JP2550218B2 - Polyester fiber - Google Patents

Description

TECHNICAL FIELD The present invention relates to polyester fibers. More specifically, the present invention relates to a polyester fiber, particularly a low-shrinkage polyester fiber, which has excellent yarn-forming efficiency during fiber production and also has good weaving efficiency during weaving with sizing.

(Prior Art) In recent years, the progress of the spinning technology in the production of synthetic fibers has been remarkable, and the spinning speed has been increasing with the development of the high-speed winder. It may also be referred to as a straight line) is becoming more common.

However, as the spinning speed increases, abrasion between the running yarn and various yarn guides (rollers, guides, etc.) increases, and not only the quality of the yarn obtained by inducing single yarn breakage is impaired, but also
Since it is necessary to set heat at a higher temperature than before in order to impart predetermined physical properties, especially heat shrinkage properties, the amount of fuming of the oil component increases, and the adhesion of scum derived from the polyester oligomer to the roller surface also increases. It also includes problems such as frequent yarn breakage.

In particular, polyester fibers for industrial materials used in sails, tents, etc. are required to have dimensional stability of yarn extremely important and heat shrinkage rate to be extremely small as compared with ordinary polyester fibers for clothing. Therefore, the above heat setting needs to be performed at a higher temperature than that of the fiber for clothing, the amount of smoke of the oil component is further decreased (heat resistance), the generation of oligomer scum is decreased (resistance to oligomer scum), and high temperature and high speed operation is possible. Oils with excellent lubricity have become important.

On the other hand, when passing through a weaving / knitting process, a yarn obtained by such a yarn is often given a sizing agent that matches each process in order to increase the efficiency of the weaving / knitting process. However, if the treatment oil applied in the spinning process is inappropriate at this time, the glue film formed on the broken yarn is softened to reduce the protective action of the yarn,
Alternatively, it is referred to as "size removal", and the size agent is dropped and accumulated at various places of the loom to increase friction with the yarn, causing fluff and yarn breakage, which causes a problem of impeding weaving / knitting efficiency.

For this reason, it has been proposed in the past to use an amide component in a spinning oil agent, but according to a recent study by the inventors of the present invention on high-speed spinning, although such an agent is good in terms of the sizing property, the spinning oil agent is It was found that if too much is used, the heat resistance or lubricity will be impaired and the spinning efficiency will be impaired.

In order to solve such a problem, the present inventors first
A polyester fiber provided with an oil agent in which a high molecular weight monohydric alcohol ester and a partial ester of a polyhydric alcohol having a hydroxyl group in the molecule are blended has been proposed (Japanese Patent Application No. Hei 2).
-125497). However, although such an oil agent improves heat resistance and scum resistance to improve spinning efficiency, stains on the surface of the heat roller may occur due to long-term operation.
There were still insufficient points.

(Object of the invention) The present invention has been made in view of the above background, and its object is to have excellent heat resistance, oligomer scum resistance and lubricity in the yarn making process, and "paste removal" in the weaving process,
It is an object of the present invention to provide a polyester fiber which does not induce scum and has good weaving efficiency.

(Structure of the Invention) As a result of intensive studies to achieve the above object, the present inventors have identified a specific monohydric alcohol ester, a specific aromatic ester, and an ethylene oxide adduct of triglyceride having a hydroxyl group in the molecule. It has been found that by adding an oil agent mixed in an amount, it is possible to simultaneously improve unprecedentedly high heat resistance, lubricity and excellent sizing characteristics, and obtain a polyester fiber of extremely high quality, and reach the present invention. did.

