JP4357312B2 - Hydrolysis resistant polyester fiber - Google Patents

Hydrolysis resistant polyester fiber Download PDF

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JP4357312B2
JP4357312B2 JP2004030870A JP2004030870A JP4357312B2 JP 4357312 B2 JP4357312 B2 JP 4357312B2 JP 2004030870 A JP2004030870 A JP 2004030870A JP 2004030870 A JP2004030870 A JP 2004030870A JP 4357312 B2 JP4357312 B2 JP 4357312B2
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polycarbonate
polyester
fiber
polyester fiber
spinning
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JP2005220489A (en
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隆雄 大河内
隆司 橋本
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日本エステル株式会社
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Description

  The present invention relates to a polyester fiber excellent in hydrolysis resistance with little deterioration of strength even when various treatments such as dyeing, alkali weight reduction, and steam treatment are repeated at high temperatures.

  Polyester fibers are widely used not only for clothing but also for industrial use because of their excellent properties and low cost.

  However, polyester fibers are known to be easily hydrolyzed, and have a drawback that they are significantly decomposed under high temperature and high humidity conditions in the presence of hot water. Accordingly, various proposals have been made to improve the hydrolysis resistance of polyester fibers and to enable the use of polyester fibers under such conditions. For example, Patent Documents 1 to 3 describe a method of adding a carbodiimide compound to polyester.

  However, when such a carbodiimide compound is used, this compound causes coloring of the polyester fiber, and it is difficult to obtain a polyester fiber of good quality and high whiteness. Moreover, since these compounds are expensive, they have caused an increase in production costs.

Patent Document 4 describes a polyester having a carboxyl end group capped by adding polycarbonate and a fiber made of this polyester. However, the present invention is not intended to obtain a polyester having a very low carboxyl end group content, but requires a certain amount of free carboxyl end groups so as to have rubber adhesive strength for use in tire cords and the like. It is. For this reason, it was not a fiber having a sufficiently low terminal carboxyl group concentration, and the amount of polycarbonate added was also small.
Japanese Patent Laid-Open No. 6-341017 Japanese Unexamined Patent Publication No. 7-216647 Japanese Patent Laid-Open No. 10-102321 JP-A-4-68327

  The present invention provides a polyester fiber that solves the above-mentioned problems, is excellent in quality, can be obtained at low cost, has a low terminal carboxyl group concentration, and is excellent in hydrolysis resistance. This is a major issue.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention comprises a polyester resin composition comprising 70 to 97% by weight of polyester and 3 to 30% by weight of polycarbonate after polymerization , the main repeating unit being ethylene terephthalate, and having a terminal carboxyl group concentration of 25 eq / t or less , wet A gist of the hydrolysis-resistant polyester fiber is characterized in that the strength retention after heat treatment is 80% or more .

  Since the polyester fiber of the present invention contains an appropriate amount of polycarbonate, the terminal carboxyl group concentration can be reduced at low cost, the hydrolysis resistance can be improved, and the dyeability can also be improved. be able to. Accordingly, products such as fabrics using the polyester fiber of the present invention are required to have high resistance to hydrolysis and little degradation even when various treatments such as dyeing, alkali weight loss, and steam are repeated at high temperatures. It becomes possible to use suitably for a use.

Hereinafter, the present invention will be described in detail.
The polyester resin composition constituting the fiber of the present invention comprises 70 to 97% by mass of polyethylene terephthalate (PET) and 3 to 30% by mass of polycarbonate. When the content of the polycarbonate is less than 3% by mass, the effect of lowering the terminal carboxyl group concentration is small, and sufficient wet heat resistance performance cannot be obtained. On the other hand, if the polycarbonate content exceeds 30% by mass, the melt viscosity of the polyester resin composition becomes high, spinning becomes difficult, and even if it is obtained, the dyeing quality is inferior.

  The polycarbonate used in the present invention is an aromatic dihydroxy compound such as 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy). Phenyl) ethane and the like.

  In order to obtain the polycarbonate used in the present invention as described above, a carbonate precursor such as bisphenol and phosgene corresponding to a conventional acid acceptor or molecular weight regulator in a solvent such as methylene chloride is usually used. (Interfacial polymerization method) or a transesterification reaction (melt polymerization method) between the corresponding bisphenol and a carbonate precursor such as diphenyl carbonate.

  Moreover, although PET which comprises the fiber of this invention is not specifically limited, It can manufacture by conventionally well-known methods, such as a transesterification method and a direct polymerization method. The PET may contain a copolymerized ester as long as the effects of the present invention are not impaired. Representative examples of copolymerized esters include aromatic dicarboxylic acids such as 3,3′-diphenyldicarboxylic acid, aliphatic dicarboxylic acids such as succinic acid, diethylene glycol, 1,4-butanediol, and 1,4-cyclohexanediol. Aliphatic, alicyclic diol, P-hydroxybenzoic acid and the like.

