JP2006193854A - Biodegradable polyester fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a biodegradable polyester fiber hardly causing fluff at spinning (drawing) of the biodegradable polyester fiber, and exhibiting excellent stability when undergoing the processes of drawing or later. <P>SOLUTION: The biodegradable polyester fiber has 0.2-2.0 wt.% oil attached thereto. The oil contains 50-80 wt.% aliphatic ester compound, 1-10 wt.% reaction product of an alkylene oxide adduct of a glyceride having one or more hydroxy groups in the molecule with a dibasic acid component, and 1-10 wt.% partial phosphoric acid ester salt of an alkylene oxide adduct, and provides 0.2-0.35 coefficient of fiber-metal static friction, and 0.2-0.35 coefficient of fiber-fiber static friction. Preferably, the coefficient of fiber-metal dynamic friction is 0.25-0.4, and the biodegradable polyester is an aliphatic polyester. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a biodegradable polyester, and more particularly to a biodegradable polyester excellent in passage through intermediate processes such as twisting, weaving and knitting processes.

  Synthetic fibers such as polyester derived from petroleum are superior to other materials in terms of strength, cost, and productivity, and are now indispensable materials in society. However, on the other hand, environmental problems on a global scale that can be said to be the merit and merits of civilized society have been closed up, and while maintaining the above characteristics of synthetic fibers, they are decomposed by microorganisms in natural environments such as cotton and silk. Development of biodegradable polymers that are rendered harmless has been strongly desired. Particularly in Europe and the United States, fermentative decomposition by compost instead of incineration is becoming the mainstream as a method of treating organic waste, and it is considered that biodegradability at the compost level will be required for general-purpose synthetic fibers in the future. As such materials, aliphatic polyesters that consist of oxygen, hydrogen, and carbon as constituent atoms and decompose to produce only water and carbon dioxide have potentially low environmental impact biodegradability. Are known. In particular, microbially produced poly-hydroxybutyric acid esters and synthetic polymer poly-ε-caprolactone, polyethylene adipate, polyglycolic acid and poly-L-lactic acid have been developed as representative biodegradable polyesters. It has been commercialized. However, the yarn strength of many of these biodegradable polyester fibers is less than about half that of aromatic polyester fibers, which is unsuitable for practical use. Recently, high melting point polymers have been developed, and the yarn strength is aromatic. Nearly the same level as polyester fiber has been obtained, and even application to industrial materials has become possible.

  However, when biodegradable polyester passes through the twisting, weaving, knitting process, etc., it generates more fuzz and yarn than aromatic polyester such as polyethylene terephthalate, and the passability of the process tends to be poor. . As one of the causes, it is considered that the biodegradable polyester generally has a low melting point and thus tends to have high friction with the plate and guides. Furthermore, it is conceivable that the oil agent applied during spinning is likely to penetrate, and it is easy to induce fuzz and yarn breakage due to a decrease in strength due to polymer swelling.

  For the problem of these biodegradable polyesters, for example, Patent Document 1 uses an oil agent based on an ester or an ether ester as a smoothing agent, and sets the dynamic friction coefficient between the fiber and the metal within an appropriate range. Improvement of process passability in the process is achieved. Furthermore, Patent Document 2 uses an oil agent based on mineral oil and / or ester to optimize the dynamic friction coefficient between the fiber and the metal and the dynamic friction coefficient between the fiber and the fiber. The improvement of yarn breakage and fluff suppression is attempted.

  However, even if the dynamic friction between the fiber and the metal or the fiber and the fiber is made appropriate, the stretching speed becomes higher, the heat setting temperature becomes higher, etc. There is a problem that not only the processability of the fibers becomes poor, but also the quality of the woven fabric that is the final product is lowered.

JP 2003-20567 A JP 2004-27374 A

  The present invention has been made paying attention to the problems as described above, and the purpose thereof is less generation of fluff during the production of the biodegradable polyester fiber (during stretching), and excellent process-passing stability after stretching. Another object is to provide a biodegradable polyester fiber.

The biodegradable polyester fiber of the present invention is a biodegradable polyester fiber to which an oil agent is attached in an amount of 0.2 to 2.0% by weight, and the oil agent comprises the following components (a) to (c) (a). 50 to 80% by weight of component, 1 to 10% by weight of component (b), 1 to 10% by weight of component (c), and a fiber-metal static friction coefficient of 0.2 to 0.35, fiber-fiber The static friction coefficient is 0.2 to 0.35.
(A) Aliphatic ester compound (b) Reaction product of alkylene oxide adduct of glyceride having one or more hydroxyl groups in the molecule and a dibasic acid component (c) Partial phosphate ester salt of alkylene oxide adduct.

  Furthermore, the fiber-metal dynamic friction coefficient is preferably 0.25 to 0.4, and the biodegradable polyester is preferably an aliphatic polyester.

  According to the present invention, there is provided a biodegradable polyester fiber that is less likely to generate fluff during yarn production (during stretching) and has excellent process passage stability after stretching.

  The biodegradable polyester fiber of the present invention is not particularly limited as long as it is a polyester fiber that can be fermented and decomposed in soil, but more specifically, for example, polyhydroxybutyrate, polyglycolic acid, Polyhydroxyalkylates (PHA) such as lactic acid, polylactones (PL) such as polycaprolactone and polypivalolactone, polybutylene succinate (PBS), polyethylene succinate (PES) and polybutylene succinate and polyethylene succinate Polymers, polyethylene adipate, polybutylene adipate, polyhexane adipate, polydecane adipate, polyethylene sebacate, polybutylene sebacate, polyhexane sebacate, polydecane sebacate, and the like obtained from aliphatic diols and aliphatic dicarboxylic acids In addition to the polyester block and / or random copolymer having a component derived from a polyester polymerization raw material such as alkylene alkylate (PAA) of 70% by weight or more, and the polyester component, for example, aromatic polyester, polyether, polycarbonate, Examples include polyamides, polyurethanes, polyorganosiloxanes and the like that are 30% by weight or less of block or random copolymerization and / or mixtures thereof. Furthermore, the biodegradable polyester fiber is preferably an aliphatic polyester or a polylactic acid fiber.

  In addition to the above components, a small amount of a third component may be copolymerized in order to adjust the alkali weight loss rate or improve the adhesion at the polymer interface. As the third component, for example, 5-metal sulfoisophthalic acid, polyethylene glycol, polypropylene glycol, pentaerythritol, glycidyl ether having an alkylene oxide block, or the like can be used.

  In the present invention, the melting point of the biodegradable polymer as described above is preferably 120 ° C. or higher, more preferably 150 ° C. or higher, from the viewpoint of heat resistance. More preferably, it is 200 degreeC or more.

  The present invention is a fiber obtained by adhering 0.2 to 2.0% by weight of an oil agent to such a biodegradable fiber, and the oil agent is an aliphatic ester compound (a) component 50 to 80% by weight, molecule 1 to 10% by weight of the component (b), which is a reaction product of an alkylene oxide adduct of glyceride having one or more hydroxyl groups therein and a dibasic acid component, is a partial phosphate ester salt of an alkylene oxide adduct ( c) It is essential that the component is 1 to 10% by weight.

  By applying such an oil agent, for example, at the time of spinning, it is possible to obtain excellent process passability with very little fuzz and yarn breakage in the processes from spinning to weaving and knitting.

  Further, each oil agent component will be described. As the aliphatic ester compound (a) component, compounds such as fatty acid monoalkyl esters, aliphatic dicarboxylic acid dialkyl esters, mono- or multi-fatty acid esters of aliphatic polyhydric alcohols, and the like, molecular weight The thing of the range of 250-550 is preferable. When the molecular weight of the ester is less than 250, the smoothness of the biodegradable fiber obtained tends to decrease because it is easily volatilized by heat. On the other hand, if it exceeds 550, the smoothness of the resulting biodegradable fiber becomes insufficient, such being undesirable. Examples of preferably used aliphatic esters include fatty acid monoalkyl esters such as octyl octanoate, octyl stearate, isotridecyl laurate, isotridecyl oleate, lauryl oleate, and the like, and aliphatic dicarboxylic acid dialkyl esters. Examples thereof include diisooctyl adipate, and examples of mono- or multi-fatty acid esters of aliphatic polyhydric alcohols include trimethylolpropane trioctanoate. Of these, fatty acid monoalkyl esters are preferred. By using such component (a), it is possible to reduce the frictional resistance and suppress the generation of fluff due to scratching.

