JPH07278966A - Production of polyester fiber - Google Patents

Abstract

PURPOSE:To provide a process for producing a polyester fiber having high strength and excellent dimensional stability with heat and suitable for industrial materials, especially for a belt. CONSTITUTION:A polyethylene terephthalate having an intrinsic viscosity of 0.8-1.1 or a polyester composed mainly of polyethylene terephthalate is spun by melt-spinning, taken up at a speed of >=3,000m/min as undrawn yarn oriented and crystallized in a state of low orientation degree and drawn under heating to produce a polyester fiber. In the above production process, the fiber is oiled with a spinning oil composed mainly of a composition consisting of (A) an ester of an aliphatic alcohol and an aliphatic carboxylic acid, (B) an ethylene oxide and/or propylene oxide adduct of an aliphatic alcohol, (C) an ethylene oxide and/or propylene oxide adduct of a fatty acid amide compound and optionally (D) a dimethylpolysiloxane.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing polyester fibers suitable for industrial materials, especially for belts.

[0002]

2. Description of the Related Art Polyester fibers represented by polyethylene terephthalate fibers have excellent physical and chemical properties, are industrially mass-produced, and are extremely useful fibers widely used in various fields. With the increasing demand for higher performance, fibers having good dimensional stability against heat have been demanded.

As a method for increasing the dimensional stability of polyester fibers against heat, a method is known in which an unstretched yarn having a high degree of molecular orientation is taken up and subjected to heat stretching by increasing the spinning speed. For example, in Japanese Examined Patent Publication No. 3-21647, a melt spun yarn is drawn at a speed of 3000 m / min or more, and an oriented and crystallized undrawn yarn is drawn at a drawing start temperature of 125 ° C. or more.
A method of drawing at a draw ratio of 1.5 to 2.0 times has been proposed, but the breaking elongation of the drawn yarn is extremely low at about 7 to 8%, and there is a problem in operation in this case as well. When the drawing is performed at a high speed as in the spin draw method which is performed as described above, the operation is extremely difficult.

As a method for producing a fiber satisfying both thermal dimensional stability and strength on an industrial scale with good production, a melt spun yarn is drawn at a speed of 3000 m / min or more, and oriented crystallization is performed in a state where the degree of orientation is low. There is a method (Japanese Patent Application No. 4-359559) for hot drawing the undrawn yarn.

On the other hand, rib V belts, timing belts, etc., which are typified by transmission belts, are formed in a tubular shape in advance from the vulcanized polyester fiber reinforced rubber composite into a sliced shape in order to simplify the manufacturing process by reducing the cost. It is cut and commercialized. However, a single yarn is frayed from the polyester fiber exposed on the side surface of the belt cut in the fiber axis direction,
May project like fluff. In that case, not only the quality of the product will deteriorate, but if you set it on the pulley and operate it as it is, the frayed part of this single thread is rubbed by the pulley and the frayed single thread scatters, and this fraying causes the belt to break. It may reduce durability.

As a method for solving this problem, after twisting the polyester fiber into a cord, the cord is impregnated with an epoxy adhesive and / or an isocyanate adhesive and heat-treated to form a polyester fiber single yarn. A method for adhering the gaps (Japanese Patent Laid-Open Nos. 60-110978 and 60-110979)
No. 60-110980). However, in the case where the conventional spinning oil agent is added, the compatibility between the oil agent and the adhesive is poor, and the oil agent and the adhesive are separated from each other, or the adhesive does not sufficiently penetrate into the inside of the fiber, so that a sufficient effect is obtained. Was not obtained. On the other hand, when a spinning oil agent that does not have such a problem is used, there is a problem that single yarn breakage occurs frequently in the manufacturing process of the polyester fiber because the yarns on the take-up roller and the drawing roller do not have a bundling property.

