JPH09158053A - Production of polyester fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for stably producing a polyester fiber having good adhesion to rubber in good spinning property for a long period. SOLUTION: A spinning oil agent containing an ethylene oxide and/or propylene oxide adduct to aliphatic amine compound is added to a melt-spun yarn and the yarn is thermally drawn. Then, a finishing oil agent containing an epoxy compound having two epoxy groups in one molecule, a blocked isocyanate compound, a silane coupling agent and an ethylene oxide and/or propylene oxide adduct to fatty acid amide compound is applied to the yarn.

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 a polyester fiber having improved adhesion to rubber.

[0002]

2. Description of the Related Art Polyethylene terephthalate and polyester fiber mainly composed of polyethylene terephthalate have excellent physical and chemical properties, are industrially mass-produced, and are very useful fibers widely used in various fields. It is a very suitable material as a rubber reinforcing material. However, polyester fibers have a drawback of poor adhesion to rubber, and various methods for improving the adhesion between polyester fibers and rubber have been conventionally proposed.

As a typical method thereof, a liquid (RF) obtained by aging raw cord or its woven fabric by mixing an initial condensate of resorcin and formaldehyde and a rubber latex is used.
In the so-called dip treatment, which is a treatment with L), after pretreatment with an adhesion improver such as an epoxy compound, an isocyanate compound, an ethylene urea compound, R
FL treatment method (JP-B-60-24226), RFL
A method of treating with RFL containing a condensed phenol compound such as 2,6-bis (2 ', 4'-dihydroxyphenylmethyl) -4-chlorophenol (Japanese Patent Publication No. 46-11251).
And JP-A-63-249784). However, although these methods can achieve the desired adhesive performance to some extent, these methods use a large amount of the adhesiveness improver, resulting in an increase in cost due to problems such as complicated treatment methods. It has the drawback of inviting.

In addition, a so-called pre-coated yarn, to which an epoxy compound has been added as an adhesion improver at the yarn stage, is
There is a method of FL processing (Japanese Patent Publication No. 37514 / etc.). That is, in the polyester fiber manufacturing process, an oil agent containing an epoxy compound is applied as a spinning oil agent, and heat treatment is performed using heat of the stretching step to improve the adhesiveness. However, in this method, a cured product of epoxy compound or a heat-deteriorated product adheres to the stretching roller or heat treatment roller, the performance of the polyester fiber is changed, or the epoxy cured product or heat adhered to the roller is frequently stopped by the operation. There was a problem that the deteriorated material had to be removed.

[0005]

SUMMARY OF THE INVENTION In view of the above situation, the present invention does not stain the stretching roller or heat treatment roller in the fiber manufacturing process, and simply performs the RFL treatment later to obtain good adhesion to rubber. It is intended to provide a method for producing a polyester fiber capable of obtaining a polyester fiber having

[0006]

Means for Solving the Problems The present invention is to solve the above-mentioned problems, and the gist thereof is to prepare a polyester fiber by melt-spinning the yarn with ethylene oxide and / or propylene of an aliphatic amine compound. An ethylene compound and / or propylene of an epoxy compound having two or more epoxy groups in one molecule, a blocked isocyanate compound, a silane coupling agent, and a fatty acid amide compound after applying a spinning oil containing an oxide adduct and hot stretching A method for producing a polyester fiber is characterized by applying a finishing oil agent containing an oxide adduct.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

In the present invention, the polyester fiber is a multifilament composed of polyethylene terephthalate and polyester mainly composed of polyethylene terephthalate, and the polyester fiber has a molecular weight, denier, number of filaments, cross-sectional shape, physical properties of yarn, fine structure, and additives. The presence or absence of the polymer and the polymer properties (terminal carboxyl group concentration, etc.) are not particularly limited.

In the present invention, the melt spun yarn is cooled and solidified, and then a spinning oil is applied.

As the ethylene oxide and / or propylene oxide adduct of the aliphatic amine compound added to the spinning oil in the present invention, ethylene oxide and / or propylene oxide is added to the aliphatic amine having 4 to 22 carbon atoms.
Those added with 2 to 20 mol are preferable.