  And in order to contain a polycarbonate in the polyester resin composition which comprises the fiber of this invention, it is preferable to mix PET and a polycarbonate in a molten state. The mixing method is as follows: 1. Method of mixing polycarbonate at the end of polymerization of PET, 2. Method of mixing PET and polycarbonate at the tip stage during spinning, 3. Nozzle of PET and polycarbonate melted and extruded separately during spinning. Examples of the method include kneading in a pack. Since PET and polycarbonate may react and foam during melt mixing, the method of defoaming and kneading the polycarbonate while reducing the pressure in the method 1 is preferable.

  Moreover, within the range which does not impair the effect of this invention, antioxidants, such as a hindered phenol type compound, other pigments, an additive, etc. may be mix | blended in the polyester resin composition.

  Furthermore, the polyester fiber of the present invention needs to have a terminal carboxyl group concentration of 25 eq / t or less. When the terminal carboxyl group concentration exceeds 25 eq / t, the hydrolysis resistance of the polyester fiber is greatly deteriorated. For this reason, the terminal carboxyl group concentration of the polyester fiber of the present invention is preferably 10 eq / t or less, and more preferably 5 eq / t or less.

  Moreover, since the polyester fiber of the present invention hardly contains a decrease in yarn quality even when 3 to 30% by mass of polycarbonate is contained in the polyester resin composition, the strength and elongation should be appropriately selected according to the application. Can do. When various treatments are repeated and used at high temperatures, the strength is preferably 3.0 cN / dtex or more, and more preferably 3.5 cN / dtex or more.

  The strength and elongation are measured in accordance with JIS L-1013, using a tensile tester AG-100G manufactured by Shimadzu Corporation, with a grip interval of 500 mm, a tensile speed of 500 mm / min, and a value when the yarn is cut. .

  Furthermore, the polyester fiber of the present invention preferably has a strength retention after wet heat treatment of 80% or more, and more preferably 85% or more, as a characteristic value excellent in wet heat resistance. The strength retention is the strength of the fiber A and the fiber (fiber B) taken out from the tube knitted fabric after the polyester fiber (fiber A) is subjected to pressure treatment at 135 ° C. for 16 hours. Is measured by the JIS method described above, and the strength retention is calculated from the value in the following equation.

Strength retention (%) = (strength of fiber B / strength of fiber A) × 100
The polyester fiber of the present invention may be a multifilament or a monofilament, and may be used as a long fiber or a short fiber. Further, the cross-sectional shape is not limited, and the cross-sectional shape may be not only a round cross-section but also a polygonal shape such as a square or a triangle or a hollow portion.

  Next, the manufacturing method of the polyester fiber of this invention is demonstrated. As described above, it is preferable to carry out melt spinning by supplying the polymer obtained by defoaming the polycarbonate while reducing the pressure at the end of the polymerization of PET and kneading the mixture into a polyester resin composition to a conventional spinning device. At this time, the POY method of winding up as a semi-undrawn yarn by high-speed spinning of 2000 m / min or more, or melt spinning by high-speed spinning of 2000 m / min or more, or low-speed spinning of less than 2000 m / min, and the wound yarn Any of a method of drawing and heat-treating and a spinning drawing method of drawing continuously without winding may be adopted.

Next, the present invention will be described more specifically with reference to examples. In addition, measurement and evaluation of various values in the examples were performed as follows.
(1) Intrinsic viscosity A mixture of phenol and ethane tetrachloride in a mass ratio of 1/1 was used as a solvent and measured at 20 ° C.
(2) Terminal carboxyl group concentration 150 mg of the obtained polyester fiber was finely cut and dissolved in 10 ml of benzyl alcohol, 10 ml of chloroform was added, and titrated with a 1/10 normal potassium hydroxide benzyl alcohol solution. It was calculated from the difference in the titration amount.
(3) Strength and elongation Measured by the above method.
(4) Strength retention rate Measured by the above method.
(5) Dyeing spots The cylindrical knitted fabric obtained in the measurement of (4) was dyed, the dyeing spots were judged visually, and evaluated in three stages.
○: Good △: Slightly uneven ×: Large occurrence of spots Dyeing condition is 2.0% omf bath ratio of Terasil Nevy Blue SGL (Bayer dye yarn)
It dye | stained by the conventional method for 60 minutes at 99 degreeC using the dyeing liquid of 1:50.

