JPS5951624B2 - Oil agent for thermoplastic synthetic fiber production - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an oil for producing fibers, particularly for producing thermoplastic synthetic fibers that involve severe heat treatment.

Conventionally, in the production of thermoplastic synthetic fibers such as polyamide and polyester fibers, in order to smoothly proceed with the drawing process, an oil agent is applied to the undrawn yarn after spinning or once wound, and then drawing is carried out. However, among thermoplastic synthetic fibers, particularly large yarns for tire cords, etc., are drawn at high temperatures and at high ratios in order to obtain high strength.

Therefore, the fibers themselves and the oil adhering to the fibers are subjected to severe heat treatment.

This heat treatment is usually carried out at 180 to 240°C, and as a result, the oil emits smoke or accumulates as tar on the heater plate, impeding smooth operation.

Therefore, it is essential for the oil agent to have excellent heat resistance.

On the other hand, thermoplastic synthetic fibers (especially polyamide fibers) tend to shrink when heated, and can be used in the spinning and drawing or subsequent processing stages, as well as in the practical stages (for example, in the case of tire cords, under high loads, etc.).
When heated (such as when driving at high speed), heat shrinks, resulting in a decline in quality or strength.

It has been pointed out that in the case of the same fiber, there is a large difference in thermal shrinkage depending on the treatment agent attached.

Therefore, it is strongly desired that the performance of the oil agent for producing thermoplastic synthetic fibers is that the oil agent treatment system has low thermal shrinkage.

The lubricating components of conventionally used oils include mineral oils such as liquid paraffin, higher fatty acid esters such as butyl stearate and oleyl oleate, dibasic acid esters such as dilauryl adipate, and trimethylolpropane trilaurate. Polyhydric alcohol esters can be mentioned, but all of these emit smoke or turn into tar during heat treatment in the stretching process, and do not have sufficient heat resistance.

In recent years, a fatty acid ester made by adding 2 moles of ethylene oxide to bisphenol A (ester of bisphenol A ethylene oxide adduct) has been proposed as a lubricating component with good heat resistance (Japanese Patent Publication No. 47-29474), but it does not have the necessary performance as an oil agent. It was found that the material had serious drawbacks such as poor smoothness and large thermal shrinkage.

Therefore, the present inventors conducted repeated studies with the aim of developing a compound having heat resistance equal to or higher than that of the ester of bisphenol A ethylene oxide adduct described above and having low heat shrinkage, and as a result, the present invention was achieved.

That is, in the present invention, Z1 is an acyl group, Z2 is H or an acyl group, and X is -
(CH2)p-1-(CH2), 5(CH2), - or -(CH2) qO(CH2), p is an integer of 1 to 8, q is an integer of 1 to 6, A1. A2 is an alkylene group having 2 to 4 carbon atoms, R1 and R2 are H or an alkyl group having 1 to 4 carbon atoms, m19m2 is an integer of 1 or more, and n is an integer of 1 to 6.

) This is an oil agent for producing thermoplastic synthetic fibers, which is characterized by containing the compound shown in the following.

In the present invention, 71 in the general formula is an acyl group, and examples include acyl groups derived from monocarboxylic acids.

The monocarboxylic acids that form the above-mentioned acyl group include acetic acid, 2-ethylhexanoic acid, lauric acid, stearic acid, behenic acid, montanic acid, oleic acid, linoleic acid,
Examples include fatty acids having 1 to 30 carbon atoms such as erucic acid, coconut oil fatty acid, palm oil fatty acid, and tallow fatty acid, and cyclic monocarboxylic acids such as benzoic acid.

Among these, preferred are fatty acids having 6 to 30 carbon atoms.

Further, Zl is H or an acyl group, and the explanation for Zl can be directly applied to the acyl group.

When the number of carbon atoms in the acyl groups represented by Zl and Z2 is both less than 6, smoke tends to be generated.On the other hand, when the number of carbon atoms in both is more than 30, taring tends to occur easily.

In the general formula, A1. A2 is an alkylene group having 2 to 4 carbon atoms, and these groups form an oxyalkylene group together with an oxygen atom.

Examples of such oxyalkylene groups include oxyethylene, oxypropylene, and oxybutylene groups.

Each oxyalkylene group may be a plurality of types of groups, and in this case, these groups may be included in a block or random (preferably block) form.

. Preferred oxyalkylene groups are oxyethylene groups or two types of groups: oxyethylene groups and oxypyrene groups.

Moreover, m05m2 indicates the number of moles of the oxyalkylene group added.

m19m2 are each an integer of 1 or more, preferably 1 to 30, particularly preferably 3 to 15.

In the general formula, R1 and R2 are H or an alkyl group having 1 to 4 carbon atoms, such as a methyl group, a butyl group, or a tertiary butyl group.

Alternatively, it represents a bisphenol residue (a group obtained by removing H from the phenolic hydroxyl group of bisphenol).

Examples of bisphenols forming the above-mentioned residues include bisphenol A, bisphenol F, and 2,2'-bis(4-hydroxyphenyl)butane.

Among these, bisphenol A is preferred.

In the general formula, X is -(CH2)p-9-(CH2),
5(CH2)9- or -(CH2) QO(CH2)
q, p is an integer from 1 to 8, and q is an integer from 1 to 6.

If p becomes larger than 8 or q becomes larger than 6, smoothness deteriorates.

