JP4149600B2 - Fiber made of copolymer polyethylene naphthalate - Google Patents

Description

【００４１】
【発明の効果】
本発明の共重合ポリエチレンナフタレートよりなる繊維は、高いヤング率を保持しつつ、優れた強伸度と結節強度とを有しており、タイヤコード、ドライヤーキャンバス、スクリーン紗等に好適に使用する事ができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyethylene naphthalate fiber , and more particularly to a copolymerized polyethylene naphthalate fiber having improved fatigue resistance while maintaining high Young's modulus and transparency.
[0002]
[Prior art]
Polyethylene naphthalate has excellent mechanical and chemical properties, and is particularly excellent in strength, Young's modulus, dimensional stability, hydrolysis resistance, and heat resistance, and is widely used as a textile product.
[0003]
However, since polyethylene naphthalate has a rigid molecular structure, its elongation and toughness are low. Therefore, its physical properties against fatigue, especially bending fatigue and friction fatigue, are extremely low. It has a problem that it is not suitable.
[0004]
In order to solve this problem, a method in which an aromatic diol alkylene oxide adduct is copolymerized with the polyethylene naphthalate (Japanese Patent Laid-Open No. 6-301147), and a method in which polyalkylene glycol is copolymerized with polyethylene naphthalate (Japanese Patent Laid-Open No. Various proposals such as No. 2-8216 and JP-A-8-34842 have been made. However, fibers obtained from polymers obtained by these methods have improved fatigue resistance, but have low compatibility between polyethylene naphthalate and the above-mentioned components, and the copolymerization amount, molecular weight, etc. of polyalkylene glycol to be copolymerized In some cases, the polymer becomes incompatible and potentially has the problem of reducing the fatigue resistance of the fiber.
[0005]
[Problems to be solved by the invention]
An object of the present invention, homopolymer of polyethylene naphthalate has, while maintaining high Young's modulus, is to provide a port triethylene naphthalate fibers improved fatigue resistance.
[0006]
[Means for Solving the Problems]
In view of the above prior art, the present inventors have intensively studied the copolymerization component of polyethylene naphthalate, and a copolymerized polyethylene naphthalate obtained by copolymerizing a specific aromatic diol alkylene oxide adduct solves the above problems. As a result, the present invention has been completed.
[0007]
That is, according to the present invention,
With naphthalenedicarboxylic acid as the main dicarboxylic acid component, ethylene glycol as the main glycol component, an aromatic diol alkylene oxide adduct component represented by the following structural formula as a copolymer component, based on the copolymer polyethylene naphthalate obtained, A fiber made of copolymerized polyethylene naphthalate obtained by copolymerization of 0.1 to 10% by weight can be provided.
[0008]
[Chemical 2]
_{H- (X 1) m-O} -R- (X 2) n-OH
(Wherein R represents a p-phenylene group, an m-phenylene group, a 4,4′-isopropylidenediphenylene group, a 4,4′-sulfonyldiphenylene group, X ₁ and X ₂ represent an oxyethylene group and / Or, it represents an oxyisopropylene group, and m and n are each an independent integer, and m + n = 20 to 60 .
[0009]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the main component of the copolymerized polyethylene naphthalate is polyethylene naphthalate in which the main dicarboxylic acid component is naphthalenedicarboxylic acid and the main glycol component is ethylene glycol.
[0010]
Here, “main” means that 80 mol% or more, preferably 90 mol% or more of the component is the component based on all components.
[0011]
Examples of naphthalenedicarboxylic acid include 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 1,5-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid is preferable.
[0012]
In the present invention, the polyethylene naphthalate described above occupies 0.1 to 10% by weight of the aromatic diol alkylene oxide adduct component represented by the structural formula as a copolymer component, based on the copolymer polyethylene naphthalate. Must be copolymerized.
[0013]
Here, m + n in the aromatic diol alkylene oxide adduct needs to be in the range of 20-60. When m + n is smaller than 20, the bending fatigue resistance of the fiber is not improved. On the other hand, when it exceeds 60, the obtained polymer becomes opaque and the bending fatigue resistance of the fiber also decreases. The range of m + n is preferably 25 to 55, more preferably 30 to 50.