Specific examples of ethylene oxide and / or propylene oxide adducts of aliphatic amines include POE (4
~ 20) lauryl amino ether, POE (2-20) stearyl amino ether, POE (4-20) oleyl amino ether, EO (5) / PO (4) monobutyl amino ether, POE (2 ~
20) lauryl ethanolamine, POE (2 to 20) lauryl diethanolamine and the like.

POE means polyoxyethylenated, EO means ethylene oxide, PO means propylene oxide,
The value in parentheses indicates the number of moles of ethylene oxide or propylene oxide added.

In addition to ethylene oxide and / or propylene oxide adducts of aliphatic amine compounds, spinning oils include epoxy compounds, blocked isocyanate compounds and silane coupling agents, and ethylene oxide and / or propylene oxide additions of fatty acid amide compounds. Ordinary spinning oils for polyester fibers containing no substance are used. For example, mineral oil, coconut oil, rapeseed oil, sperm oil and other natural oils, esters of higher alcohols or polyhydric alcohols and higher fatty acids, synthetic oils such as alkyl polyethers, sulfur adducts of such synthetic oils, etc. A smoothing agent, and a surfactant sufficient to emulsify and disperse the smoothing agent,
If necessary, an antistatic agent, a heat-resistant agent, a coloring agent, etc. may be added. Although it is not always necessary to use a surfactant as an emulsifying agent or a dispersing agent, generally, castor oil, a compound obtained by adding an alkylene oxide to a higher alcohol, a polyethylene oxide, an ester of a polyethylene glycol and a higher fatty acid, or the like is preferably used.

The proportion of each component of the spinning oil is 3 to 20% by weight of an ethylene oxide and / or propylene oxide adduct of an aliphatic amine compound, 30 to 80% by weight of a leveling agent, and 20 of an emulsifier.
The combination is preferably 70% by weight to 100% by weight with appropriate amounts of other additives. Within this range, the original smoothness and bundling properties of the spinning oil agent are not lost, there is no roller stain, and the desired effect of improving the adhesiveness is exhibited.

The spinning oil agent is applied to the yarn spun by the usual roller type oil supply method or nozzle type oil supply method,
The applied amount is 0.05 to 1% by weight, preferably 0.1 to 0.5% by weight. The spinning oil is usually applied in the form of a straight oil diluted with a low-viscosity mineral oil or the like, but may be applied in the form of an aqueous emulsion.

The yarn to which the spinning oil is applied is heat-stretched by a conventional method, and then is formed of an epoxy compound having two or more epoxy groups in one molecule, a blocked isocyanate compound, a silane coupling agent and a fatty acid amide compound. A finish oil containing ethylene oxide and / or propylene oxide adduct is applied.

The epoxy compound added to the finishing oil agent in the present invention has two or more epoxy groups in one molecule, and is usually a halogen-containing epoxy compound such as epichlorohydrin and a polyhydric alcohol or a polyhydric phenol. It is synthesized by the reaction. Examples of polyhydric alcohols or polyhydric phenols of this kind include glycerol, ethylene glycol, diethylene glycol, propylene glycol, sorbitol, polyethylene glycol, trimethylolpropane or their derivatives, and other polyhydric alcohols, resorcinol, catechol, hydroquinone or these. There are polyhydric phenols such as derivatives.
Further, cyclohexane epoxide obtained by oxidizing an unsaturated bond with peracetic acid, diglycidyl ether and the like can also be used.

Specific examples of the epoxy compound include the following compounds. (The name in parentheses indicates the product name of the product marketed by Nagase Kasei Co., Ltd.) Glycerol polyglycidyl ether (“Denacol EX-313”, “Denacol EX-314”) Polyglycerol polyglycidyl ether (“Denacol EX- 512 ”,“ Denacol EX-521 ”) Diglycerol polyglycidyl ether (“ Denacol EX-421 ”) Resorcin diglycidyl ether (“ Denacol EX-201 ”) Sorbitol polyglycidyl ether (“ Denacol EX-611 ”,“ Denacol EX-201 ”) -614 ") Ethylene glycol diglycidyl ether (" Denacol EX-811 ")

The blocked isocyanate compound added to the finishing oil agent in the present invention is a compound obtained by reacting a polyol compound such as polyester polyol or polyether polyol with polyisocyanate and using a carbamoyl sulfonate group as a blocking agent. It is desirable to use a deisocyanate compound, an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound, which is modified with a water-soluble or water-emulsifiable compound with a blocked isocyanate compound using methyl ethyl ketoxime as a blocking agent.