[0007]

The present invention has high strength,
It has excellent dimensional stability against heat, and can be treated with an epoxy-based adhesive and / or an isocyanate-based adhesive as a cord, and the adhesiveness with rubber can be improved by simply performing ordinary RFL treatment. When a fiber-reinforced rubber composite is cut in the direction of the fiber axis, a polyester fiber having the characteristics of not fraying the single filament of the polyester fiber exposed on the cut surface and protruding in a fluff shape from the cut surface is manufactured with good operability. The present invention intends to provide a method for producing a polyester fiber which can be manufactured.

[0008]

[Means for Solving the Problems] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that the melt-spun yarn is 3000
It is effective to add a spinning oil agent having a specific composition in a method for producing a polyester fiber which is taken as an undrawn yarn that is oriented and crystallized in a state of a low degree of orientation at a speed of m / min or more and is hot-drawn. And has reached the present invention.

That is, the gist of the present invention is as follows. Polyethylene terephthalate having an intrinsic viscosity of 0.8 to 1.1 or polyester composed mainly of this is melt-spun and
At the speed of 00 m / min or more, it is taken as an oriented and crystallized undrawn yarn in a low degree of orientation, and hot-drawn to produce a polyester fiber. A method for producing a polyester fiber, which comprises applying an oil agent that (A) Ester of aliphatic alcohol and aliphatic carboxylic acid or its ethylene oxide and / or propylene oxide adduct 2 to 20% by weight (B) Ethylene oxide and / or propylene oxide adduct of aliphatic alcohol 20 to 80% by weight (C) Ethylene oxide and / or propylene oxide adduct of fatty acid amide compound 10 to 50% by weight (D) Dimethylpolysiloxane 0 to 5% by weight

The present invention will be described in detail below. In the present invention, polyethylene terephthalate having an intrinsic viscosity (measured at a temperature of 20 ° C. with an equal weight mixture of phenol and tetrachloroethane as a solvent) in the range of 0.8 to 1.1 or a polyester mainly composed thereof is melt-spun, and 3000
The undrawn yarn is drawn at a speed of m / min or more. If the intrinsic viscosity is lower than this range, the strength properties of the fiber will be inferior,
On the other hand, if it is higher than this range, the spinning stress is high and the spinnability is deteriorated, which is not preferable. Further, if the spinning speed is less than 3000 m / min, fibers having good dimensional stability cannot be obtained.

In the present invention, it is necessary to obtain an undrawn yarn that is oriented and crystallized in a state where the degree of orientation is low. To this end, melt spinning at a high speed and setting an extreme temperature gradient on the spinning line may control the crystallization and orientation of the undrawn yarn. For example, the spinning temperature is set to 290 to 310 ° C, and the atmospheric temperature 10 cm below the spinneret is controlled to 300 to 350 ° C by disposing a heating cylinder or the like. If the spinning temperature and this atmospheric temperature are lower than this range, the initial stress is high and it is difficult to take off at a high speed of 3000 m / min or more. If the spinning temperature and this atmospheric temperature are higher than this range, the subsequent cooling becomes incomplete. The occurrence of oriented crystallization is delayed, resulting in a highly oriented undrawn yarn. Furthermore, in order to keep the ambient temperature below 60 ° C 30 to 70 cm below the spinneret where oriented crystallization is expected to occur, cool air at 10 to 25 ° C should be applied at a wind speed of 60 m / min or more.
Cool by spraying over a length of 20 cm.

Thus, the density of the undrawn yarn is 1.360.
g / cm ³ or more, the spinning conditions are set so that the birefringence is 0.07 to 0.09, and the obtained undrawn yarn is not wound up,
When heat-stretched at a draw ratio of 1.5 or more, a polyester fiber having high strength and excellent dimensional stability against heat can be obtained.

In the present invention, the fiber means a multifilament, and the single yarn fineness, the total fineness, the number of filaments, the cross-sectional shape, the presence or absence of additives, and the polymer properties (terminal carboxyl group concentration etc.) are not limited. Not a thing.

In the present invention, when the polyester fiber is produced under the above-mentioned conditions, as a spinning oil, the above (A) to
An oil agent containing a composition composed of four components (D) as a main component is applied. In the oil agent component, EO means ethylene oxide, PO means propylene oxide, PEO means polyoxyethylenation, and the value in parentheses means the number of moles added.

