JP2009185409A - Method for producing dope-dyed polytrimethylene terephthalate-based polyester fiber - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a dope-dyed polytrimethylene terephthalate-based polyester fiber suitable for a trim material for a vehicle in high quality in good yield. <P>SOLUTION: The method for producing the dope-dyed polytrimethylene terephthalate-based polyester fiber having ≥1.5 dtex fineness includes carrying out the melt-spinning by mixing a polybutylene terephthalate composition containing a pigment such as a chromatic color pigment and a black pigment with a polytrimethylene terephthalate. The polybutylene terephthalate composition containing 10-60 wt.% of the pigment based on the polybutylene terephthalate having 0.75-1.30 dL/g intrinsic viscosity is used. The polybutylene terephthalate composition is mixed so as to be 0.5-8.0 wt.% based on the total weight of the polytrimethylene terephthalate having 0.80-1.40 dL/g intrinsic viscosity and the polybutylene terephthalate composition, and the resultant mixture is melt-spun at ≤1,200 m/min spinning speed. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing an original polytrimethylene terephthalate-based polyester fiber suitable for vehicle interior materials, carpet use, and the like.

  Polytrimethylene terephthalate-based polyester fibers maintain the excellent dimensional stability, light resistance, low moisture absorption, and heat setting properties that are inherent to polyester, and are excellent in low elastic modulus, elastic recovery rate, and easy dyeability. With its characteristics, polytrimethylene terephthalate-based polyester fiber manufacturing technologies are being studied from various angles with the aim of putting it into practical use for stuffed cotton, non-woven fabrics and spun yarn fabrics.

By the way, polytrimethylene terephthalate-based polyester fibers are often dyed to the necessary color according to their use when used for nonwoven fabrics and spun yarns. There is a growing need for polyester fiber.
As a method for producing an original polytrimethylene terephthalate-based polyester fiber, a resin containing a high concentration of a chromatic pigment or a black pigment is kneaded with a molten resin substantially composed of polytrimethylene terephthalate to obtain a fiber. The method is common.

For example, as a research example on the production technology of an original polytrimethylene terephthalate-based polyester fiber, Patent Document 1 (Japanese Patent Laid-Open No. 2002-348447) discloses a master batch made of polytrimethylene terephthalate, which defines the number of carboxyl group terminals. There is a method for producing an original polytrimethylene terephthalate-based polyester fiber used. According to this method, by reducing the number of carboxyl groups, a decrease in the molecular weight of the masterbatch can be suppressed, and as a result, an original polytrimethylene terephthalate-based polyester fiber having a conventional high elongation can be produced.
However, when producing a masterbatch for coloring polytrimethylene terephthalate, there is a problem that toxic acrolein gas is generated by heating and melting of polytrimethylene terephthalate. In order to prevent release to the environment, there is a problem that it is necessary to install a large-scale facility for making the heated and melted part a closed system, sucking the generated acrolein gas, and performing incineration.

Patent Document 2 (Japanese Patent Application Laid-Open No. 2003-89926) discloses a black original having excellent light-shielding properties by mixing and spinning a modified polyethylene terephthalate resin containing carbon black and a polytrimethylene terephthalate resin not containing carbon black. Invented polytrimethylene terephthalate polyester fiber. This technology uses a method of kneading different types of resins, and has good light-shielding properties and lightness. Originally, black trimmed polytrimethylene terephthalate with high elongation and elastic recovery rate inherent in polytrimethylene terephthalate polyester. It is a manufacturing method of a polyester fiber.
However, polyethylene terephthalate and polytrimethylene terephthalate have greatly different melting points and melt viscosities, and tend to cause yarn breakage and yarn defects in melt spinning, and the range of spinning conditions that can be adopted for commercial production is narrow. There's a problem.
JP 2002-348447 A JP 2003-89926 A

  The present invention uses a coloring masterbatch that does not require a special device such as acrolein suction in the production of a coloring masterbatch for obtaining an original polytrimethylene terephthalate-based polyester fiber. Efficiently provide original polytrimethylene terephthalate-based polyester fiber containing practical chromatic or black pigment suitable for automotive interior materials, carpets, etc. There is to do.

The present invention relates to a method for producing an original polytrimethylene terephthalate-based polyester fiber having a fineness of 1.5 dtex or more, wherein a polybutylene terephthalate composition containing a pigment and polytrimethylene terephthalate are mixed and melt-spun. For polybutylene terephthalate having a 0.75 to 1.30 dL / g (measured at 35 ° C. in a mixed solvent of 40% by weight of 1,1,2,2-tetrachloroethane and 60% by weight of phenol) Polytrimethylene terephthalate having a specific viscosity (measured in an orthochlorophenol solution at 35 ° C.) of 0.80 to 1.40 dL / g using a polybutylene terephthalate composition containing 1 to 60% by weight of the pigment and the polybutylene 0.1% of the polybutylene terephthalate composition relative to the total weight of the terephthalate composition. 8.0 were mixed so that the weight% to a method for producing a dyed polytrimethylene terephthalate polyester fiber characterized by melt-spinning under the following spinning speed 1,200m / min.
Here, the pigment is preferably a chromatic pigment or a black pigment.

  According to the present invention, in the production of a coloring masterbatch for obtaining an original polytrimethylene terephthalate-based polyester fiber, a coloring masterbatch that does not require a special device such as acrolein suction is used, and the color tone is excellent. Polytrimethylene terephthalate-based polyester fiber that contains practical chromatic or black pigment suitable for automotive interior materials, carpets, etc. It can be provided efficiently.

