JPS609971A - Oil agent for synthetic fiber - 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 The present invention uses a combination of a specific polyether and a specific antioxidant to prevent heater stains, thread breakage, and
The present invention also relates to an oil agent for synthetic fibers that significantly reduces smoke generation during processing.

Generally, an oil agent is applied to synthetic fibers such as polyester and polyamide to provide lubricity, cohesiveness, and antistatic properties, and to facilitate smooth spinning and processing.

On the other hand, synthetic fibers used as industrial materials for tires: l-F, V-belts, conveyor belts, etc.
Heat treated with a heater above °C, 220 °C during processing
Heat setting is performed at a temperature of 60 to 180 seconds at a temperature of 0.degree. C. or higher, which is extremely harsh for oil agents.

Therefore, the lubricants for synthetic fibers used as industrial materials have high lubricity, cohesiveness, and antistatic properties, as well as high heat resistance to reduce heater contamination during the spinning process and smoke generation during processing. is required.

BACKGROUND ART Compositions containing ethylene oxide and propylene oxide as one component in a higher alcohol or alkylphenol have been known as lubricants for synthetic fibers having high levels of lubricity, focusing, antistatic properties, and heat resistance. For example, Japanese Patent Publication No. 56-11785 discloses a technology for obtaining a lubricating oil agent that does not emit smoke or turn into tar by using an adduct of propylene oxide and ethylene oxide, which are alcohols, as an oil agent for producing bulky textured yarns of polyester synthetic fibers. ing. The ratio of ethylene oxide to propylene oxide used here (hereinafter referred to as EO/PO ratio)
is 2 o/s O to 0/100 in molar ratio. JP-A-49-36996 discloses propylene oxide and ethylene oxide adducts (specifically disclosed EO/PO molar ratio 5/30.5/15) as an oil agent for synthetic fibers.
is used to reduce tarring. Japanese Unexamined Patent Publication 1987-
121668 discloses propylene oxide and ethylene oxide adducts (EO/PO weight ratio 13/87 to 35/65) as one component of a lubricant composition for finishing synthetic fibers.
) has been shown to prevent smoke and varnish formation during bulk processing, crimping, texture processing, etc. Furthermore, JP-A-56-140179 discloses a technique for obtaining a lubricant with good heat resistance by using a propylene oxide and ethylene oxide adduct (50% by weight or less of ethylene oxide) as a treatment composition for false-twisted yarn. are doing. However, these techniques are insufficient for use as oil agents for industrial materials such as tire cords, and are insufficient for processing at high temperatures and for long periods of time in processing steps. As a lubricant for industrial materials such as tire cords, JP-A-5
2-31197, the number of ethylene oxide units/number of propylene oxide units 0.10 to 0.65 (EO/P
The use of an adduct of propylene oxide and ethylene oxide in a weight ratio of 7/93 to 32/68) is disclosed, and the purpose of this is to prevent adhesion of tire cords due to air bubbles.

Synthetic fiber oils containing adducts of propylene oxide and ethylene oxide are known, but generally the heat resistance tends to decrease as the ethylene oxide content increases, so the propylene oxide content is quite large. height) is used in the area. Even in that case, when used in industrial materials such as tire cord oil, tar, smoke, etc. were produced, which was not satisfactory.

Contrary to the conventional general understanding, the present invention is an oil agent for treating synthetic fibers for industrial materials by blending a hindered phenolic antioxidant with propylene oxide and ethylene oxide adduct, which have a relatively high ethylene oxide content. The present invention provides an oil agent that exhibits excellent heat resistance even when used as G).

That is, in the present invention, ethylene oxide and propylene oxide are added to a hydroxy compound having 8 or more carbon atoms in a weight ratio of 90/90.
Average molecular weight obtained by reacting at 10 to 55/45: 90
The present invention relates to an oil agent for synthetic fibers containing a polyether compound having a molecular weight of 0 to 500 and a hindered phenol antioxidant having a molecular weight of 300 or more.

Hydroxy compounds used in the present invention include higher alcohols (which may have side chains and may be secondary alcohols), alicyclic alcohols, alkyl or phenylphenols, naphthols, and bisphenols. etc., and a hydroxy compound having 8 or more carbon atoms is preferable. When the number of carbon atoms is less than 8, sufficient heat resistance cannot be obtained.

A particularly preferred hydroxyl compound is 1 having 8 to 18 carbon atoms.
saturated higher alcohols such as octyl alcohol,
Inoctyl alcohol, decyl alcohol, isodecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, heptyl alcohol, inhexadecyl alcohol, stearyl alcohol, instearyl alcohol, etc., and monohydric alcohol having an alkyl group having 4 to 14 carbon atoms. alkylphenols such as butylphenol, nonylphenol, dodecylphenol, etc.