The component (A) is an ester of an aliphatic alcohol and an aliphatic carboxylic acid or EO and / or P thereof.
It is an O addition product, and has an action of enhancing the yarn bundle converging property in the yarn making process. As the aliphatic alcohol and the aliphatic carboxylic acid, those having 6 to 22 carbon atoms are preferable, and EO
And / or the number of added moles of PO is preferably 4 to 20. (A sulfur atom or phosphorus atom may be introduced to improve heat resistance.) Specific examples of the component (A) include dioleyl adipate,
Examples thereof include oleyl oleate, lauryl oleate, isostearyl oleate, isotridecyl palmitate, diglycidol dioleate, dioleyl thiodipropionate, POE (20) glycerin dioleate and the like. The compounding amount of the component (A) is 2 to 20% by weight, preferably 5 to 15% by weight. If this amount is less than 2% by weight, the spinnability is deteriorated, and if it is more than 20% by weight, the anti-raveling effect is deteriorated.

The component (B) is an EO and / or PO adduct of an aliphatic alcohol, and has a function of penetrating the adhesive to a deep portion when the cord is treated with the adhesive. The aliphatic alcohol preferably has 4 to 22 carbon atoms, and the number of added moles of EO and / or PO is 4
~ 20 is preferred. Specific examples of the component (B) include POE (6)
Stearyl ether, POE (6) oleyl ether, POE (1
0) Cetyl ether, POE (8) lauryl ether, PO (5) / E
Examples include O (5) monobutyl ether, POE (20) glycerin ether, POE (20) hydrogenated castor oil ether and the like.
The blending amount of the component (B) is 20 to 80% by weight, preferably 25 to
70% by weight. If it is out of this range, the effect of preventing fraying is reduced.

The component (C) is an EO of a fatty acid amide compound.
And / or a PO adduct, which has a function of penetrating the adhesive to a deep portion and curing the adhesive when the cord is treated with the adhesive. The fatty acid amide compound preferably has 4 to 22 carbon atoms, and EO
And / or the number of added moles of PO is preferably 4 to 20.
Specific examples of the component (C) include POE (5) oleic acid amide, POE (10) oleic acid amide, POE (15) oleic acid amide, POE (8) lauric acid amide, POE (10) stearic acid amide, POE (10) lauric acid ethanolamide, POE (1
Examples thereof include 0) oleic acid ethanolamide and POE (10) oleic acid diethanolamide. The blending amount of the component (C) is 10 to 50% by weight, preferably 15 to 45% by weight.
If it is out of this range, the effect of preventing fraying is lowered, and if it is too large, the spinnability is deteriorated.

The component (D) is dimethylpolysiloxane, which has a function of lowering the frictional resistance with the stretching roller or the heat treatment roller and suppressing the accumulation of thermally deteriorated substances of the oil agent on the stretching roller or the heat treatment roller. The dimethylpolysiloxane preferably has a viscosity of 50 centipoises or less, preferably 10 to 40 centipoises. The component (D) is not an essential component, and it is possible to operate without blending it, but it is 5% by weight or less, preferably 0.5 to 2
It is preferable that the content is in the range of wt% because the operability is improved.
However, if the compounding amount of the component (D) is too large, there arises a problem in the adhesiveness with rubber and the anti-fray property.

The spinning oil in the present invention includes (A) to
The total of the four components of (D) is 100% by weight, and if necessary, an emulsifier, an antistatic agent, a heat-resistant agent, etc. may be mixed and used. The spinning oil is usually used in the form of a straight oil (non-water oil) diluted with a low-viscosity mineral oil or the like, but may be used as an aqueous emulsion oil.

The spinning oil agent is applied to the yarn immediately after spinning and cooling by a usual roller-type oil supply method or nozzle-type oil supply method. The amount of application is 0.1 to 1.0% by weight, preferably 0.2 to
0.8% by weight.