The following compounds may be mentioned as specific examples of the blocked isocyanate compound. (The names in parentheses indicate the product name and manufacturer name.) Polyester blocked isocyanate (“Elastron E-37”: Daiichi Kogyo Seiyaku Co., Ltd.) Polyether blocked isocyanate (“Elastron BN-04”: No. Ichigo Pharmaceutical Co., Ltd. Crude MDI methyl ethyl ketoxime block (“FS-9000”: Meisei Chemical Industry Co., Ltd.) HMDI methyl ethyl ketoxime block body (“NBP-870”, “NBP-880”: Meisei Chemical Industry Co., Ltd.)

The silane coupling agent added to the finishing oil agent in the present invention is a silane compound having at least two kinds of functional groups having different reactivities in one molecule (provided that a silane compound having two or more epoxy groups is used). Except), those having a functional group selected from an amino group, an epoxy group, and a vinyl group are desirable.

Specific examples of the silane coupling agent include:
The following compounds may be mentioned. (The names in parentheses indicate the product name and manufacturer name.) N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane (“KBM602”: Shin-Etsu Chemical Co., Ltd.) (“SZ6023”: Toray Dow Corning Silicone Co., Ltd. N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane (“KBE602”: Shin-Etsu Chemical Co., Ltd.) N-β (aminoethyl) γ-aminopropyltrimethoxysilane (“KBM603”: Shin-Etsu Chemical Co., Ltd.) (“SH6020”: Toray Dow Corning Silicone) γ-glycidoxypropyltrimethoxysilane (“KBM403”: Shin-Etsu Chemical Co., Ltd.) (“SH6040”: Toray Dow Corning Silicone) γ-Gly Sidoxypropyltriethoxysilane (“KBE403”: Shin-Etsu Chemical Co., Ltd.) γ-glycidoxypropylmethyldiethoxysilane (“KBM402”: Shin-Etsu Chemical) Gosha) vinyltrimethoxysilane ( "KBM1003": Shin-Etsu Chemical Co., Ltd.) ( "SZ6300": Dow Corning Toray Silicone Co., Ltd.)

As the ethylene oxide and / or propylene oxide adduct of the fatty acid amide compound added to the finishing oil agent in the present invention, 2 to 20 mol of ethylene oxide and / or propylene oxide are added to the fatty acid amide compound having 4 to 22 carbon atoms. Those added are preferable.

Specific examples of the ethylene oxide and / or propylene oxide adduct of the fatty acid amide compound include:
POE lauric acid amide, POE lauric acid ethanolamide, POE lauric acid diethanolamide, POE oleic acid amide, POE oleic acid ethanolamide, POE oleic acid diethanolamide, POE stearic acid amide,
Examples thereof include POE stearic acid ethanolamide and POE stearic acid diethanolamide (the number of moles of EO added to POE is 2 to 20).

As the finishing oil agent, in addition to an epoxy compound, a blocked isocyanate compound, a silane coupling agent and an ethylene oxide and / or propylene oxide adduct of a fatty acid amide compound, mineral oil, coconut oil, rapeseed oil, sperm oil and the like can be used. Natural oils, esters of higher alcohols or polyhydric alcohols with higher fatty acids, synthetic oils such as alkyl polyethers, leveling agents such as sulfur adducts of such synthetic oils, and interfaces sufficient to emulsify and disperse the leveling agents. Activator and, if necessary, antistatic agent, heat-resistant agent,
A colorant or the like is added. Although it is not always necessary to use a surfactant as an emulsifying agent and a dispersing agent, generally, castor oil, an adduct of an alkylene oxide added to a higher alcohol, or polyethylene oxide or an ester of a polyethylene glycol and a higher fatty acid is preferably used. .