  Next, the reaction product as component (b) is a reaction product of an alkylene oxide adduct of glyceride having one or more hydroxyl groups in the molecule and a dibasic acid component, and if necessary, a dibasic acid component. And an ester compound obtained by reacting a monobasic acid component. Here, as the glyceride having one or more hydroxyl groups in the molecule, triglyceride is particularly preferable, and examples thereof include triglycerides such as ricinoleic acid and 1,2-hydroxystearic acid, and typical examples thereof include castor oil. Examples of the alkylene oxide added to the triglyceride include ethylene oxide, propylene oxide, and butylene oxide, and ethylene oxide is particularly preferable. The added mole number of alkylene oxide is 5 to 50 moles, preferably 10 to 30 moles. The addition method of alkylene oxide may be a conventional method, and when two or more types are added, they may be added randomly or in blocks.

  Next, examples of the dibasic acid component to be reacted with the alkylene oxide adduct include maleic acid, succinic acid, adipic acid, sebacic acid, and thiodipropionic acid. Moreover, as a monobasic acid component used together as a terminal blocker as needed, higher fatty acids, such as an oleic acid, a stearic acid, and behenic acid, can be mentioned as a preferable example. The molecular weight of the reaction product composed of the above-mentioned components is preferably about 3500 to 7000, and if it is too low, the oil film strengthening effect of the oil will be reduced, while if it is too high, not only will the viscosity increase and handling becomes difficult, but also the running friction of the yarn will be high. Thus, there is a tendency that fluff is likely to occur during yarn production and weaving.

  In the present invention, the content of the reaction product of component (b) in the oil must be 1 to 10% by weight, preferably 3 to 8% by weight. When the content is less than 1% by weight, the effect of reinforcing the oil film becomes insufficient, and during yarn production and weaving, the friction between fibers and fibers when they are scratched under high contact pressure increases and single yarn breakage occurs frequently. It is not preferable. On the other hand, if the amount exceeds 10% by weight, the static friction between the fibers is excessively reduced, the package winding shape becomes unstable and the unwinding property is deteriorated. Becomes larger and troubles such as thread breakage and single thread breakage occur frequently. In the present invention, by using such a component (b), it is possible to reduce the fiber-fiber static friction coefficient and prevent the generation of fluff due to abrasion between yarns during twisting or weaving.

Next, the partial phosphate ester salt of the alkylene oxide adduct as the component (c) will be described.
The component (c) is obtained by adding ethylene oxide or propylene oxide to alcohol, converting the terminal to phosphoric ester, neutralizing with alkali, and forming a salt. Examples of the alcohol include caprylyl alcohol having 8 to 18 carbon atoms, capryl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and branched alcohols thereof. A branched alcohol having good compatibility with silicone and mineral oil is preferable. Those obtained by adding 1 to 10 moles of ethylene oxide and / or propylene oxide to these alcohols are preferred, and the number of moles added is more preferably 2 to 8 moles having good compatibility with silicone and mineral oil. Examples of the alkali to be neutralized include alkali metals and amines. Examples of the alkali metal include sodium, potassium, and lithium. Examples of the amine include secondary and tertiary amines, and examples of the secondary amine include diethylamine, dipropylamine, dibutylamine, and dioctylamine. Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, and trioctylamine. Of these, amine salts are preferred. The amine salt can reduce the fiber-metal static friction coefficient, and even when used in a non-aqueous system, it is possible to obtain a uniform oil agent with good compatibility of the oil agent.

  The content ratio of the partial phosphate ester salt of the alkylene oxide adduct as the component (c) is 1 to 10% by weight based on the oil. If the content ratio is less than 1% by weight, the oil film strength between the metal and the yarn is inferior and tends to become fluff, and if the content ratio exceeds 10% by weight, it becomes difficult to prevent the occurrence of fluff due to reduced smoothness. By using such a component (c), it is possible to reduce the fiber-metal static friction coefficient and suppress the occurrence of fluff during yarn production (during stretching). The reason is not clear, but the partial phosphate ester salt of the alkylene oxide adduct that is the component (c) of the present invention is adsorbed to the drawing roller, the friction between the roller and the running yarn is reduced, and the oil agent layer on the fiber is destroyed. It is estimated that the yarn is protected.

  The biodegradable polyester fiber of the present invention is a biodegradable fiber to which an oil containing the essential components (a) to (c) described above is applied, and has a fiber-metal static friction coefficient of 0.2 to 0.00. It is important to make the range 35. Biodegradable fibers are generally lower in strength than polyester fibers, and the smoothness of the oil agent (fiber-metal dynamic friction coefficient) that imparts fluff and yarn breakage easily due to friction with guides and rollers during yarn drawing. ) Is important, but even if the smoothness is good, if the fiber-metal static friction coefficient is high, the stretchability becomes poor and it is difficult to suppress fluff. Although the reason is not clear according to our research, it has been found that fluff can be significantly improved by setting the fiber-metal static friction coefficient in the range of 0.2 to 0.35. This static friction coefficient can be lowered mainly by using the component (c).

Furthermore, in the present invention, it is essential that the fiber-fiber static friction coefficient is in the range of 0.2 to 0.35. By making such a range, the oil film between the fibers is reinforced, and during yarn twisting and weaving, the occurrence of single yarn breakage is prevented even under conditions where the fibers are scratched under high contact pressure, and fluff is less likely to occur Good process passability. This fiber-fiber static friction coefficient can be lowered mainly by using the component (b).
The fiber-metal dynamic friction coefficient is preferably in the range of 0.25 to 0.4.

  The oil agent used in the present invention comprises the above components (a) to (c) as main components, but other components such as esters, nonionic surfactants, anionics as necessary. Surfactants, antioxidants, compatibilizers, and stability improvers may be added as long as the object of the present invention is not impaired.

  In order to attach such an oil agent to the biodegradable fiber, an emulsion emulsified in water may be used, or the stock solution may be used as it is, and any method can be adopted. Among them, the method of using the undiluted solution as it is (straight type treatment) has an advantage that the emulsifier usually used in combination easily swells the biodegradable fiber and easily generates scum, but there is no need to use this emulsifier. It is preferable.

  Generally, any generally known means can be used to apply the oil agent to the biodegradable fiber. Among them, a method of applying a measured amount through an oiling nozzle that reduces resistance to the yarn is more preferable. This is the preferred method.

  The amount of the oil agent attached to the biodegradable fiber needs to be 0.2 to 2.0% by weight as an active ingredient with respect to the fiber. When the adhesion amount is less than 0.3% by weight, the smoothness and antistatic property are insufficient, and troubles such as fluff, yarn breakage, and scum are caused. On the other hand, even if it exceeds 3.0% by weight, the effect of suppressing the occurrence of fluff, yarn breakage, and scum is small, and on the contrary, excessive oil agent will contaminate the yarn guide and the like, causing a new problem. It is not industrially profitable.

  Such a biodegradable polyester fiber of the present invention has less fuzz generation during the production process such as yarn production and stretching, and has excellent process passage stability after stretching, and is widely used as a substitute for conventional synthetic fibers. It can be done.

  Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the measured value in an Example was measured with the following method.