Example 1
Ethylene terephthalate is polycondensed by a conventional method to obtain PET with an intrinsic viscosity of 0.64, and then polycarbonate ("Caliber 301-30" manufactured by Sumitomo Dow) is added to 5 mass% of the total amount, and the pressure is reduced again. The mixture was melt kneaded while defoaming. This polyester had an intrinsic viscosity of 0.66 and was cut into chips by a conventional method. Next, this chip was dried by a conventional method, supplied to an extruder at 295 ° C., and melt spinning was performed from a spinning device. The spinneret has 48 spinning holes with a hole diameter of 0.25 mm. The melted and spun yarn is cooled by an air flow and passed through an oiling device, and an oil agent is applied so that the amount of adhesion is 0.5 mass%. Granted. Subsequently, after converging by converging with a converging guide, it was taken up with a roller having a spinning speed of 3500 m / min and wound up with a winder.
The obtained fiber was 255 dtex / 48f, and there was no defect due to fluff and single yarn breakage. Next, this fiber was drawn at a speed of 700 m / min using a normal drawing device to obtain a fiber of 167 dtex / 48f.

Examples 2-3 and Comparative Examples 1-2
Except having changed the addition amount of polycarbonate into the value of Table 1, it carried out similarly to Example 1 and obtained the polyester fiber.

Example 4
Example 1 except that PET and polycarbonate having an intrinsic viscosity of 0.64 were mixed and melt-kneaded so as to have a mass ratio (PET / polycarbonate) of 95/5 at the tip stage, and spinning was performed from a single-hole spinneret. In the same manner as above, a polyester fiber was obtained.

Example 5
PET with an intrinsic viscosity of 0.64 is supplied to Extruder A, Polycarbonate is supplied to Extruder B, and the mass ratio (PET / Polycarbonate) is 95/5. A polyester fiber was obtained in the same manner as in Example 1 except that spinning was performed from the above spinneret.

Comparative Example 3
A polyester fiber was obtained in the same manner as in Example 4 except that the mass ratio (PET / polycarbonate) at the tip stage was 50/50.

Comparative Example 4
A polyester fiber was obtained in the same manner as in Example 5 except that the mass ratio (PET / polycarbonate) was 50/50.

  Table 1 shows the evaluation results of the strength, elongation, terminal carboxyl group concentration, wet heat resistance and dyeing spots of the polyester fibers obtained in Examples 1 to 5 and Comparative Examples 1 to 4.

As is clear from Table 1, since the polyester fibers of Examples 1 to 5 contained an appropriate amount of polycarbonate, the terminal carboxyl group concentration was low, the strength retention was high, and the heat and moisture resistance was excellent. Further, the strength and elongation were values with no problem, and the dyeability was excellent.

  On the other hand, since the polyester fiber of Comparative Example 1 had a low polycarbonate content, the terminal carboxyl group concentration was high, the strength retention was low, and the heat and moisture resistance was poor. Since the polyester fiber of Comparative Example 2 had a large amount of polycarbonate added, the spinnability was poor and dyeing spots were also generated. Since the polyester fibers of Comparative Examples 3 to 4 contained too much polycarbonate, foaming occurred during spinning and spinning could not be performed.

Claims (1)

  1. It consists of a polyester resin composition of 70 to 97% by weight of polyester and 3 to 30% by weight of polycarbonate after polymerization, the main repeating unit being ethylene terephthalate, and having a terminal carboxyl group concentration of 25 eq / t or less , strength retention after wet heat treatment Is a hydrolysis-resistant polyester fiber, characterized in that it is 80% or more .
JP2004030870A 2004-02-06 2004-02-06 Hydrolysis resistant polyester fiber Active JP4357312B2 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7849955B2 (en) 2008-02-05 2010-12-14 Crown Equipment Corporation Materials handling vehicle having a steer system including a tactile feedback device

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007150084A (en) * 2005-11-29 2007-06-14 Dainippon Printing Co Ltd Solar cell module, rear face protection sheet therefor and rear face lamination therefor

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7849955B2 (en) 2008-02-05 2010-12-14 Crown Equipment Corporation Materials handling vehicle having a steer system including a tactile feedback device
US7980352B2 (en) 2008-02-05 2011-07-19 Crown Equipment Corporation Materials handling vehicle having a steer system including a tactile feedback device
US8172033B2 (en) 2008-02-05 2012-05-08 Crown Equipment Corporation Materials handling vehicle with a module capable of changing a steerable wheel to control handle position ratio
US8412431B2 (en) 2008-02-05 2013-04-02 Crown Equipment Corporation Materials handling vehicle having a control apparatus for determining an acceleration value
US8718890B2 (en) 2008-02-05 2014-05-06 Crown Equipment Corporation Materials handling vehicle having a control apparatus for determining an acceleration value
US9421963B2 (en) 2008-02-05 2016-08-23 Crown Equipment Corporation Materials handling vehicle having a control apparatus for determining an acceleration value

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