The proportion of each component of the finishing oil agent is 15 to 50% by weight of the epoxy compound and 5 to 5 of the blocked isocyanate compound.
40% by weight, 1 to 10% by weight of silane coupling agent, 1 to 10% by weight of ethylene oxide and / or propylene oxide adduct of fatty acid amide compound, and a combination such that the total amount of other additives is 100% by weight is preferable. . Within this range, the original smoothness and bundling functions of the finishing oil agent are not lost, and the desired effect of improving the adhesive performance is preferably exhibited.

The finishing oil agent is applied to the yarn after heat treatment by a usual roller-type oil supply method or nozzle-type oil supply method, and the applied amount is 0.2 to 2% by weight, preferably 0.3 to 1% by weight. The finishing oil is usually used in the form of an aqueous emulsion.

The polyester fiber obtained by the present invention is twisted into a cord in the usual manner, and the cord is woven or woven into a cord woven fabric to obtain a normal RFL.
Adhesion to rubber becomes remarkably good only by treatment. Such an improvement in the adhesive performance is not limited to the improvement of the polyester fiber itself, but is directly connected to the improvement of the quality of the rubber product to be reinforced, and brings a great practical effect.

[0029]

In the present invention, the ethylene oxide and / or propylene oxide adduct of the aliphatic amine compound blended in the spinning oil agent and the ethylene oxide and / or propylene oxide adduct of the fatty acid amide compound blended in the finishing oil agent are the finishing oil agents. It becomes a curing agent for the epoxy compound blended in, and the blocked isocyanate compound blended in the finish oil agent and the silane coupling agent synergistically bond them strongly to the polyester fiber and also firmly bond to RFL. Will firmly adhere to rubber.

Further, in the present invention, the spinning oil agent applied in the spinning step does not contain an epoxy compound, a blocked isocyanate compound and a silane coupling agent, and the finishing oil agent containing these is a hot-stretching film which rotates at the maximum peripheral speed. Since it is applied downstream of the roller, it is possible to avoid the accumulation of these cured products and thermally deteriorated products on the stretching rollers at each stage up to the stretching roller rotating at the maximum peripheral speed. As a result, long-term continuous operation of hot stretching becomes possible, and uniform product quality can be achieved, resulting in great practical effects.

[0031]

EXAMPLES Next, the present invention will be described in detail with reference to examples. In addition, "part" means a weight part, and measurement and evaluation were performed by the following methods. (1) Spinnability Stretching roller, heat treatment roller, and touch roller of winder, solidified or hardened material of epoxy compound, blocked isocyanate compound and silane coupling agent will be deposited, making stretching and winding difficult and cleaning. The evaluation was performed according to the following three grades depending on the time required to perform. ○: 2 days or more, △: 8 hours to 2 days, ×: less than 8 hours (2) Adhesive strength A ply with cords embedded in carcass compound rubber for automobile tires so that the cord density is 35 cords / 2.5 cm. Two
The sheets were stacked, vulcanized under a pressure of 20 kg / cm2 for 30 minutes at 150 ° C, and then taken out. At a temperature of 20 to 25 ° C, the peel strength required for peeling at a pulling speed of 5 cm / min was measured using an autograph. It was measured.

Examples and Comparative Examples 1 to 10 (a) Preparation of Spinning Oil Agents A to E 50 parts of low-viscosity mineral oil was heated to 40 ° C., and the oil agent composition having the composition (parts) shown in Table 1 was heated to 50 ° C. The mixture was stirred while slowly adding 50 parts of the mixed solution heated to, and then cooled to room temperature.

[0033]

[Table 1]

(B) Preparation of Finishing Oil Agents A to 80 parts of water was heated to 40 ° C., and 20 parts of a liquid oil composition having the composition (parts) shown in Table 2 heated to 40 ° C. was slowly added. After stirring, the mixture was cooled to room temperature.