(1) OPU measurement method Immediately after drying 3 g of drawn yarn composed of biodegradable fibers of 83 dtex / 36 filaments at 105 ° C. × 2 hours, the weight (A) is measured, and an aqueous cleaning solution mainly composed of sodium alkylbenzenesulfonate. Immerse in 300 cm ³ and apply ultrasonic waves at 40 ° C. for at least 10 minutes. The washing solution is discarded, washed with running water at 40 ° C. for 30 minutes, and then air-dried at room temperature. Thereafter, the weight (B) is measured immediately after drying at 105 ° C. for 2 hours.
OPU% = (A−B) / B × 100
OPU is calculated from the above equation.

(2) Fiber-metal dynamic friction coefficient Using a drawn yarn made of biodegradable fibers of 83 dtex / 36 filaments, a satin chrome pin having a diameter of 60 mm as a friction body at a running speed of 300 m / min with a fiber-metal running friction measuring machine (surface Using the roughness 6s), the friction body exit side tension (T ₂ ) was measured at a contact angle of 180 degrees and a friction body entry side tension of 10 g (T ₁ ). The fiber-metal dynamic friction coefficient (μ ₁ ) was calculated from the following equation regarding the friction of the belt running on the cylinder.
μ ₁ = 1 / π × ln (T ₂ / T ₁ )

(3) Fiber-metal static friction coefficient Using stretched yarn made of biodegradable fiber of 83 dtex / 36 filaments, using a fiber-metal running friction measuring machine, using a satin chrome pin (surface roughness 6s) with a diameter of 60 mm as a friction body. At a running speed of 1 cm / min at which a stick slip phenomenon occurs, a contact angle of 180 degrees, a friction body entry side tension of 30 g (T ₁ ) and a friction body exit side tension (T ₂ ) are measured, and a fiber-metal static friction coefficient ( μ ₂ ) was calculated by the following formula.
μ ₂ = 1 / π × ln (T ₂ / T ₁ )

(4) Fiber-Fiber Static Friction Coefficient Using a drawn yarn made of biodegradable fiber of 83 dtex / 36 filaments, using a satin chrome pin (surface roughness 6s) with a diameter of 60 mm as a friction body with a fiber-metal running friction measuring machine. At a running speed of 1 cm / min at which a stick-slip phenomenon occurs, a contact angle of 180 degrees, a friction body entry side tension of 30 g (T ₁ ), and a friction body exit side tension (T ₂ ) are measured. μ ₃ ) was calculated by the following formula.
μ ₃ = 1 / π × ln (T ₂ / T ₁ )

(5) Number of fluff The stretched yarn of biodegradable fiber 83 dtex / 36 filament was measured with a fluff tester to determine the number of fluff per million m.

[Examples 1 to 6]
A block copolymer (melting point: 230 ° C.) obtained by transesterifying polyethylene terephthalate and polycaprolactone was melted and discharged at 240 ° C. to form 16 filament yarns. After solidifying the yarn, 1.2% by weight of each oil agent shown in Table 1 is applied to the yarn weight through a measuring oiling nozzle, and then taken up through a take-up roller having a surface speed of 1000 m / min. Subsequently, the yarn was drawn 2.7 times between the take-up roller and the drawing roller to obtain a drawn yarn of 83 dtex / 36 filament. The strength of the drawn yarn was 2.1 g / dtex. The evaluation results are also shown in Table 1.

Claims (3)

A biodegradable polyester fiber to which 0.2 to 2.0% by weight of an oil agent is adhered, wherein the oil agent comprises the following components (a) to (c): (a) component of 50 to 80% by weight, (b 1) -10% by weight of component (c), 1-10% by weight of component (c), and a fiber-metal static friction coefficient of 0.2-0.35, and a fiber-fiber static friction coefficient of 0.2-0.35. A biodegradable polyester fiber characterized by being.
(A) Aliphatic ester compound (b) Reaction product of alkylene oxide adduct of glyceride having one or more hydroxyl groups in the molecule and a dibasic acid component (c) Partial phosphate ester salt of alkylene oxide adduct   The biodegradable polyester fiber according to claim 1, wherein the fiber-metal dynamic friction coefficient is 0.25 to 0.4.   The biodegradable polyester fiber according to claim 1, wherein the biodegradable polyester is an aliphatic polyester.