That is, according to the present invention, the following components (A), (B) and (C) are contained as essential components on the surface of the polyester fiber, and the content of each of the components (A), (B) and (C) is ~ Polyester fiber (A) component characterized in that 0.3 to 1.0% by weight of an oil agent satisfying the formulas (iii) are attached at the same time. Aliphatic monohydric alcohol ester having a molecular weight of 550 to 750 which is liquid at room temperature. Component (B) Aromatic ester represented by the following formula and liquid at room temperature [Wherein R ₁ and R ₂ are alkyl groups having 8 to 25 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, and n and m are integers of 1 or 2]. ] Component (C) An alkylene oxide adduct of triglyceride which is liquid at room temperature and has one or more hydroxyl groups in the molecule (i) W _A + W _B = 20 to 75 (ii) W _C = 2 to 15 (iii) W _A / W _B = 95/5 to 60/40 [where W _A , W _B and W _C are the contents (% by weight) of components (A), (B) and (C) with respect to the active oil component] Represents ] Is provided.

The aliphatic monohydric alcohol ester (A), which is an essential component of the oil agent imparted to the polyester fiber of the present invention, is an ester compound obtained from a monovalent higher alcohol and a monovalent or divalent aliphatic carboxylic acid. The molecular weight thereof should be 550 to 750, preferably 600 to 700, and should be liquid at room temperature. Specifically, a higher alcohol having 20 to 34 carbon atoms is used as the monohydric higher alcohol, and higher fatty acids such as stearic acid, oleic acid and palmitic acid or dibasic acids such as adipic acid, sebacic acid and thiodipropionic acid are used. A monoester or a diester compound such as isoeicosyl stearate, isopentacosyl palmitate, isopentacosyl oleate, isopentacosyl erucinate, or the like, or diisostearyl chito can be used. Dipropionate, dioleoyl adipate,
Examples thereof include diesters such as diisostearyl sebacate.

Here, only aliphatic monohydric alcohol esters having a molecular weight of more than 750 or becoming solid at room temperature or polyhydric alcohol esters having no hydroxyl group such as coconut oil and rapeseed oil which are triglycerides were used as the component A. In this case, the size loss during weaving may increase, or the friction between the running yarn and the yarn guide may increase during yarn production, resulting in breakage of single yarn, which is not preferable.

Further, in the case of an aliphatic monohydric alcohol ester having a molecular weight of less than 550, not only is it a factor that causes volatilization due to heat at the time of spinning to generate smoke and pollute the working environment, but also a heat roller,
It is not preferable because tar is formed in the yarn guide and the like, which may cause breakage of single yarn.

The aromatic ester (B), which is an essential component of the oil agent used in the present invention, is a diester compound represented by the following general formula, in which alkylene oxide is added to bisphenol A and then esterified with an aliphatic monocarboxylic acid.

In the formula, R ₁ and R ₂ represent an alkyl group having 8 to 25 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and n and m each represent an integer of 1 or 2. When the carbon number of R ₁ and R ₂ is less than 8, lubricity tends to decrease, abrasion resistance tends to deteriorate, and raw yarn feathers also tend to increase. On the other hand, if the carbon number exceeds 25, it is difficult to obtain industrially, which is not preferable. Further, when the number of added moles of alkylene oxide (n or m) is 0, the property of the aromatic ester becomes solid at room temperature, so that the adhesiveness of the sizing agent in the sizing step is hindered. In the above case, since the hydrophilicity increases and the glue film is plasticized, the protective action of the glue film formed on the yarn is reduced and the weaving / knitting effect deteriorates.

Examples of the component (B) that is usually preferably used include dilaurate of bisphenol A added with 2 moles of ethylene oxide.

The oil agent used in the present invention contains 20 to 75% by weight, preferably 30 to 65% by weight of the total amount of the components (A) and (B) detailed above with respect to the active agent of the oil agent. Need to be If this content is less than 20% by weight,
The lubricity required for high-speed spinning cannot be imparted, and the occurrence of single yarn breakage tends to increase, and there is little improvement effect on problems such as "paste removal" during weaving. On the other hand, when it exceeds 75% by weight, a problem occurs in the emulsion stability of the oil agent system, which is not preferable.

Further, in the present invention, the weight ratio (A / B) of the component (A) and the component (B) needs to be within the range of 95/5 to 60/40. When the ratio of the B component is less than 5% by weight with respect to the total amount of A and B, the heat resistance of the oil agent decreases, and when it exceeds 40% by weight, the friction of the thread becomes high and the post-processing When weaving with sizing, the adhesiveness of the sizing film on the yarn is reduced, or the cohesive force of the sizing film is weakened, resulting in weakening the sizing effect.