[0035]

[Table 2]

(C) Preparation of RFL To 125 parts of water was added 19 parts of a 10% sodium hydroxide aqueous solution, and then 17 parts of resorcin was added and dissolved with stirring. Then
Add 30 parts of 37% formaldehyde aqueous solution, stir, and 25 ℃
For 30 minutes. 41% solid content of the obtained reaction solution
VP latex of "Pilatex J-1904" (trade name of Sumitomo Dow Co., Ltd.) and SBR latex having a solid content of 40%: "JSR-2108" (trade name of Japan Synthetic Rubber Co., Ltd.) of 190 parts. The mixture was added with stirring, and 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.

(D) Production of Polyester Fiber A polyethylene terephthalate chip having an intrinsic viscosity (measured at a temperature of 20 ° C. of an equal weight mixture of phenol and ethane tetrachloride as a solvent) of 0.97 was melt-spun to give
I got a yarn of 00d / 192f. After applying the spinning oil prepared by the above method to the unstretched yarn which was spun from the spinneret and cooled and solidified by the roller lubrication method so that the amount of the oil attached was 0.3 parts by weight per 100 parts of the fiber, It is taken up by the first roller at 70 ℃, and 3.5 between the first roller and the second roller at 120 ℃.
The first stage is doubled, and then the second roller and 220 ℃
The second so that the total draw ratio with the roller is 6.1 times.
It was stretched in stages and then 4% relaxed between the 3rd roller and the 4th roller at 180 ° C, and 100 parts of the finishing oil solution prepared by the above method was added between the 4th roller and the winder. It was applied by a metering nozzle type oil supply method so that the amount of oil adhered was 0.6 parts, and was wound at a speed of 2500 m / min.

(E) Treatment of cord Two 1500d / 192f yarns obtained by the above method are twisted at a twist number of 40 times / 10 cm for upper twist and 40 times / 10 cm for upper twist to obtain a cord, which is manufactured by Ritzler By using a computer made by
Immerse in the RFL bath prepared by the above method and apply RFL so that the amount of solids deposited becomes 4.5 to 5.5% by weight.
After drying at ℃ for 120 seconds, it was heat-treated at 200 ℃ for 120 seconds.

Table 3 shows the results of evaluation of the spinnability and the adhesive strength of the treated cord.

[0040]

[Table 3]

As is clear from Table 3, in the examples of the present invention, the spinnability and the adhesive strength were good. On the other hand, in Comparative Examples 1 to 5, the spinnability was good, but the adhesive strength was poor, and in Comparative Examples 6 to 10, the adhesive strength was good, but there was a problem in the spinnability and it was not satisfactory. It was

Comparative Example 11 The test was repeated under the same conditions as in Example except that the position of application of the finishing oil agent was moved in front of the third roller which was the highest peripheral speed roller in the stretching step. The resin film was deposited on the third roller with the lapse of the yarn making time, and after one hour, fluff was generated on the yarn, which required cleaning of the roller.

[0043]

EFFECTS OF THE INVENTION According to the present invention, stains on the stretching roller and the heat treatment roller in the polyester fiber manufacturing process are remarkably reduced, and long-term continuous stable operation becomes possible. Further, the polyester fiber obtained by the present invention is twisted into a cord according to a usual method, and in a state of the cord or a state of weaving the cord into a cord woven fabric, an adhesive property with a rubber is obtained only by performing a usual RFL treatment. It is good and brings great practical effects.

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[Procedure amendment]

[Submission date] December 26, 1995

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0040

[Correction method] Change

[Correction contents]

[0040]

[Table 3]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number for FI FI technical display location D06M 15/564 D06M 15/564 15/568 15/568 (72) Inventor Hiroshi Shinpad Okazaki City, Aichi Prefecture 4-1 Hinakitamachi Unitika Stock Company Okazaki Factory

Claims (1)

[Claims] 1. When producing a polyester fiber, a spinning oil containing an ethylene oxide and / or propylene oxide adduct of an aliphatic amine compound is applied to a melt-spun yarn, and after hot drawing, the molecular weight per molecule is increased. A method for producing a polyester fiber, which comprises applying a finishing oil agent containing an epoxy compound having two or more epoxy groups, a blocked isocyanate compound, a silane coupling agent, and an ethylene oxide and / or propylene oxide adduct of a fatty acid amide compound. .