[0014]
The aromatic diol alkylene oxide adduct of the present invention can be produced by adding ethylene oxide and propylene oxide to an aromatic diol in a nonpolar solvent. At this time, ethylene oxide and propylene oxide are used alone. Even if it uses, both may be used as a random copolymer or a block copolymer combining two types.
[0015]
The copolymerization amount of the aromatic diol alkylene oxide adduct component of the present invention needs to be 0.1 to 10% by weight. When the copolymerization amount is less than 0.1% by weight, the bending fatigue resistance of the fiber is not improved. On the other hand, if it exceeds 10% by weight, the resulting polymer becomes opaque, and the bending fatigue resistance of the fiber also decreases. The copolymerization amount of the aromatic diol alkylene oxide adduct component is preferably 0.5 to 7% by weight, more preferably 1 to 5% by weight.
[0016]
The copolymerized polyethylene naphthalate in the present invention may be copolymerized with other dicarboxylic acids as long as the effects of the present invention are not impaired. Other dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid, benzophenone dicarboxylic acid, phenyl indane dicarboxylic acid, 5-sulfoxyisophthalic acid metal salt, 5-sulfo Aromatic dicarboxylic acids such as phosphonium salts of xyisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, cyclohexanedicarboxylic acid, and aliphatic dicarboxylic acids such as decalin dicarboxylic acid, etc. It may be used either in combination or in combination of two or more.
[0017]
The copolymerized polyethylene naphthalate in the present invention may be copolymerized with other glycols as long as the effects of the present invention are not impaired. Other glycols include propylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, neopentylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, cyclohexanediol, cyclohexanedimethanol, etc. Aliphatic glycol, o-xylylene glycol, m-xylylene glycol, p-xylylene glycol, 1,4-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxyethoxy) benzene, 4,4′-bis (2-hydroxyethoxy) biphenyl, 4,4′-bis (2-hydroxyethoxyethoxy) biphenyl, 2,2-bis [4- (2-hydroxy) Ethoxy) phenyl] propane, 2,2-bis [4- (2-hydroxyethoxyethoxy) phenyl] propane, 1,3-bis (2-hydroxyethoxy) benzene, 1,3-bis (2-hydroxyethoxyethoxy) Benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxyethoxy) benzene, 4,4′-bis (2-hydroxyethoxy) diphenylsulfone, 4,4′-bis Aromatic glycols such as (2-hydroxyethoxyethoxy) diphenylsulfone, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane, resorcinol, catechol, dihydroxynaphthalene, dihydroxybiphenyl, diphenols such as dihydroxydiphenylsulfone, etc. Can be mentioned. These may be used alone or in combination of two or more.
[0018]
The copolymerized polyethylene naphthalate in the present invention may copolymerize a polycarboxylic acid or polyhydroxy compound having three or more functional groups such as trimellitic acid or pentaerythritol within a range not impairing the effects of the present invention.
[0019]
In the copolymerized polyethylene naphthalate in the present invention, additives such as a lubricant, a pigment, a dye, an antioxidant, a light stabilizer, a heat stabilizer, a light-shielding agent, and a matting agent can be blended as necessary.
[0020]
The copolymerized polyethylene naphthalate in the present invention is a dicarboxylic acid component containing the naphthalenedicarboxylic acid and / or its lower alkyl ester as a main component, a glycol component containing ethylene glycol as a main component, and the fragrance described above as a copolymer component. It can be produced by subjecting a group diol alkylene oxide adduct to a polycondensation reaction.
[0021]
Examples of the lower alkyl ester of naphthalenedicarboxylic acid include dimethyl ester, diethyl ester, dipropyl ester and the like. Preferably, it is dimethyl ester.
[0022]
Here, there is no particular limitation on the addition timing of the aromatic diol alkylene oxide adduct as a copolymerization component in the production of the copolymerized polyethylene naphthalate of the present invention, but when producing polyethylene naphthalate by a direct polymerization method. Is added after completion of the esterification reaction, and when polyethylene naphthalate is produced by the transesterification method, it may be added after completion of the transesterification reaction.
[0023]
The copolymerized polyethylene naphthalate of the present invention may be subjected to a solid phase polymerization reaction depending on the purpose and application to further increase the degree of polymerization.