[0021]

EFFECTS OF THE INVENTION According to the present invention, as a spinning oil agent, when the adhesive agent is treated with the adhesive as a cord and a component that enhances the yarn bundle converging property in the spinning process, the adhesive is permeated to a deep portion or the adhesive is cured. Since a mixture of the ingredients to be mixed is used in a well-balanced manner, the spinnability is good and the adhesion to rubber is good just by performing the ordinary RFL treatment, and the polyester fiber reinforced rubber composite is obtained by using this cord. When cut in the fiber axis direction as a body, it is possible to prevent fraying of single filaments of the polyester fiber exposed on the cut surface and fluff-like protrusion from the cut surface. Further, by using the spinning dope that contains the component (D) in an effective amount, it is possible to suppress stains on the stretching roller and the heat treatment roller, reduce time and labor for cleaning, and improve productivity.

[0022]

EXAMPLES Next, the present invention will be described in detail with reference to examples. In addition, "part" means a weight part and the measuring method is as follows. (a) Using a cord strength / elongation autograph, measure according to JIS-L-1017. (b) Dry heat shrinkage According to JIS L-1017, the sample is heat-treated at 150 ° C for 30 minutes without tension and measured. (c) Spinnability The number of windings of the single yarn around the roller due to breakage of the single yarn by the take-up roller and the stretching roller in the yarn making process is evaluated in the following three stages. ○: 0 to 3 times / 1 day △: 4 to 10 times / 1 day ×: 11 times or more / 1 day (d) Anti-raveling The treated cords are arranged in parallel between two 3 mm thick rubber sheets. Sandwich and vulcanize at 150 ° C for 30 minutes under a pressure of 50 kg / cm ² to obtain a rubber sheet. This sheet is cut with a cutter knife in the fiber axis direction of the cords arranged in rubber,
Make sure the end of the cord is exposed on the cut surface. Then, while observing the protruding state of the single yarn of the polyester fiber from the end face with the naked eye, rub the end face with sandpaper (# AA-120) 10 times and observe the frayed state of the single yarn. Evaluate with. ◯: No protrusion of single yarn or fraying of single yarn is observed. Δ: The single yarn does not jump out, but the single yarn is unraveled. X: Single yarn jumping out and single yarn fraying are recognized. (e) Adhesiveness Using a rubber composition having the composition shown in Table 1, JIS-L-1017 A
Measure according to the method.

[0023]

[Table 1]

Examples 1 and 2 and Comparative Examples 1 to 3 [Preparation of Spinning Oil Agents (a) to (e)] 50 parts of low-viscosity mineral oil of RW 30 seconds was heated to 40 ° C., and each component was mixed in the proportions (parts) shown in Table 2. 50 parts of the oil agent composition blended in (4) was heated to 50 ° C., stirred slowly while being added, and then cooled to room temperature.

[0025]

[Table 2]

[Preparation of Isocyanate Adhesive] Tris (p-isocyanatephenyl) thiophosphate with a solid concentration of 27% was added to 75 parts of toluene;
25 parts of "E" (trade name of Sumitomo Bayer Urethane Co., Ltd.) was slowly added and dissolved by stirring.

[Preparation of RFL Solution] To 125 parts of water, 19 parts of 10% aqueous sodium hydroxide solution was added, then 17 parts of resorcin was added and dissolved by stirring, and then 30 parts of 37% aqueous formaldehyde solution was added and stirred. The mixture was reacted at 25 ° C for 30 minutes. The resulting reaction liquid was VP latex having a solid content of 41%; "Pilatex J-1904" (trade name of Sumitomo Dow Co., Ltd.) and SBR latex having a solid content of 40%; "JSR-2108" (Japan Synthetic Rubber). Brand name of the company) 190 parts of the mixed solution was added with stirring, 431 parts of water was added with stirring, and the mixture was stirred and mixed for 10 minutes and then aged at 25 ° C. for 24 hours.