The alkylene oxide adduct of triglyceride having a hydroxyl group in the molecule, which is another essential component of the oil agent used in the present invention, needs to be liquid at room temperature. Further, the content is 2 to 15 relative to the active ingredient of the oil agent.
It should be contained in an amount of 5% by weight, preferably 5 to 10% by weight.

The present invention is presumed to be because such an alkylene oxide adduct of glyceride has excellent compatibility with a polyester oligomer (mainly a cyclic trimer) and dissolves an oligomer precipitated by a treatment such as heating during polyester fiber production in an oil agent system. However, it was found that the effect of suppressing the accumulation of oligomer scum on the roller, the yarn guide, etc. is great. Therefore, if the amount used is too small, these effects do not appear, while if the amount is too large, the effect of the above-mentioned component A (paste removal resistance) is reduced, and
Since the friction between the running yarn and the yarn guide also increases and single yarn breakage tends to increase, the amount used is 2 to 15% by weight as described above.
It is necessary to

Further, in the case of a glyceride alkylene oxide adduct that does not have a hydroxyl group in the molecule or is solid at room temperature, oligomers are likely to be deposited on the cooling roller after heat setting, and thus the running property of the yarn is lost. As a result, single yarn breakage occurs, squeeze out increases, and friction between the running yarn and the yarn guide during yarn production increases, which is not preferable.

The alkylene oxide added in the component (C) is an alkylene oxide having 2 to 4 carbon atoms, and ethylene oxide is particularly preferable. The number of added moles is 4 with respect to the glyceride having a hydroxyl group.
-30 mol, especially 8-15 mol is desirable. When the number of added moles deviates from this range, it is estimated that the solubility of the polyester oligomer decreases, but the effect of suppressing oligomer scum deposition tends to decrease.

Examples of the C component include alkylene oxide adducts of hydrogenated castor oil, and aliphatic monocarboxylic acid monoesters or diesters thereof. Specifically, POE (8) hydrogenated castor oil ether (POE
In (n), the average number of moles of oxyethylene oxide added is n.
It is shown to be molar. The same applies hereinafter), POE (12) hydrogenated castor oil ether, POE (25) hydrogenated castor oil dilaurate and the like are preferable.

It is particularly preferable that the oil agent used in the present invention further comprises the following components (D) and (E) together in an amount of 1% by weight or more. In the component (D) among these components, the phosphate anion part (phosphate residue) is oriented on the metal surface such as thread guide, while the amine cation part (organic amine residue) is oriented on the fiber surface. It is presumed that the friction under high contact pressure can be reduced in combination with the components (A) to (C). And therefore, with less scum buildup on the roller surface,
It is presumed that the drawability is improved, the fluff of the drawn yarn is reduced, and further, the abrasion resistance of the fiber is improved, whereby hardening is exhibited.

As the component (D), a salt consisting of a phosphoric acid partial ester and an organic amine is used.

The phosphoric acid partial ester preferably used is C
_At least one phosphoric acid partial ester selected from _{8 to 22} higher alcohols, C _{8 to 22} alkyl group-containing phenols, and alkylene oxide adducts thereof (10 moles or less) can be mentioned, for example, octyl alcohol and lauryl. Alcohol, oleyl alcohol, isostearyl alcohol, phosphoric acid mono- or diesters such as nonylphenol, or polyoxyalkylene glycol monoalkyl ether obtained by adding 10 mol or less of ethylene oxide and / or propylene oxide to these higher alcohols and alkylphenols, Examples thereof include phosphoric acid mono- or diesters such as polyoxyalkylene glycol monoalkyl phenyl ether.

As the organic amine used in combination with the phosphoric acid partial ester, the organic amine represented by the following general formula is preferable.