Higher alcohols become dihydric or higher, or have a carbon number of 18.
When the number of carbon atoms exceeds 8, the lubricity decreases, and when the number of carbon atoms is less than 8, the smoke reduction effect disappears. Furthermore, if the higher alcohol becomes unsaturated, heater stains tend to increase.

When phenols have a valence of two or more, lubricity tends to decrease. Furthermore, if the number of carbon atoms in the alkyl group exceeds 14, the lubricity will be reduced, and if it is less than 4, smoke will easily occur. Saturated alkyl groups are preferable, and unsaturated alkyl groups tend to stain the heater.

A block or random copolymer in which ethylene oxide and propylene oxide are added to a hydroxy compound can be synthesized by a known method.

The average molecular weight of the polyether used in the present invention is 900
~5000. Preferably it is 1000 to 3000, and the weight ratio of ethylene oxide to propylene oxide is 90/10 to 55/45, preferably 80/20 to 60.
/40.

If the average molecular weight of the polyether is less than 900, smoke generation will not be reduced even when combined with a hindered phenolic antioxidant, and if it exceeds 5,000, the lubricity will deteriorate.

When using a hindered phenol antioxidant, the polymerization ratio of ethylene oxide and propylene oxide is 90.
/10, heater contamination increases rapidly, and 55
If it is less than /45, the smoke reduction effect will be lost, so it is not suitable.

The oil agent of the present invention contains a hindered phenol antioxidant with a molecular weight of 300 or more, and an example thereof is 2.2-
Methylene-bis(4-methyl-6-tert-butylphenol), 4,4-butylidene-bis(3-methyl-6-tert-butylphenol), bis(3-methyl-4-hydroxy-5-tert-benzyl) Sulfide, tris(3,5-di-tert-butyl-
4-hydroxyphenyl)ine cyanurate, tetrakis[methylene-3(3,5-di-tert-butyl-
4-hydroxy)gropionate]methane, 6-(4-
Examples include hydroxy-3,5-di-tert-butylanilino-2,4-bis-octyl-thio-1,3,5.

The molecular weight of the hindered phenolic antioxidant is 2.6-
Di-tert-butyl-para-cresol-like 3
If it is less than 00, the antioxidant itself will volatilize during heating and will not be effective in reducing smoke generation.

Diphenylamine antioxidants such as 4,4-bis(4-α,α-dimethylbenzyl)diphenylamine are effective in reducing smoke generation, but are undesirable because they cause yellowing and discoloration of fibers.

The polyether of the present invention is preferably contained in the oil agent in an amount of 50.0 weight or more, and the hindered phenol antioxidant is contained in an amount of 0.5 to 5.0 weight, preferably 1.0 to 3.0 weight.
Weight engaged.

If the weight of polyether is less than 50.0%, heater fouling or fuming will increase. If the amount of the hindered phenol antioxidant is less than 0.5 weight, smoke generation cannot be suppressed.

Other substances can be added to the oil agent of the present invention as long as they do not impair lubricity, cohesiveness, antistatic properties, and heat resistance.

Of course, depending on the required properties of the oil agent, it may be composed only of polyether and hindered phenol antioxidant without using other substances.

In processed yarns made of synthetic fibers such as polyester and polyamide, oil agents turn into sludge on the heating plates or heating rollers during the yarn spinning and false twisting process, and this accumulates and causes heater stains, leading to yarn breakage and roller winding. , which can easily cause problems such as staining.

Therefore, it is necessary to periodically clean the heater, but in order to improve operability, various attempts have been made to make the heater cleaning cycle as long as possible.

During these studies, an ethylene oxide-propylene oxide copolymer was discovered as a material that does not cause sludge formation on the heater, and an oil based on this copolymer has good lubricity, cohesiveness, and antistatic properties. It has been put into practical use because of its superior properties and extremely low heater contamination.

Due to its structure, ethylene oxide-propylene oxide copolymer is easily decomposed by heat, and most of the decomposed products are volatilized, so it is difficult to accumulate in the heater as sludge. It has also been revealed that it does not volatilize and produces very little smoke during yarn spinning and false twisting.

However, when polyether is heat-treated during spinning and false twisting, the oven time is less than 1 second, so it does not decompose and volatilize and does not generate smoke, but it is Heat treatment for 60 seconds or more at temperatures below causes thermal decomposition and significantly increases smoke generation.

It is also already known that oxidized rainproofing agents have the effect of suppressing thermal decomposition at high temperatures, but conventionally oxidized rainproofing agents have been simply oxidized to ethylene oxide-propylene oxide copolymers containing relatively large amounts of propylene oxide, which are common as lubricants for synthetic fibers. It is difficult to prevent heater stains and smoke generation during processing simply by adding an inhibitor, and the ratio of ethylene oxide to propylene oxide in polyether is 90/10 by weight.
-55/45 is a necessary condition for preventing smoke generation during the processing process.

Ethylene oxide, which works synergistically with the above facts and hindered phenolic antioxidants, produces good results.
The present invention was achieved by discovering the structure of a propylene oxide copolymer.

The effects of the present invention are most exerted particularly when used as an oil agent for polyester industrial materials.

The oil agent of the present invention is an aqueous emulsion with a concentration of 5% to 25% by weight, and is applied to the synthetic fiber yarn immediately after spinning by a known oiling method such as roller oiling or plate oiling.
2.0 @Quantity/attached.

According to the present invention, it is possible to obtain a synthetic fiber that has excellent lubricity, cohesiveness, and antistatic property, and has significantly reduced heater stains in the spinning process and smoke generation in the processing process.

Next, the present invention will be specifically explained using examples.

Example 1 Oil agent A, N2.0 Da shown in Table 1 was placed in a stainless steel plate with a diameter of 1o (7), and the oil agent was spread to form a thin film using a rubber aging tester (manufactured by Satake Chemical Co., Ltd.: Model 122CM). I did a smoke test. The temperature of the test machine was set to 240°C, and the generated smoke was measured using a dust meter (manufactured by Shibata Chemical Co., Ltd.: Model P-
5) and expressed as the cumulative count 3 minutes after adding the sample as shown in Table 1.

Note that EO/PO in Table 1 indicates ethylene oxide/propylene oxide, and the weight ratio of EO/PO is indicated in parentheses.

As is clear from Table 1, I with EO/PO added to a hydroxyl compound outside the scope of the present invention, and EO/P
K in which O is below the range of the present invention generates a lot of smoke.

J in which the molecular weight of the polyether is below the range of the present invention.

The molecular weight of the antioxidant is below the present invention, M the antioxidant content is below the range of the present invention, N the content of the polyether of the present invention is below the range of the present invention, and conventionally used polyesters. O, in which no antioxidant is added to the ether, generates a lot of smoke.

A and H of the present invention generate less smoke.

Example 2 Oils P and V shown in Table 2 were made into a 25% aqueous emulsion, and a polyester filament yarn (
5100 denier/196 filament) with 0 solids content
．． Roller stretching was carried out immediately after adhesion of 6% without winding up.

The first stage stretching ratio is 1.4@, and the total stretching ratio is 5.1.
Two-stage stretching was performed to double the size, the temperature of the set roller was set at 250°C, and the yarn was wound at a yarn speed of 3500 m/sin.

The number of yarn breakages during stretching, staining of the set roller, and coloration of the drawn yarn by fume 1 were investigated, and the results are shown in Table 3.

Table 3 *2 Number of thread breakages during drawing (0 times, 748 hours) *3 Using 50 g of drawn thread as a sample, smoke generation was evaluated in the same manner as in Example 1, and the results were expressed as an integrated value over 2 minutes.

*4 Set roller dirt set at 250°C at 48°C
Observation after time extension.

As is clear from Table 3, S using a diphenylamine-based antioxidant, which is not included in the present invention, is excellent in terms of yarn breakage, roller staining, and smoke generation, but coloring of the drawn yarn is observed.

T1 whose average molecular weight of polyether exceeds the range of the present invention
Since U using a polyether other than the one according to the present invention has poor lubricity, the yarn breaks many times during drawing.

Conventional oils V and W cause large roller stains,
The number of thread breakages increases over time.

Compared to these, P and R of the present invention are superior in all aspects of yarn breakage, roller stains, smoke generation, and coloration.

Procedural amendment (voluntary) September 19, 1988 Patent Application No. 112325 2. Name of the invention 3. Person making the amendment 3. Relationship to the case Patent applicant 4. Agent 5. Date of amendment order (Voluntary) 7. Contents of the amendment (1) In the fourth line from the bottom of page 4 of the specification, the words "adhesion" are corrected to "adhesion deterioration."

(2) On page 9, line 3, the phrase "volatizes when heated" is corrected to "volatizes when heated."

that's all

Claims (1)

[Claims] 1. A hydroxy compound having 8 or more carbon atoms and ethylene oxide and propylene oxide in a weight ratio of 90/10 to 5.
Average molecular weight obtained by reacting at 5/45: 900-50
An oil agent for synthetic fibers containing a polyether compound of 0.00 and a hindered phenol antioxidant with a molecular weight of 300 or more. 2. Hydroxy compound with 8 or more carbon atoms has 8 to 18 carbon atoms
The oil agent according to item 1, which is a monohydric higher alcohol or a monohydric alkylphenol having a saturated alkyl group having 4 to 14 carbon atoms. 3. Polyether compound content of 50 weight or more and hindered phenol antioxidant 0.5 to 5.0 weight
%. 4. The oil agent according to item 1, which is used for synthetic fibers for industrial materials.