JPH0255548B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Fields> The present invention relates to a method for thermally stabilizing an epoxy compound, and more particularly, to improving the adhesion of polyester yarn, a polyvalent epoxy compound is added to a spinning oil during spinning and drawing, as has been proposed for a long time. or mix it with
In the process of drawing and heat-treated polyester yarn in a non-catalytic system, the reactive agent is applied on the drawn yarn after heat treatment, either by attaching it separately or by mixing it in the drawing oil before and after drawing, or by applying it separately and then heat treating it. The present invention relates to a method for stabilizing an epoxy ring in which a certain epoxy compound remains unchanged as much as possible. <Conventional technical fields> Polyester fibers are generally produced by melt spinning, have high strength, a high Young's modulus, and have good dimensional stability, so they are used for rubber structures such as tire cords, conveyor belts, and V-belts. Although it has favorable physical properties as a reinforcing fiber, the surface of the polymer is inert, so resorcin formalin latex dispersion (hereinafter referred to as
RFL) alone cannot provide sufficient adhesive strength. Specifically, various methods and compounds have been used for a long time to improve the adhesion between polyester fibers and rubber. Among these, the most typical compound is a method in which a polyvalent epoxy compound is mixed with a spinning oil or drawing oil in the presence of a catalyst, or it is separately attached to the yarn in the spinning or drawing process and then heat-treated. In addition, polyester fibers are coated with a polyvalent epoxy compound in the absence of catalysts, stretched and heat-treated, wound, twisted into cords, and then reacted with isocyanate, etc., or used in RFL processing. A method has been proposed in which a blocked isocyanate or/and ethylene urea compound that reacts with an epoxy compound and hardens is mixed into the RFL processing agent. In all of these methods, it is necessary that reactive epoxy groups remain on the fiber, and the higher the concentration of reactive epoxy groups that can remain, the better the rubber adhesion. become. However, highly reactive polyvalent epoxy compounds cause thermal polymerization when heat-treated on fibers, and furthermore, when used in combination with spinning oil or drawing oil, when heat-treated, The weight loss of effective epoxy compounds is often unexpectedly significant. This is true even if a high molecular weight polyvalent epoxy compound that does not volatilize during heat treatment is used. <Object of the invention> The object of the invention is to apply a polyvalent epoxy compound to polyester fibers in the absence of a catalyst, and after stretching and heat treatment, the polyvalent epoxy compound remains on the yarn in a state with as much reactivity as possible. It's about letting people know. <Structure of the Invention> That is, the present invention involves adhering a fiber treatment agent containing 30% or more of a polyvalent epoxy compound with an average molecular weight of 200 to 3000 in the spinning process of polyester fibers, and then heat-treating the fibers at 200°C or higher in the absence of a catalyst. In this case, a compound having at least one hindered phenol group in the molecule represented by the general formula (1) is used as the treatment agent.

[Formula] or

[Formula] or [However, R' represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, and Z represents another organic residue. ] At least one compound containing 0.05 to 5.0% (by weight) based on the epoxy compound is added to heat stabilize the epoxy ring, or at least one of the hindered phenol compounds and a thioester type This is intended to protect the epoxy ring from thermal changes by containing the compound. The polyester fiber targeted in the present invention refers to polyethylene terephthalate having a degree of polymerization capable of forming fibers or at least 80% of the total structural units.
refers to a fiber-formable copolyester consisting of ethylene terephthalate, and the intrinsic viscosity of the polyester is preferably 0.5 to 1.2 (measured in an O-chlorophenol solution at 25°C). In addition, the epoxy compounds used in polyester fibers, which are the object of the present invention, are not particularly limited, but include known polyvalent epoxy compounds that have been commonly tried for polyester fibers, such as ethylene glycol, glycerin, pentaerythritol, Polyglycidyl ethers of sorbitol, polyethylene glycol, dimerized or multimerized forms of glycerin, other aliphatic polyhydric alcohols, triglycidyl isocyanurates with heterocyclic rings, and other aromatic aliphatic glycidyl ethers that have glycidyl ether groups. Epoxy compounds may be used alone or in combination. However, from the viewpoint of ease of use, it is preferable to use those that are easily soluble in water or aliphatic polyglycidyl ethers that are easily dispersible in water. These epoxy compounds are used separately or in combination with a spinning oil or a drawing oil in the spinning or drawing process. On the other hand, what is a compound having at least one hindered phenol group in the molecule represented by general formula (1)?