However, R ₁ ′ is a C _8-22 saturated or unsaturated alkyl group, R ₂ ′ and R ₃ ′ are hydrogen or a C _1-5 alkyl group, respectively.
_A'is a _C2-4 alkyl group, _{n'and m'are} m '+, respectively.
An integer satisfying n '= 0 to 10 is shown. R ₁ ′ has 7 carbon atoms
Below, extreme pressure lubrication performance is deteriorated (friction increases), while when the carbon number is 23 or more, it becomes difficult to obtain commercially, which is not preferable. It is more desirable that R ₂ ′ and R ₃ ′ are both alkyl groups.

Specific components (D) include the above-mentioned phosphoric acid mono- or diesters, stearylamine, laurylmethylamine and their ethylene oxide and propylene oxide adducts, and further octyldimethylamine,
Examples thereof include reaction products with lauryldimethylamine, oleyldimethylamine, isostearyldimethylamine, lauryldiethylamine and the like.

In the present invention, the component (D) reduces friction under high contact pressure as described above, but since the component is easily colored by heating, it is desirable to use the component (E) together.

As the component (E), even if the phosphate residue is the same as the phosphate residue of the component (D),
Further, they may be different, for example, at least one phosphoric acid partial ester selected from C _8-22 higher alcohols, C _8-22 alkyl group-containing phenols, and alkylene oxide adducts thereof (10 moles or less). The alkali metal salts of can be mentioned. Among them, lauryl phosphate potassium salt, isocetyl phosphate potassium salt, isostearyl phosphate sodium salt and the like are preferable.

On the other hand, when the oil agent contains the above-mentioned component (D) and component (E), the component (E) is released as an incompatible component from the oil agent during high temperature heating (for example, during heat setting after stretching), so that the heating roller, There may be a problem that scum easily accumulates on the hot plate or the like. Use this problem (E)
It is sufficient to reduce the degree of neutralization of the component, but in this case, the effect of reducing friction under high contact pressure is reduced, and other factors such as causing corrosion of metals used for threading etc. The problem occurs.

It has been found that such a problem can be solved by using the component (F) HO (CH ₂ CH ₂ O) _n H (however, n = 1 to an integer of 20) in combination. That is,
Since the compound is an organic compound having high polarity, it is considered that it suppresses the free precipitation of the component (E) and suppresses the generation of scum. Examples of the component (F) that is preferably used include low molecular weight ethylene oxide polymers such as ethylene glycol, diethylene glycol, and triethylene glycol, but if the molecular weight becomes too large, the viscosity of the oil agent will increase.
A degree of polymerization of 20 or less is desirable because it may cause fuzz and yarn breakage.

The content of the component (F) is 10% by weight or less, preferably 2 to 5% by weight, based on the active ingredient of the oil agent. Even if it is used beyond this range, the compatibility is not improved, and rather the emulsion stability of the oil agent is impaired, which is not preferable.

The polyester fiber of the present invention, as described above, (A),
The components (B) and (C) are essential components, and (i) to (ii)
An oil agent containing i) in a range satisfying the formula at the same time, preferably a fiber to which an oil agent further containing components (D), (E) and (F) is attached, but does not impair the object of the present invention. It goes without saying that an oil agent containing another oil agent component may be attached within the range. Examples of such compounding agents include heat-resistant thioester-based smoothing agents, emulsifiers for use as emulsions, antistatic agents for preventing static electricity, antioxidants for improving heat resistance, and extreme pressure lubrication of oil agents. Examples thereof include organic or inorganic additives for improving the properties and oil film strength.

The oil agent may be applied to the polyester fiber at any time after the spun yarn is solidified, but it is usually applied to the yarn before the take-up roller.

As a preferred means for applying, the above-mentioned oil agent is formed into an aqueous emulsion, and a method of applying it through a metering oiling nozzle can be mentioned, but the application amount is 0.3 to 1.0% by weight relative to the fiber weight as the oil agent pure content. Therefore, the weaving efficiency of the fibers obtained by the above treatment is improved. If this amount is less than 0.3% by weight, sufficient effect cannot be obtained. On the other hand, if it exceeds 1.0% by weight, the effect does not increase any more, and excess oil agent adheres to the roller, thread guide, etc. Not preferable.