[Production of Polyester Fiber] Intrinsic viscosity is 0.
90 polyethylene terephthalate chips were fed to an extruder type melt spinning machine, the spinning temperature was set to 305 ° C, spun from a spinneret having 300 spinning holes with a diameter of 0.5 mm, and the length was set just below the spinneret. After passing through a heating tube of 10 cm and a temperature of 330 ° C, use a cylindrical cooling device with a length of 30 cm to make it 18 ° C
Was blown onto the yarn at a speed of 72 m / min to cool the yarn. Next, the spinning oil agent shown in Table 2 prepared by the above-mentioned method by the roller type oil supply method was applied to the yarn in an amount of 0.6% by weight. Apply a thread with oil to the surface temperature of 70
℃, surface speed 3200m / min, take up with a heat take-up roller, take-up roller and surface temperature 140 ℃, surface speed 4800m
/ Min to 1.5 times with the first stretching roller, then the first stretching roller and the surface temperature 200 ℃, surface speed 6000m
After stretching at a draw ratio of 1.25 times between the second stretching roller and the second stretching roller, the surface temperature is 200 ° C. and the surface speed is 5800 m.
After performing a relaxation heat treatment of 0.97 times with a heat treatment roller for 1 / min, it was wound up to obtain 1000d / 300f polyester fiber.

[Treatment of Cord] While twisting two obtained polyester fibers, a twist of 115 times / m is applied to obtain a twisted cord, and then three twisted cords are twisted and reversely twisted. The cord is twisted in the direction of 115 times / m and twisted into a cord, and the cord is dipped in the isocyanate adhesive solution prepared by the above method (solid content: 2.5 to 3.5% by weight).
After drying with hot air at ℃, it was heat-treated at 240 ℃ for 100 seconds. Then, after soaking in the RFL bath prepared by the above method (amount of solid content 4.5 to 5.5% by weight) and drying at 120 ° C. for 60 seconds,
Heat treatment was performed at 240 ° C for 100 seconds.

Table 3 shows the strength and elongation of the treated cord thus obtained, the dry heat shrinkage, the resistance to fraying, the adhesiveness, and the spinnability in the raw yarn manufacturing process.

[0031]

[Table 3]

As is apparent from Table 3, Example 1 of the present invention
Was good in all of strength, dimensional stability, spinnability, fray resistance, and adhesiveness. In Example 2, although some problems remained in the spinnability, the characteristic values of strength, dimensional stability, fray resistance, and adhesiveness were satisfactory.
On the other hand, in Comparative Examples 1 and 3, there were problems in fray resistance and adhesiveness, and in Comparative Example 2, all were unsatisfactory.

[0033]

EFFECTS OF THE INVENTION According to the present invention, a high strength, excellent dimensional stability against heat, a cord is treated with an epoxy adhesive and / or an isocyanate adhesive, and a conventional RFL is used.
Adhesion with rubber becomes good just by processing, and
When the polyester fiber reinforced rubber composite is cut in the fiber axis direction by using this cord, a polyester fiber having a characteristic that does not fray or protrude from the cut surface of the single filament of the polyester fiber exposed on the cut surface is obtained. It can be manufactured with good operability. Further, when a spinning oil agent containing an effective amount of component (D), dimethylpolysiloxane, is applied, the deposition of heat-deteriorated substances of the oil agent on the stretching roller and the heat treatment roller is suppressed, and the polyester fiber having the above-described characteristics with good productivity. Can be manufactured.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 15, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

[0007]

The present invention has high strength,
Excellent dimensional stability against heat, and the cord treated with an epoxy-based adhesive and / or an isocyanate-based adhesive enables good adhesion between the rubber only performs normal RFL treatment, and, by using this code When the polyester fiber reinforced rubber composite is cut in the axial direction of the fiber, the polyester fiber having the property of not fraying the single filament of the polyester fiber exposed on the cut surface and protruding in a fluff shape from the cut surface is manufactured with good operability. It is intended to provide a method for producing a polyester fiber that can be used.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction content]