[Formula] or

[Formula] or [However, R' represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, and Z represents another organic residue. ] Specifically, 2,5-di-tert-butyl-4-methylphenol, n-octadecyl-3-(3',
5′-di-tert-butyl-4′-hydroxyphenyl)
-Propionate, 2,2'-methylene-bis-
(4-methyl-6-tert-butylphenol), 2
-tert-butyl-6-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl)-4-methylphenylacrylate, 4,4'-butylidene-bis-(3-methyl-6- tert-butylphenol),
4,4′-thio-bis-(3-methyl-6-tert-
butylphenol), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N'-
Hexamethylene-bis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 1,
6-hexanediol-bis-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, octadecyl-3-(3,5-di-t-
-butyl-4-hydroxyphenyl)-propionate, 2:1 nickel complex of 3,5-di-t-butylhydroxybenzylmonoethylphosphonate, 2,4-bis(n-octadecyl)-6-
(4-Hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2,2'-methylenebis[4-methyl-6-t-butylphenol], 2,2'-methylenebis- (4-ethyl-6
-t-butylphenol), tris-(2-methyl-4-hydroxy-5-t-butylphenyl)
Butane, diethyl ester of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid, 2
-thiodiethyl-bis-[3-(3,5-di-t
-butyl-4-hydroxyphenyl)-propionate]. All of these compounds have long been known as antioxidants, and are often used as effective heat stabilizers to prevent heat deterioration of polymeric substances. Although there are some proposals for using it to prevent the epoxy ring from forming, as in the present invention, it is effective in suppressing the thermal polymerization of the epoxy ring itself and reducing the thermal reaction of the epoxy ring with other components. Nothing has been reported so far. Furthermore, in the present invention, when a known sulfur-containing ester compound is used in combination with the addition of the hindered phenol compound, the effect can be further increased. That is, the thioester compound is already well known as a heat stabilizer for polymers, and esters of thiodipropionic acid are preferably used. i.e. dilaurylthiodipropionate,
Examples include distearylthiodipropionate, dioleylthiodipropionate, diisostearylthiodipropionate, and various other compounds are synthesized with only alkyl groups, such as these modified alkylthiodipropionates. The present invention is not limited to any ester compound of thiodipropionic acid. These thioester compounds, in addition to their effects in the present invention, are smoothing agents for fibers, that is, heat-resistant smoothing agents themselves, and are useful in terms of lubrication, so their combined use is suitable. Therefore, there is no particular restriction on the amount of the thiodipropionate-based ester compound (usually it can be used in the range of 5 to 75%), but in terms of heat resistance, it is better to mix it in a large amount. The hindered phenol compound, which is the object of the present invention, is solid and has a relatively high melting point, and from a functional point of view it is not necessary to add it in large amounts, and it may be added in an amount of 0.05 to 5.0% (by weight) based on the epoxy compound. 0.05%
If it is less than 5.0%, the effect will be small, and if it exceeds 5.0%, the stability of the emulsion in the spinning oil or drawing oil used in combination will be poor, which is not preferable. Desirably, the effect can be expected sufficiently within the range of about 0.1 to 3.0%. In addition, in order to mix these stabilizers into a spinning oil or drawing oil, since they do not dissolve as they are, they must be mixed and dissolved in advance in the spinning oil base or drawing oil base used together with the epoxy compound, or used. Either method may be used since it can be easily mixed by heating and dissolving it in the polyvalent epoxy compound in advance. The spinning oil or drawing oil containing 30% or more of the epoxy compound thus obtained is applied to the polyester fiber before it is heat treated. Although not particularly limited in the present invention, the method for attaching the epoxy compound may include a method in which the epoxy compound is included in the spinning oil, a method in which the epoxy compound is attached separately from the spinning oil, or a method in which the epoxy compound is attached in the drawing process. It may be applied at any step before the polyester fibers are heat treated. However, it is preferable to attach it to undrawn yarn and then subject the undrawn yarn to drawing and heat treatment in the same manner as ordinary polyester fibers are drawn and heat treated. Stretching is usually 5.0 to 5.8 times and then