The above X is a dicarboxylic acid residue (two C from dicarboxylic acid
The dicarboxylic acids forming the above residues include aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid, azelaic acid, and sebacic acid, thiodiacetic acid, thiodipropionic acid, and thiocicaproic acid. Oxydicarboxylic acids such as thiodicarboxylic acid, oxydiacetic acid, oxydipropionic acid, and oxycaproic acid are mentioned.

Preferred among these is thiodicarboxylic acid.

In the general formula, n indicates the degree of polymerization of the compound.

n is an integer from 1 to 6, preferably from 1 to 2.

When n exceeds 6, the viscosity increases and emulsification becomes difficult,
Moreover, smoothness deteriorates.

n can be determined by gel permeation chromatography.

The compounds in the present invention can be produced by various known methods.

For example, an adduct obtained by adding an alkylene oxide having 2 to 4 carbon atoms to bisphenol by a conventional method and at least one type of aliphatic dicarboxylic acid, thiodicarboxylic acid, or oxycarboxylic acid having hydroxyl groups at both ends. Monocarboxylic acid monoester of alkylene oxide adduct of bisphenol , a method of reacting an alkylene oxide adduct of bisphenol and a dicarboxylic acid, and if necessary, the terminal O of the above reactant.
Examples include, but are not limited to, a method of monoesterifying an H group with a monocarboxylic acid.

The esterification method may be a known method, for example, the reaction may be carried out at 80 to 180°C in the presence of a catalyst (sulfuric acid, hypophosphorous acid, para-toluenesulfonic acid, etc.).

The oil agent of the present invention can be obtained by blending the compound represented by the general formula with a known oil component.

The content of the above compound in the oil agent is not particularly limited, but is usually 30 to 80% by weight, preferably 40 to 70% by weight.
It is.

The method of using the oil agent of the present invention may be the same as usual. For example, it can be used in the form of water-free (crude oil) or in the form of an emulsion emulsified with water and spun by a known oiling method such as a roller oiling method, a spray method, or a dipping method. Lubricate during the process or immediately before stretching.

Further, the amount of the oil applied may be the same as usual, for example, 0.5 to 3.0% by weight based on the fiber.

The oil agent of the present invention has excellent heat resistance, with a temperature of 180 to 240
It does not emit smoke or deposit as tar on the heater plate even when heat treated at high temperatures of ℃.
The thermoplastic synthetic fiber to which the oil agent of the present invention is attached has the greatest characteristic of having small thermal shrinkage even when subjected to heat treatment.

Therefore, the oil agent of the present invention is excellent as an oil agent for producing thermoplastic synthetic fibers such as nylon and polyester, which involve severe thermal processes.

The present invention will be explained below with reference to Examples, but the present invention is not limited thereto.

Example 1 The thermal stability and smoke generation properties of the compounds vIJ ('A1-3) according to the present invention shown in Table 1 and the lubricant components (A4-7) of conventional oils were evaluated, and the results are shown in Table 2.

It can be seen from Table 2 that the compounds of the present invention have extremely excellent heat resistance.

(Note 1) Test method (1) Precisely weigh 0.5g of the thermal stability sample into a 100ml beaker, and
Evaluation after heating for 2 hours in a circulating air drying machine at 00°C.

(2) Smoke generation: Evaluate the state of smoke generation when a sample is dropped onto a hot plate at 200°C.

(Note 2) Explanation of evaluation (1) Coloring ○...Almost no coloring.

△... Slightly colored.

×...It is quite colored.

(2) Tarification ○...Almost no tar was formed.

△... Slightly tarry.

×・・・It has become quite tarry.

(3) Smoke-emitting property ○...Almost no smoke is emitted.

△・・・・・・Slightly smoking.

×・・・・・・Smoke intensely.

Example 2 1% of the oil agent listed in Table 3 was applied to a sample yarn obtained by washing and drying a commercially available 1260 denier nylon cord yarn, and
The heat shrinkage rate of each was measured.

The results are shown in Table 4.

Table 4 shows that the yarn treated with the oil of the present invention has a small heat shrinkage rate.

(Note 3) Hydrogenated castor oil EO25 is ethylene oxide 2 of hydrogenated castor oil.
5 molar adduct is shown.

Note that Compound 1 represents Compound A1 listed in Table 1.

The same applies to others. (Note 4) Measurement method* Apply a 10g weight to the oil-treated sample thread and weigh it correctly at 50%.
Measure 0 mm, mark two points, take a weight, hang it in a dryer at 200°C, leave it for 15 minutes, take it out, cool it to room temperature, apply a weight again, and measure the length between the two points.

This was repeated 10 times, and the heat shrinkage rate (%) was calculated using the following formula.

l: Length between two points (mn+)
A 20% aqueous solution of each of the oils A and E was applied with a purity of 1% by a roller oiling method.

After winding and adjusting this oil-treated undrawn yarn,
Stretching was carried out using a conventional hot stretching method (temperature of about 200° C.).

At this time, smoke generation on the hot plate and staining of the hot plate were evaluated, and at the same time, the number of thread breakages during stretching of 107 m was evaluated.

Claims (1)

[Claims] 1 General formula (in the formula, Z1 is an acyl group, Z2 is H or an acyl group, X is -(CH2), -, -(CH2), S (CH2)
Q- or -(CH2) QO(CH2) Q-, I)
is an integer of 1 to 8, q is an integer of 1 to 6, A1. A2 is an alkylene group having 2 to 4 carbon atoms, R1 and R2 are H or an alkyl group having 1 to 4 carbon atoms, ml, m2 is an integer of 1 or more, n
represents an integer from 1 to 6. ) An oil agent for producing thermoplastic synthetic fibers, characterized by containing a compound represented by: