JPS6112971A - Heat stabilization of epoxy ring - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a method for thermally stabilizing an epoxy compound, and more particularly, to a method for thermally stabilizing an epoxy compound, which has been proposed for a long time to improve the adhesiveness of polyester yarn. Catalyst-free drawn and heat-treated polyester yarns are prepared by mixing the epoxy compound into the spinning oil, applying it separately, or mixing it into the drawing oil before and after drawing, or applying it separately and then heat treating it. The present invention relates to a method for stabilizing epoxy rings in which a reactive epoxy compound remains on drawn yarn after heat treatment in a yarn spinning process without being changed as much as possible.

<Conventional technical field> 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 as reinforcing fibers for tire hoods, conveyor belts, and V-belt rubber structures. Although it has favorable physical properties, since the surface of the polymer is inert, it is not possible to obtain sufficient adhesive strength with resorcin formalin latex dispersion (hereinafter referred to as RFL) alone, as with polyamide fibers.

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 it is subsequently heat-treated. In addition, polyester fibers are coated with polyvalent epoxy compounds in the absence of catalysts, stretched and heat treated, then wound, twisted into cords, and then reacted with incyanate, etc. A method has been proposed in which a RFL treatment agent is mixed with a block german sifnate or/and an ethylene urea compound that reacts with an epoxy compound and hardens during RFL treatment. In all of these methods, it is essential that reactive epoxy groups remain on the fibers, and the higher the concentration of remaining reactive epoxy groups, the better the rubber adhesion. It will be excellent. However, highly reactive polyvalent epoxy compounds heat up on fibers! 6. When processed, thermal polymerization occurs, or when used in combination with spinning oil or drawing oil, the amount of effective epoxy compounds is often reduced unexpectedly when heat treated. . The same holds true even if a high molecular weight polyepoxy compound that does not volatilize during heat treatment is used.

<Object of the Invention> The object of the present invention is to apply a polyvalent epoxy compound to polyester fibers in the absence of a catalyst, and after drawing 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 has an average molecular weight of 200 or more to 3
When a fiber treatment agent containing 30 or more polyvalent epoxy compounds of 000 or less is attached to polyester fibers and heat released at 200゛0 or more in the absence of a catalyst, the treatment agent is represented by general formula (1). The epoxy ring is stabilized by heating by adding at least one compound having at least one hindered phenol group in the molecule in an amount of 0.05 to 5.0 (by weight) to the polyvalent epoxy compound. Furthermore, by containing at least one kind of underarm hindered phenol compound and a thioester compound, it is intended to protect the epoxy ring from heat change.

In the present invention, the polyester fiber to be considered refers to polyethylene terephthalate having a degree of polymerization that allows fiber formation, or a copolymer polyester capable of forming fibers in which at least 80 units of all structural units are ethylene terephthalate. The viscosity (measured in O-cool phenol solution at 25°0) is preferably 0.5 to 1.2.

In addition, the epoxy compounds used in polyester fibers, which are the object of the present invention, are not particularly limited, but include 9 examples of known polyvalent epoxy compounds that have been commonly tried for polyester fibers: evaporator, ethylene glycol, glycerin, hupentaerythritol, Epoxies with glycidyl ether groups such as sorbitol, polyethylene glycol, dimerized or multimerized glycerin, other aliphatic polyglycidyl ethers, triglycidyl incynurate having a heterocyclic ring, and other aromatic aliphatic glycidyl ethers. 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 dispersed 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, the compound having at least one hindered phenol group in the molecule represented by general formula (1) specifically includes 2,5-di-tert-butyl-4-methylphenol and styrenated phenol.

n-octadecyl-3-(3',5'-tart
-butyl 4'-human l-xyphenyl)-propionate, 22L-methylenebis-(4-methyl-6-tar)
tert-butylphenol) 2-tert-butyl-6-(
tert-butyl-5'-methyl τ-hydroxybenzyl)-4-methylphenyl 7cryl), 4.
4'-Butylidene-bis-(3-methyl-6-tert
-butylphenol), 414'-thio-bis=(3
-methyl 6-tart butylphenol), pentaerythrityl-tetrakis (3'-(3,5-di-t
-butyl-4-hydroxyphenyl)purpione-)
, N,N'-hexamethylene-bis-(3,5-di-
t-butyl-4-hydroxy-hydrocinnamide)
1,6-hexanethiolubis-3- (3,5-
di-t-butyl-4-hydroxyphenyl) p-bionate! Octadecyl 3- (3,5-di-t-butyl-
4-hydroxyphenyl)-purpione), 3.
2:1 nickel complex of 5-di-t-butylhydroxybenzyl monoethylphosphonate.

2.4-binet(n-octadecyl)-6-(4-hydroxy-3,5-di-t-butylanilino) 1,3
．． 5-) Su7jin, 2. z-methylenebis[4-methyl-6-t-butylphenol)' + 212'-methylenebis-(4-ethyl-6-t-butylphenol) t"t3s5-tri^(4-1-butyl-3-hydroxy-2 ,6 dimethyl)incyanuric acid, tris-
(2-methyl-4-human-xy-5-t-butyl-4-
Hydroxy-5-tert-butylstylphenyl)butane, diethyl ester of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid, 2,2-thiodiethyl-
Bis-[3-(3,5-di-t-butyl-4-human-xyphenyl)-propionate] and the like can be mentioned.