Further, the oil agent used in the present invention exerts its effect when applied to polyester fiber which is heat-treated at high temperature. Therefore, in the present application, the effect is particularly large when targeting the polyester fiber that needs to be heat-set at a high temperature, particularly the low shrinkage polyester fiber having a dry heat shrinkage rate of 5% or less at 150 ° C. When the dry heat shrinkage exceeds 15%, it is not always necessary to perform high-temperature heat treatment during spinning, so the oil agent according to the present invention is not necessarily used.

(Effects of the Invention) Since the polyester fiber of the present invention is provided with an oil agent having low friction under high contact pressure, good heat resistance, and good solubility for polyester oligomer, it is possible to spin at high speed and heat set at high temperature. In addition, it exhibits excellent heat resistance, scum resistance, and lubricity, and good spinning efficiency can be obtained. Further, when weaving the fibers with sizing, no spillage of glue occurs, and good weaving efficiency can be obtained.

(Example) Hereinafter, the present invention will be described in more detail with reference to Examples.

In the examples, heat resistance, white powder stains on a heat setting roller, oligomer scum resistance, raw yarn fluff, scratch resistance, glue film property, and glue removal property were evaluated by the following methods.

(1) Heat resistance During spinning, the state of smoke generated from the heat-setting roller heated to 220 ° C and the state of stains on the surface of the heat roller (heat deterioration of the adherent oil agent) are visually observed and judged according to the following criteria did.

Roller stain resistance Grade Low stain generation: ○ Medium: △ High: × Smoke resistance Grade Low smoke generation: ○ Medium: △ High: × (2) Oligomer scum resistance Spinning was started by the method shown in the example, and spinning was started 1 The generation state of oligomer scum adhering to the cold roller immediately after the heat setting roller heated to 220 ° C. after the day was visually observed and judged according to the following criteria.

Grade Oligomer scum Almost none: ○ Small to medium: △ Large: × (3) White powder stain As in (2) above, stains on the heat-setting roller heated to 220 ° C one day after the start of spinning, other than deterioration of the oil agent The degree of white powdery dirt was visually determined according to the following criteria.

Grade White powder dirt Almost none: ○ Small, Medium: △ Large: × (4) Raw yarn fluff: 160 original yarns are collected, and the number of fluffs (single yarn breaks) within 200,000 m is counted and integrated. From this, the number of fluffs per 10 ⁶ m was determined, and evaluated according to the following three grades.

Fluff number (Ke / 10 ⁶ m) Grade 0~0.2: ◎ 0.2~0.5: ○ 0.5~2.0: △ 2.0 or more: × (5) Scratch Resistance fibers and metal (F / M) and the fiber and the fiber (F / The scratch resistance of F) was evaluated according to the measuring methods shown in the following table.

Evaluation Criteria Evaluation of fluff Grade Grade Almost no fluff: ◎ Small fluff: ○ Large fluff: △ Thread breakage: × (6) Evaluation of glue film properties As a substitute evaluation for observing the properties of the glue film on the fibers when the fibers were pasted, the following model experiments were performed.

A casting solution was obtained by pouring a mixed aqueous solution of a polyvinyl alcohol and a polyacrylic acid ester as a main component and an oily agent at an effective component ratio of 5/1 onto a glass plate, followed by air drying and heat treatment. The film was sampled in a strip shape and a tensile test was conducted, and the following criteria were evaluated.

In comparison with a film sample obtained only from a sizing agent that is not mixed with an oil agent, a film having a film strength of 30% or more or an elongation of 250% or less was marked as "○", and a film outside this range was marked as "X".

(7) Evaluation of "paste removal" property As a substitute characteristic for the "paste removal" phenomenon in the actual weaving process, a part of the glue film on the yarn surface against friction acting in the axial direction of the sizing yarn Was evaluated by the frequency of peeling from the yarn surface.

