according to Examples 1 to 4, it was found that the water content was 160% or more and the chlorine content was small. According to the above Comparative Example 1, the rate of water-solubility was remarkably low as compared with Example 1. This is because the residual acid catalyst in the 2-step reaction causes the oligomeric halohydrin ether to be polymerized and to affect the epoxidation reaction And the results of Comparative Example 3, Comparative Example 5, and Comparative Example 7 also show the same results. It can be seen that the rate of hydrogenation depends on the amount of the Lewis acid catalyst, and the neutralization step and the remaining acid catalyst are carried out in the first solvent The effect can be minimized by eliminating it during recovery.

In the case of Comparative Example 2, when the reaction was continued at a reaction temperature of 60 ° C without continuous dehydration, isomer formation was large and the hydrolyzable chlorine content was high, resulting in poor separation and waste water generation. And the results of Comparative Example 4, Comparative Example 6, and Comparative Example 8 also show the same results. In the case of Comparative Examples 3, 5 and 7, the chlorine content was not high but the acceptance rate was low.

As a result of the measurement of the mixture of water-dispersed isocyanate and water-based crosslinking agent, the viscosity, gelling time and remnants of the mixture are shown in Table 4, respectively. The gelling time was measured by mixing and stirring 1 g of the aqueous crosslinking agent with 6 g of the water-dispersed isocyanate, and measuring the amount of the test sample once per 1 g.

Referring to Table 4, according to Example 1-4, it was found that there was almost no residue, unlike the case of Comparative Example 1-8.

Evaluation example  2

The polyester fiber-reinforced rubber sheets surface-treated in Example 5 were subjected to peeling tests according to Comparative Examples 9 to 12 and Comparative Examples 10-1 to 12-2. The peeling test was carried out in an Instron according to ASTM D 4393D at 25 ° C at a rate of 100 mm / min, and the adhesive strength is shown in Table 5 below.

division Adhesion (Kg / ㎠) Adhesion (kg / cm 2) after aging test (100 ° C / 24 hours) Example 5 22.4 21.3 Example 6 19.8 19.1 Example 7 24.3 22.8 Example 8 22.6 21.4 Comparative Example 9-1 17.3 12.8 Comparative Example 9-2 16.8 12.2 Comparative Example 10-1 16.4 13.3 Comparative Example 10-2 16.2 12.9 Comparative Example 11-1 19.7 16.5 Comparative Example 11-2 19 14.6 Comparative Example 12-1 17.2 12.5 Comparative Example 12-2 16.4 12.1

As shown in Table 5, it was found that the polyester fiber-reinforced rubber sheets surface-treated in accordance with Examples 5 to 8 had significantly improved adhesive strength as compared with the vulcanized rubber sheets obtained in Comparative Examples 9-1 to 12-2 there was.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the scope of the present invention . Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

Claims (7)

Mixing at least one polyhydric alcohol and at least one first organic solvent selected from the group consisting of dioxane, benzene and toluene at 80 to 100 캜;
A second step of adding Lewis acid catalyst and epichlorohydrin to the mixture of the first step and dropwise adding the mixture at 60 to 90 캜;
A third step of adjusting the pH of the reaction mixture obtained according to the second step to neutral and conducting the reaction at 70 to 80 ° C;
And a fourth step of adding a strong alkali aqueous solution to the reaction product of the third step followed by a condensation reaction,
At least one second organic solvent selected from the group consisting of methyl isobutyl ketone, methyl ethyl ketone, methyl butyl ketone, and methyl n-butyl amyl ketone and water washing water are added to the reaction product obtained in the fourth step to separate the salt layer and the resin layer 5 < th > And
And a sixth step of recovering and removing the second organic solvent from the resultant obtained by the fifth step,
The fourth step of performing the condensation reaction may include a step A in which a strong alkaline aqueous solution corresponding to 2/3 of the strong alkaline aqueous solution necessary for the reaction with the halohydrin ether is added to the reaction product obtained in the third step,
Adding a second organic solvent to the reaction product obtained in the step A, adding a strong alkaline aqueous solution corresponding to 1/3 of the strong alkaline aqueous solution required for the reaction with the halohydrin ether, and reacting the resultant; , The reaction temperature of step B is controlled to be smaller than the reaction temperature of step A,
Wherein the reaction temperature in step A is 50 to 60 ° C, the reaction temperature in step B is 30 to 40 ° C, and the phosphoric acid-based material is added to the reaction product obtained in step 6 to react at 70 to 80 ° C. 7, wherein the phosphoric acid-based material is selected from the group consisting of phosphoric acid, sodium triphosphate (Na ₃ PO ₄ ), sodium diphosphate (Na ₂ HPO ₄ ), sodium hexametaphosphate [(NaPO ₃ ) ₆ ] Or more,
Wherein the polyhydric alcohol is a mixture of one or more selected from the group consisting of compounds represented by formulas (1a), (1b) and (1c), glycerin, sorbitol and isobide,
Wherein the epichlorohydrin is a compound represented by the following formula (2).
[Formula 1a]

Wherein R < ₅ > is -H,
[Chemical Formula 1b]

Wherein R ₃ is -H, R ₄ is -OH,
[Chemical Formula 1c]

Wherein R < ₅ > is H, R < ₆ &
(2)

Wherein R < ₆ > is -OH or -Cl. delete delete delete delete The method of claim 1, wherein the Lewis acid catalyst _{BF 3, BF 3 · Et 2} O, BF 3 · H 2 O, Sn (BF 4) 2, Fe (BF 4) 2, Ca (BF 4) 2, Zn (BF ₄ ) ₂ , Mg (BF ₄ ) ₂ , Cu (BF ₄ ) ₂ and tin chloride. delete