That is, the gist of the present invention is as follows. Polyethylene terephthalate having an intrinsic viscosity of 0.8 to 1.1 or polyester composed mainly of this is melt-spun and
At the speed of 00 m / min or more, it is taken as an oriented and crystallized undrawn yarn in a low degree of orientation, and hot-drawn to produce a polyester fiber. A method for producing a polyester fiber, which comprises applying an oil agent that (A) Ester of aliphatic alcohol and aliphatic carboxylic acid 2 to 20% by weight (B) Ethylene oxide and / or propylene oxide adduct of aliphatic alcohol 20 to 80% by weight (C) Ethylene oxide and / or fatty acid amide compound Or propylene oxide adduct 10 to 50% by weight (D) dimethylpolysiloxane 0 to 5% by weight

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0015

[Correction method] Change

[Correction content]

The component (A) is an ester of an aliphatic alcohol and an aliphatic carboxylic acid, and has the function of enhancing the yarn bundle converging property in the yarn making process. As the aliphatic alcohol and aliphatic carboxylic acid, those having 6 to 22 carbon atoms
Preferred . (A sulfur atom or phosphorus atom may be introduced to improve heat resistance.) Specific examples of the component (A) include dioleyl adipate,
Oleyl oleate, lauryl oleate, isostearyl oleate, isotridecyl palmitate, diglycidol dioleate, dioleyl thiodipropione
Etc. door of the like. The compounding amount of the component (A) is 2 to 20% by weight, preferably 5 to 15% by weight. If this amount is less than 2% by weight, the spinnability is deteriorated, and if it is more than 20% by weight, the anti-raveling effect is deteriorated.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

The component (B) is an EO and / or PO adduct of an aliphatic alcohol, and has a function of penetrating the adhesive to a deep portion when the cord is treated with the adhesive. The aliphatic alcohol preferably has 4 to 22 carbon atoms, and the number of added moles of EO and / or PO is 4
~ 20 is preferred. Specific examples of the component (B) include POE (6)
Stearyl ether, POE (6) oleyl ether, POE (1
0) Cetyl ether, POE (8) lauryl ether, PO (5) / E
O (5) monobutyl ether, POE (20) glycerin ete
Etc. Le, and the like. The blending amount of the component (B) is 20 to 80% by weight, preferably 25 to 70% by weight. If it is out of this range, the effect of preventing fraying is reduced.

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

[0025]

[Table 2]

[Procedure Amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction content]

As is apparent from Table 3, Example 1 of the present invention
Was good in all of strength, dimensional stability, spinnability, fray resistance, and adhesiveness. In Example 2, although some problems remained in the spinnability, the characteristic values of strength, dimensional stability, fray resistance, and adhesiveness were satisfactory.
On the other hand, in Comparative Examples 1 and 3, there are problems in fray resistance and adhesiveness, and in Comparative Example 2, yarn-forming property, fray resistance, and
The adhesiveness was unsatisfactory.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 5/24 KKE C08L 67/02 KJV D01D 5/096 Z D01F 6/62 301 H 302 C 306 K D06M 13/224 // (C08L 67/02 71:02 83:04) (72) Inventor Uchida et al. 23 Central Park Research Institute Unitika Corporation, Uji City, Uji City, Kyoto Prefecture (72) Inventor Masaru Sugawa, Uji Kyoto Prefecture 23 Ujikozakura, Ushi, Japan Centralika Research Institute, Central Research Institute

Claims (1)

[Claims] 1. A polyethylene terephthalate having an intrinsic viscosity of 0.8 to 1.1 or a polyester composed mainly of polyethylene terephthalate is melt-spun and taken at a speed of 3000 m / min or more as an undrawn yarn oriented and crystallized in a state of low orientation. A method for producing a polyester fiber, which comprises applying, as a spinning oil agent, an oil agent mainly composed of the following four-component composition when the polyester fiber is heat-stretched to produce a polyester fiber. (A) Ester of aliphatic alcohol and aliphatic carboxylic acid or its ethylene oxide and / or propylene oxide adduct 2 to 20% by weight (B) Ethylene oxide and / or propylene oxide adduct of aliphatic alcohol 20 to 80% by weight (C) Ethylene oxide and / or propylene oxide adduct of fatty acid amide compound 10 to 50% by weight (D) Dimethylpolysiloxane 0 to 5% by weight