Using a sizing agent mainly composed of polyvinyl alcohol and a polyacrylic acid ester, polyester fibers were sizing by a usual roller sizing method so that the target adhesion amount was 5.0% by weight, and a sizing yarn was obtained. Next, 20 pieces of this sizing thread are arranged at equal intervals, fixed terminals are installed so that both ends are not disturbed, and one end is fixed by a chuck 4 as shown in FIGS. / Apply a weight 6 to the book and apply tension to the whole sample through the pulley 5. Put it on the picture
1, 2 and 3 are reeds installed at intervals of 10 cm and a movable table 7
The movable base 7 can be reciprocated over a width of 5 cm in parallel with the yarn axis. The sample sizing yarn is set so as to have an opening angle of 108 ° in the central reed 2 as shown in FIG.

Then, the movable table 7 was reciprocated to the left and right, and after 10 reciprocations, the peeling state of the glue film in the rubbing portion of the reed and the yarn was carefully observed, and the ratio of the number of peeled samples to all 20 samples was calculated as follows. Expressed by grade.

In addition, the determination was made here by averaging the results of three times.

Percentage of peeled lines Grade less than 25%: ○ 25 to 50%: exceeds Δ 50%: × (8) Overall evaluation The following four levels were used.

Very good: ◎ Good: ○ Slightly insufficient: △ Not possible: × Example 1 Polyethylene terephthalate having an intrinsic viscosity of 1.00 was melt-discharged to form a 48 filament yarn. This yarn was applied through an oiling roller so that the oil agent emulsion shown in Table 1 was made into a pure oil agent content so as to be 0.5% by weight of the thread weight. After that, with a take-off roller, take off at 600 m / min. 9
After preheating at 0 ° C., heat setting at 220 ° C. while stretching 5.0 times between the take-up roller and the stretching heat setting roller, and then winding via an empty roller 250 d / 48 f, strength 8.0 g A drawn yarn having a dry content of 5% at 150 ° C./d was obtained.

The results of evaluation of the drawn yarn obtained at this time by the above-mentioned measuring method are summarized in Table 2.

As is clear from this result, the polyester fiber to which the oil agent in the range of the present invention is attached has excellent heat resistance and lubricity, and has excellent sizing properties in the weaving process, and has a remarkable effect on yarn forming and post-processability. Is obtained.

Example 2 In Example 1, it processed like Example 1 except having changed the adhesion amount of the oil agent used in Experiment No. 6. The results obtained at this time are summarized in Table-3.

[Brief description of drawings]

1 and 2 are schematic diagrams of the apparatus used for evaluating the glue removal characteristics, FIG. 1 is a side view, and FIG. 2 is a plan view.

Claims (2)

(57) [Claims] 1. The following (A),
The components (B) and (C) are contained as essential components, and the respective contents are the following (i) to (ii) with respect to the oil agent effective component.
A polyester fiber characterized in that 0.3 to 1.0% by weight of an oil agent satisfying the formula (i) is attached at the same time. Component (A) Aliphatic monohydric alcohol ester which is liquid at room temperature and has a molecular weight of 550 to 750 (B) Component Aromatic ester which is liquid at room temperature and is represented by the following formula [Wherein R ₁ and R ₂ are alkyl groups having 8 to 25 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, and n and m are integers of 1 or 2]. ] Component (C) An alkylene oxide adduct of triglyceride which is liquid at room temperature and has one or more hydroxyl groups in the molecule (i) W _A + W _B = 20 to 75 (ii) W _C = 2 to 15 (iii) W _A / W _B = 95 / 5-60 / 40 [where W _A , W _B and W _C are the contents (% by weight) of the components (A), (B), and (C) relative to the active ingredient of the oil agent, respectively] ) Is represented. ] 2. The oil agent according to claim 1, which contains the following components (D) and (E) in an amount of 1% by weight or more and 10% by weight or less of the following component (F) with respect to the active ingredient of the oil agent. Polyester fiber. (D) Component Alkyl Phosphate and / or Alkylene Oxide-Addition Alkyl Phosphate Salt with Alkylamine and / or Alkylene Oxide Adduct (E) Component Alkyl Phosphate Alkali Metal Salt (F) Component Glycol HOCH ₂ CH _{2 n} OH [where n = 1 to 20 is represented. ]