Heat treated at a temperature of 180°C, preferably 200°C or higher. As described above, the epoxy compound-containing oil used to improve adhesiveness contains at least 30% or more of the epoxy compound, but in order to obtain high-grade adhesiveness, it is especially used in a mixture of 50% or more. In addition, the amount of adhesion can be determined using commonly known methods such as oiling roller method, spray method, dipping method,
It may be attached by any method such as a metal ring method. The adhesion amount is 0.25 to 100g of fiber.
About 0.4%, of which the epoxy compound is
It is preferable that the amount is about 0.1 to 0.2% (by weight). <Actions and Effects of the Invention> As described above, the present invention is applicable to all conventionally known antioxidants, which are effective as heat stabilizers for preventing heat deterioration of polymeric substances and the like. Hindered phenols, which are used in oils and are known to prevent fuming when heated or volatile due to thermal decomposition, have a completely different function:
This was done based on the new knowledge that it is effective in suppressing the thermal polymerization of the epoxy ring itself and reducing the thermal reaction of the epoxy ring with other components. Since reactive epoxy groups can remain at a high concentration even on fibers, treated yarns with excellent rubber adhesion can be provided. In addition, regarding the quantitative determination of the particularly reactive epoxy part of the epoxy compound attached to polyester fibers, the yarn obtained by deoiling with cyclohexane and concentrating the cyclohexane from the stretched and heat-treated yarn was used with the usual epoxy quantitative method. Three methods were used, including the hydrochloric acid dioxane method, the sodium sulfite method, and the hydrobromic acid ice vinegar method, and the stability of the epoxy ring was determined and confirmed before and after heat treatment. Of course, when the epoxy compound was used alone, when the oil agent and the epoxy compound were used together, and when the epoxy compound was used in combination with the oil agent, quantitative measurements were carried out before and after heating for the extracts from the threads, and the rate of change was examined. <Measurement of change rate of epoxy ring 1> (1) Weigh 1 g of a sample made of a commercially available epoxy compound (100%) and place it in a 4 cm diameter dish.
Heat in a hot air dryer at 200℃ for 60 minutes and 90 minutes,
After cooling, dissolve the sample in dioxane.
This was carried out using the hydrochloric acid-dioxane method, which is usually carried out using 0.2NHCl. At this time, the epoxy oxygen content of the unheated epoxy compound was simultaneously measured, and the rate of change was determined as the percentage of Epon rings before and after heating. (2) Blend a sample consisting of a commercially available epoxy compound (100%) and a spinning oil so that the ratio of the epoxy compound to the spinning oil is 50/50 and 70/30,
The rate of change was determined using a method similar to (1). <Measurement of the change rate of epoxy rings 2> In this method, 500 g of yarn obtained after spinning and drawing and heat treatment of polyester is deoiled using cyclohexane according to a commonly known method for measuring the oil adhesion rate (with a Soxhlet extractor). After the cyclohexane was distilled, the epoxy oxygen percentage was determined using the hydrochloric acid-dioxane method, and the rate of change was determined from measurements before and after the heat treatment. The present invention will be further explained in detail with reference to Examples below, in which (%) and parts all indicate parts by weight or weight percent. Note that the examples used in this embodiment are limited in type, but are not limited thereto in any way.
The epoxy compounds and compounds having a hindered phenol group in the molecule that were used in the examples are listed below. [1] As an epoxy compound E-1 Diglycerin polyglycidyl ether (Nagase Sangyo, trade name Denacol EX-421) E-2 Sorbitol polyglycidyl ether (Nagase Sangyo, trade name Denacol EX-611) [2] Hindered phenol compound As A-1 4,4'-butylidene-bis(3-methyl-6-t-butylphenol) (Sumitomo Chemical Sumilizer BBM) was used. Example 1 and Comparative Example 1 Diglycerin polyglycidyl ether (E-
1) and polyglycidyl ether of sorbitol (E-2), respectively, as a hindered phenol compound, the above-mentioned A-1.
Create samples with and without addition of 2.5% of
1.0 g of each was collected in a stainless steel dish, heat treated at 200℃ for 60 minutes and 90 minutes, and the epoxy oxygen (%) was determined by the hydrochloric acid-dioxane method before and after the heat treatment. We asked how it would change over time. The results are shown in Table-1.