[0024]
There is no particular limitation on the production of the copolymerized polyethylene naphthalate fiber of the present invention, and it can be produced by a conventionally known method for producing a normal polyester fiber. After spinning, a method of winding an undrawn yarn and drawing it separately , A method of continuously drawing an undrawn yarn without winding it up once, a method of omitting the drawing process by melt spinning at a spinning speed of 5000 m / min or more, and cooling the undrawn yarn in a coagulation bath after melt spinning After solidification, any of a heating medium, contact heating such as a heating roller, or a method of stretching with a non-contact heater can be employed. Further, during melt spinning, a hydrolysis inhibitor such as carbodiimide and a chain extender such as bisoxazoline may be added.
[0025]
Although there is no particular limitation on the single fiber fineness of the fiber made of the copolymerized polyethylene naphthalate of the present invention, the fiber made of the copolymerized polyethylene naphthalate of the present invention has high fatigue resistance while having a high Young's modulus. In addition, it is possible to form a thin fiber having a single fiber fineness of about 2 to 15 De, and for example, an extremely fine scrubbing brush or the like can be manufactured.
[0026]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto. In addition, each value in an Example was measured with the following method.
[0027]
(1) Intrinsic viscosity:
The measurement was performed at 35 ° C. in a mixed solvent of phenol / tetrachloroethane (weight ratio 6: 4).
(2) Diethylene glycol (hereinafter sometimes referred to as DEG) content:
The polymer was decomposed using hydrazine hydrate and quantified using gas chromatography (“263-70” type, manufactured by Hitachi, Ltd.).
(3) High elongation, nodule strength (fiber):
It measured based on the method of JISL1070 description.
(4) Young's modulus (fiber):
The apparent Young's modulus was calculated from the initial tensile resistance measured in accordance with the method described in JIS L1073.
(5) Haze:
After the pellets were dried at 180 ° C. for 3 hours, a plate having a thickness of 4 mm and a side of 10 cm was formed at a molding temperature of 310 ° C. and a mold temperature of 15 ° C. using an injection molding machine 100DM manufactured by Meiki Seisakusho. The color was measured with a turbidimeter Color & Color Difference Meter MODEL “1001DP” manufactured by Color Industries Co., Ltd.
[0028]
[Example 1]
After transesterification of 100 parts by weight of dimethyl naphthalene-2,6-dicarboxylate and 67 parts by weight of ethylene glycol using 0.03 parts by weight of manganese acetate tetrahydrate as a transesterification catalyst, Phosphate 0.023 parts by weight was added to substantially complete the transesterification reaction.
Subsequently, 0.024 parts by weight of antimony trioxide and 2 parts by weight of adduct of 30 moles of bisphenol A ethylene oxide (m + n = 30) were added, followed by a polycondensation reaction in a conventional manner under high temperature and high vacuum, and an intrinsic viscosity of 0 A .64 dl / g copolymerized polyethylene naphthalate pellet was obtained.
This modified polyethylene naphthalate pellet was dried at 180 ° C. for 3 hours, melt-spun at 310 ° C. using a die having a pore diameter of 0.27 mm and a hole number of 24 holes, and taken up at 400 m / min.
The obtained undrawn yarn was stretched to 65% of the maximum draw ratio on a supply roller heated to 150 ° C., and then subjected to constant length heat treatment on a hot plate heated to 240 ° C., and 75 De / A 24 fil drawn yarn was obtained. The properties of the obtained fiber are shown in Table 1.
[0029]
[Example 2]
In Example 1, the same operation was performed except that the charged amount of bisphenol A ethylene oxide 30 mol adduct was changed to 4 parts by weight to obtain a drawn yarn. The properties of the obtained fiber are shown in Table 1.
[0030]
[Example 3]
In Example 1, the same operation was carried out except that a bisphenol A propylene oxide 23 mol adduct (m + n = 23) was used instead of the bisphenol A ethylene oxide 30 mol adduct to obtain a drawn yarn. The properties of the obtained fiber are shown in Table 1.
[0031]
[Example 4]
A stretched yarn was obtained in the same manner as in Example 1 except that 4,4′-dihydroxydiphenylsulfone ethylene oxide 30 mol adduct (m + n = 30) was used instead of the bisphenol A ethylene oxide 30 mol adduct. The properties of the obtained fiber are shown in Table 1.
[0032]
[Example 5]
In Example 1, instead of the 30 mol adduct of bisphenol A ethylene oxide, a similar operation was performed except that a 30 mol adduct of hydroquinone ethylene oxide (m + n = 30) was used to obtain a drawn yarn. The properties of the obtained fiber are shown in Table 1.
[0033]
[Example 6]
88.5 parts by weight of naphthalene-2,6-dicarboxylic acid and 30 parts by weight of ethylene glycol were slurried at room temperature, charged into an autoclave equipped with a stirrer, and subjected to esterification at 270 ° C. under a pressure of 3 kg / cm ² .
Subsequently, 0.024 parts by weight of antimony trioxide and 2 parts by weight of adduct of 30 moles of bisphenol A ethylene oxide (m + n = 30) were added, followed by a polycondensation reaction in a conventional manner under high temperature and high vacuum, and an intrinsic viscosity of 0 0.63 dl / g copolymerized polyethylene naphthalate pellets were obtained.
The obtained copolymer polyethylene naphthalate pellets were subjected to the same operation as in Example 1 to obtain drawn yarn. The properties of the obtained fiber are shown in Table 1.
[0034]
[Comparative Example 1]
In Example 1, a 2,6-polyethylene naphthalate homopolymer was produced in the same manner as in Example 1 except that 30 mol of bisphenol A ethylene oxide adduct was not added, and the obtained polymer was used in the same manner as in Example 1. Thus, a drawn yarn was obtained. The properties of the obtained fiber are shown in Table 1, and the obtained drawn yarn had insufficient knot strength.
[0035]
[Comparative Example 2]
In Example 1, the same operation was performed except that the charged amount of the 30 mol adduct of bisphenol A ethylene oxide was changed to 12 parts by weight to obtain a drawn yarn. The properties of the obtained fiber and film are shown in Table 1. The obtained drawn yarn has insufficient knot strength and is also opaque in haze evaluation.
[0036]
[Comparative Example 3]
In Example 1, a drawn yarn was obtained in the same manner as in Example 1, except that a bisphenol A ethylene oxide 15 mol adduct (m + n = 15) was used instead of the bisphenol A ethylene oxide 30 mol adduct. The properties of the obtained fiber are shown in Table 1, and the obtained drawn yarn had insufficient knot strength.
[0037]
[Comparative Example 4]
In Example 1, a drawn yarn was obtained in the same manner as in Example 1 except that polyethylene glycol (molecular weight 1500) was used instead of the bisphenol A ethylene oxide 30 mol adduct. The properties of the obtained fiber are shown in Table 1, and the obtained drawn yarn had insufficient knot strength.
[0038]
[Comparative Example 5]
In Example 1, a drawn yarn was obtained in the same manner as in Example 1 except that polyethylene glycol (molecular weight 3000) was used instead of the 30 mol adduct of bisphenol A ethylene oxide. The properties of the obtained fiber are shown in Table 1, and the obtained drawn yarn had insufficient knot strength.
[0039]
[Comparative Example 6]
In Example 1, the same operation was performed except that the bisphenol A ethylene oxide 7 mol adduct (m + n = 7) was used instead of the bisphenol A ethylene oxide 30 mol adduct to obtain a drawn yarn. The properties of the obtained fiber are shown in Table 1, and the obtained drawn yarn had insufficient knot strength.
[0040]
[Table 1]

[0041]
【The invention's effect】
The fiber made of the copolymerized polyethylene naphthalate of the present invention has excellent high elongation and knot strength while maintaining a high Young's modulus, and is suitably used for tire cords, dryer canvas, screen wrinkles and the like. I can do things.

Claims (1)

Naphthalenedicarboxylic acid as a main dicarboxylic acid component, ethylene glycol as a main glycol component, an aromatic diol alkylene oxide adduct component represented by the following structural formula as a copolymer component, based on the copolymer polyethylene naphthalate obtained, A fiber made of copolymerized polyethylene naphthalate, 0.1 to 10% by weight copolymerized.
[Chemical 1]
_{H- (X 1) m-O} -R- (X 2) n-OH
(In the formula, R represents p-phenylene group, m-phenylene group, 4,4′-isopropylidenediphenylene group, 4,4′-sulfonyldiphenylene group, X ₁ and X ₂ represent oxyethylene group and / or Or, it represents an oxyisopropylene group, and m and n are each an independent integer, and m + n = 20 to 60 .