These compounds have long been known as antioxidants, and are often used as effective heat stabilizers to prevent thermal deterioration of polymeric substances, and to reduce the smoke-emitting properties of oils when heated. There are some proposals that are used to prevent volatility due to decomposition, but methods such as the present invention are effective in suppressing thermal polymerization of the epoxy ring itself and reducing thermal reactions with other components of the epoxy ring. 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. dilauryl thiodipropionate, diste 7
Examples include lylthiodip-bionate, dioleylthiodipropionate, diisostearylthiodipropionate, and various other compounds that contain only a furkyl group, such as modified furkylthiodipropionate, but this one is particularly important. 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. However, 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 it is better to mix it in a larger amount in terms of heat resistance.

The hindered phenol compound, which is the subject of the present invention, is solid and has a relatively high melting point, and it is not necessary to add it in a large amount from a functional point of view.
% (weight) may be added. If it is less than 0.054, the effect will be small, and if it exceeds 5.0%, the stability of the emulsion in the spinning oil or drawing oil used together will be poor, which is not preferable.

Desirably, the effect can be expected sufficiently within the range of about o,i to 3.0-.

These stabilizers can also be used as spinning oil or as a spinning oil.

In order to mix it into the drawing oil, it is not dissolved in the raw process, so it is necessary to mix and dissolve it in the spinning oil base or drawing oil paste used together with the epoxy compound.
Either method may be used since it can be easily mixed by heating and dissolving it in advance in the polyvalent epoxy compound to be used.

The spinning oil or drawing oil containing 30 or more of the epoxy compounds 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 for ordinary polyester fibers. Stretching is usually carried out by a factor of 5.0 to 5.8 times, and then heat treatment is carried out at a temperature of 180 DEG C., preferably 200 DEG C. or higher. in this way,
The epoxy compound-containing oil used to improve adhesion contains at least 30% of the epoxy compound, but in order to obtain high quality adhesion, it is preferably used in a mixture of 50% or more. Further, the amount of adhesion may be determined by any of the commonly known methods, such as one-type oiling roller method, one-type spray method, and metaling method. The amount of adhesion is 0.25 to 0.25% per 100g of fiber.
4-degree, in which the epoxy compound is 0.1-
It is preferable to deposit about 0.2 inch (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. Hindered phenol, which is known to be used to prevent oils from smoking when heated and from becoming volatile due to thermal decomposition, has a completely different function: suppressing the thermal polymerization of the epoxy ring itself and preventing other epoxy rings from forming. This was done based on new knowledge that it is effective in reducing thermal reactions with components, and this allows for high concentrations of reactive epoxy groups even on fibers after heating. Since it is possible to "remain", it is possible to provide a treatment system with excellent rubber adhesion.

In addition, for quantifying the particularly reactive epoxy part of the epoxy compound attached to polyester gtM1, use the usual epoxy quantitative method for the drawn and heat-treated yarn, which is deoiled with cyclohexane, and the cyclohexane is concentrated to form a sheath. 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 the 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, the quantification of the extracts from the yarn was carried out before and after heating, and the rate of change was examined.

Measurement of change rate of epoxy ring-1> (11) Sample Ig consisting of a commercially available epoxy compound (100%) was weighed, placed in a dish with a diameter of 4 crn, and heated at 200°C.
The sample was heated in a hot air dryer for 60 minutes and 90 minutes, and after cooling, the sample was dissolved in dioxane and subjected to a conventional hydrochloric acid-dioxane method using 0.2 NHCl. At this time, the epoxy oxygen content of the immature epoxy compound was simultaneously measured, and the rate of change was determined as the percentage of Epon rings before and after heating.

(Prevention) A sample consisting of a commercially available epoxy compound (100%) and a spinning oil were mixed so that the ratio of the epoxy compound to the spinning oil was 50.
/ 50 and 70/30, (1)
The rate of change was calculated using a similar method.

<Measurement of change rate of epoxy ring-2> In terms of the properties, 500 I! of yarn obtained after spinning and drawing of polyester and heat treatment! Then remove the oil using cyclohexane using a Soxhlet extractor according to the commonly known method for measuring the oil adhesion rate.
After cyclohexane was distilled, the amount of epoxy oxygen was determined using the hydrochloric acid-%-J-xane method, and the rate of change was determined from the measurements before and after the heat treatment.

The present invention will be further explained in detail with reference to Examples below. In the Examples, ``(') and ``part'' each indicate parts by weight or percent by weight.

Note that the examples used in this embodiment are limited in type, but are not limited thereto in any way. The epoxy compounds used in Examples and the compounds having a hindered phenol group in the molecule are listed below.