We calculated the rate of change in [Table].
Example 2, Comparative Example 2 Diglycerin polyglycidyl ether (E-1) was used in the same manner as in Example 1, and the amount of hindered phenol compound (A-1) added was shown in Table-2.
In addition to the above changes, the changes were determined depending on whether or not dioleyl thiodipropionate was added as a thiodipropionic acid ester compound. The results are shown in Table-2.

[Table] Example 3, Comparative Example 3 Diglycerin diglycidyl ether (E-1)
A smoothing agent consisting of dioleyl adipate (20 parts) and isotridecyl stearate (30 parts) as a spinning oil base for polyester fibers, and lauryl ether (15 parts) of POE (3 mol) as an emulsifier, POE (12 mol) Castor oil ether (15
), POE (5 mol) nonyl phenyl ether (10 parts), POE (4 mol) oleyl alcohol ether (10 parts) was used to prepare E-1.
and (B) in a ratio of 50/50 or 70/30 to obtain an epoxy compound-containing oil agent, and for each, A-1
We investigated how the survival rate of epoxy rings changes depending on the presence or absence of epoxy rings. The results are shown in Table 3.

[Table] Example 4, Comparative Example 4 Polyethylene terephthalate fiber yarn made from a 0.4 mmφ x 250H nozzle ([η] = 0.90)
(solvent, O-chlorophenol, temperature 35℃)
The epoxy compound E used in Example 3 was wound onto a bobbin at a speed of 400 m/min.
-1 and (B) as the base oil, the mixing ratio is
A 10% aqueous emulsion liquid prepared to have a ratio of 80/20 was applied using an oiling roller during spinning, and then stretched and heat treated. That is, the stretching was carried out using a stretching machine capable of two-stage heating stretching, stretching 3.5 times at 78°C, then 5.8 times at 180°C in the first and second stages, and heat setting at 200°C. A drawn heat-treated yarn of 1500 denier/250 filaments was obtained. At this time, E-1/B=80/20 with and without addition of hindered phenol A-1 at 2.5% based on the epoxy compound were simultaneously obtained, and the yarn thus obtained was decomposed with cyclohexane. The epoxy oxygen (%) of the deoiled component obtained by oiling was measured, and the amount of epoxy oxygen in A-1 was 5.5% as epoxy oxygen, while that of the yarn without the addition was 3.9%. It was hot.

Claims (1)

[Scope of Claims] 1. In the spinning process of polyester fibers, a fiber treatment agent containing 30% or more of a polyvalent epoxy compound with an average molecular weight of 200 to 3000 is applied, and then a non-catalytic condition is applied.
When heat-treated at 200°C or higher, the fiber treatment agent contains at least one hindered phenol group in the molecule, which is represented by the following general formula (1).
[Formula] or [Formula] or [However, R' represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, and Z represents another organic residue. ] 0.05 to 5.0% (weight) of at least one compound containing the following to the epoxy compound is used. 2. In the spinning process of polyester fibers, a fiber treatment agent containing 30% or more of a polyvalent epoxy compound with an average molecular weight of 200 to 3000 is applied, and then a non-catalytic environment is applied.
When heat-treated at 200°C or higher, the fiber treatment agent contains at least one hindered phenol group in the molecule, represented by the following general formula (1).
[Formula] or [Formula] or [However, R' represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, and Z represents another organic residue. ] A method for thermally stabilizing an epoxy ring using a combination of 0.05 to 5.0% (by weight) of at least one compound containing the following based on the epoxy compound and a thioester compound.