α] Epoxy compounds include E-1 glycerin polyglyceryl ether (Nagaushi Sangyo trade name Denacol EX-314) E-2 diglycerin polyglycerin ether (Nagaushi Sangyo trade name Denacol EX-421) E-3 polyglycerin polyglycidyl ether (Nagaushi Sangyo trade name Denacol EX-421) Product Name: Denacol EX-512) E-4 Bisphenol Polyglycidyl Ether (Gel Co., Ltd. Product Name: Ebico E-5 Sorbitol Polyglycidyl Ether (Nagaushi Sangyo Denacol EX-512) A-1 Tris-(2-methyl) as a hindered phenol compound -4-hydroxy-5-t-butylphenol)butane (ICI, Dopanol CA) A-21,3,5-)lis(4-t-butyl-3-hydroxy-2,6-dimethyl)incyanuric acid (Cyanamide, Cy7nox 1750) A-34,4'-butylidene-bis-(3-methyl-6
-t-butylphenol) (Sumitomo Chemical Sumilizer BBM) A-5 Pentaerythrityl-tetrakis (3-(3,5
-di-t-butyl-hydroxyphenyl)probionate] (Ciba Geigy, Irganox-1,010) was used.

Example-1 and Comparative Example-1 Each of diglycerin polyglycidyl ether (E-2), sorbitol polyglycidyl ether (E-5), and bisphenol type polyglycidyl ether (E-4) was used, and each was hindered. As a phenol compound, the above-mentioned A-2 and A-3 were combined with h 2,5 /16
Samples with and without addition were prepared, 1.0 g of each was collected in a stainless steel dish, heat treated at 200°C for 60 minutes and 90 minutes, and before and after the heat treatment were determined by the acid-resistant dioxane method. The epoxy oxygen (2) of each was determined, and whether it changed to (5) before or after heating was determined. Display the results -
Shown in 1.

Example 2, Comparative Example 2 Diglycerin polyglycidyl ether (E-2) was used in the same manner as in Example 1, and the amount of the hindered phenol compound (A = 3) was increased to 0.01 or more. Table 2 shows the results of determining how the temperature changes depending on whether or not dioleyl thiodipropionate is added as a thiodipropionic acid ester compound.

Example-3, Comparative Example-3 Using diglycerin diglycidyl ether (E-2), consisting of dioleyl adipate (20'all) and intridecyl stearate (30 parts) as a spinning oil base for polyester fibers. POE as a smoothing agent and emulsifier
(3 mol) of lauryl ether (15 parts) POE (12
A formulation consisting of castor oil ether (15 parts), POE (5 moles), nonylphenyl ether (io parts), POE (4 moles), onyl alcohol ether (io parts), etc. (using chicken, E-2 and ( B) ratio of 5 o/s
0 or 7 o/30 to form an epoxy compound-containing oil agent, and how the residual rate of epoxy rings changes depending on the presence or absence of A-1 or A-3, respectively. .

The results are shown in Table-3.

Example-4, Comparative Example-4 Polyethylene terephthalate fiber yarn (■=0.90,
(solvent, O-chlorophenol, temperature 35°C) at 40
It is wound onto a bobbin at a speed of 0 m/min, but before one winding is taken up, the epoxy compound E-2 used in Example-3 and (B) as a pace oil are used ~\The mixing ratio becomes 80/20. The 10% aqueous emulsion solution prepared in the above manner was applied by an oiling roller during spinning, and then stretched and
Heat treatment was performed. That is, the stretching was carried out using a stretching machine capable of two-stage heating stretching, stretching 3.5 times at 78°C and then at 180°C.
And the first stage and #! ! Stretched to 5.8 times in two stages,
Heat set at 200℃, 1500 denier/250
A filament elongation heat treatment system was obtained. At this time, E-2
/U = 80/20, Hindered Fer A-3 was obtained by adding 2.5% C to the epoxy compound and not adding it at the same time, and deoiling the yarn with cyclohexane from the yarn thus obtained. Regarding the deoiling component, epoxy oxygen
The amount of epoxy oxygen added to A-3 was 5.5, while that of yarn without addition was 3.5.
It was 9chi.

Claims (2)

[Claims] (1) When a fiber treatment agent containing 30% or more of a polyvalent epoxy compound with an average molecular weight of 200 to 3000 is attached to polyester fibers and heat-treated at 200°C or higher in the absence of a catalyst, the following general treatment agents may be used as the treatment agent: As shown by formula (1),
At least one hindered ferno group in the molecule ▲ There is a mathematical formula, chemical formula, table, etc. ▼ or ▲ There is a mathematical formula, chemical formula, table, etc. ▼ or ▲ There is a mathematical formula, chemical formula, table, etc. ▼... (1) [However, R ' represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, and Z represents another organic residue] in an amount of 0.05 to 5.0% (by weight) based on the epoxy compound. ) is used to thermally stabilize an epoxy ring. (2) When a fiber treatment agent containing 30% or more of a polyvalent epoxy compound with an average molecular weight of 200 to 3000 is attached to polyester fibers and heat-treated at 200°C or higher without a catalyst, the treatment agent is A method for thermally stabilizing an epoxy ring using a thioester compound and at least one compound having at least one hindered phenol group in an amount of 0.05 to 5.0% (by weight) based on the epoxy compound.