<Polybutylene terephthalate composition>
The polybutylene terephthalate composition used in the present invention is a composition containing a pigment, preferably a chromatic pigment or a black pigment, in polybutylene terephthalate.

Polybutylene terephthalate:
The polybutylene terephthalate (PBT) used in the polybutylene terephthalate composition which is the masterbatch of the present invention has a smaller physical property difference such as melting point and melt viscosity than the polytrimethylene terephthalate (PTT), and has a problem at the time of melting. Polybutylene terephthalate in which the main repeating unit is butylene terephthalate without generation of any cracked gas. Other polyesters, such as polyethylene terephthalate, are not preferred because they differ greatly in physical properties (melting point, melt viscosity), etc. from polytrithymethylene terephthalate, and blending into polytrimethylene terephthalate significantly reduces the physical properties of the resulting fiber. .

  Polybutylene terephthalate is a polyester obtained by polycondensation of terephthalic acid and 1,4-butanediol. Such polybutylene terephthalate may be copolymerized with an acid component and / or a glycol component within a range that does not substantially lose rigidity, toughness and moldability.

  Here, examples of the copolymerizable acid component include dicarboxylic acids other than terephthalic acid, such as isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenylethercarboxylic acid, diphenoxyethane. Examples thereof include dicarboxylic acid, diphenyl ketone dicarboxylic acid, diphenyl sulfone dicarboxylic acid, succinic acid, adipic acid, sebacic acid, cyclohexane dicarboxylic acid, tetralin dicarboxylic acid, decalin dicarboxylic acid, trimellitic acid, and pyromellitic acid. In these dicarboxylic acids, the carboxyl group may be esterified with a lower alcohol such as methanol or ethanol.

Examples of the copolymerizable glycol component include glycols other than 1,4-butanediol, such as 1,6-hexanediol, 1,5-hexanediol, 1,4-hexanediol, and 1,3-hexanediol. 2,5-hexanediol, 2,4-hexanediol, cyclohexanedimethanol, ethylene glycol, polyethylene glycol, 1,3-propanediol, 1,2-propanediol, 2-methyl-1,4-butanediol, 2-methyl-2,4-butanediol, 1,3-butanediol, polytetramethylene glycol, 1,5-pentanediol, 1,4-pentanediol, 1,3-pentanediol, 2,4-pentanediol , Neopentyl glycol, tricyclodecane dimethylol, xylylene Call, bisphenol A, bisphenol B, bis-hydroxyethoxy bisphenol A, glycerol, trimethylolpropane, pentaerythritol and the like.
As the copolymer component, an acid component or a glycol component may be used alone, or an acid component and a glycol component may be used in combination, and two or more kinds of acid components and / or glycol components may be used.

  Polybutylene terephthalate is produced by a known method. That is, after the esterification or transesterification reaction, a polycondensation reaction is performed under high vacuum. If necessary, such PBT may be further subjected to solid phase polymerization.

(Intrinsic viscosity of PBT)
The intrinsic viscosity of the polybutylene terephthalate (measured at 35 ° C. in a mixed solvent of 40% by weight of 1,1,2,2-tetrachloroethane and 60% by weight of phenol) is 0.75 to 1.30 dL / g, Preferably, it is in the range of 0.80 to 1.20 dL / g, and when it is less than 0.75 dL / g, the polymerization degree of the polybutylene terephthalate composition (masterbatch) obtained from this, and the polytrimethylene terephthalate-based polyester There is a problem that the mechanical properties such as the strength of the resulting fiber are lowered. On the other hand, when it exceeds 1.30 dL / g, the dispersibility of the pigment deteriorates, which is not preferable.
In addition, if the intrinsic viscosity of polybutylene terephthalate is out of the range of 0.75 dL / g to 1.30 dL / g, the difference in melt viscosity from polytrimethylene terephthalate is too large, resulting in non-uniform dispersion of the pigment and yarn breakage, etc. This is not preferable because it induces

Pigment:
The pigment used in the present invention is not particularly limited, but is preferably a chromatic pigment or a black pigment.
As used herein, the term “pigment” is defined as the first page of the “Pigment Handbook” (published by the Japan Pigment Technical Association, published by Seibundo Shinko Co., Ltd.). It is an organic compound that is mixed with a colorant to give a beautiful color to a coating film or molded product. On the other hand, colored powders used for clothing and the like are called dyes and are generally dissolved in water or a solvent and are distinguished from pigments. A chromatic color pigment is a pigment showing a color such as yellow, orange, red, blue, purple, green, fluorescent color, metallic luster and the like. Those showing fluorescent color are also called fluorescent pigments, and those showing metallic luster are called metal powder pigments, but here they are included in chromatic pigments.

  The pigment used in the present invention is not particularly limited as long as it is a chromatic pigment or a black pigment, and for example, those shown in Chapter 2 of the above-mentioned document “Pigment Handbook” can be used. For example, for chromatic pigments, titanium yellow, yellow iron oxide (Bengara), red iron oxide, ultramarine, bitumen, cobalt blue, cobalt purple, aluminum powder, copper powder, silver powder, gold powder, zinc dust, naphthol yellow, hansa yellow, pigment yellow , Benzine Nero, Permanent Yellow, Vulcan Fast Yellow, Tartra Gin Lake, Anthra Pyrimidine Yellow, Vulcan Fast Orange, Indanthrene Brilliant Orange, Perinono Range, Permanent Red, Para Red, First Scar Red, Resor Red, Bordeaux, Alizarin Lake, Permanent red, first violet, copper phthalocyanine blue, metal-free phthalocyanine blue, indanthrene blue, phthalocyanine green, polychloro copper phthalocyanine, sulfurized potassium Siumu, strontium sulfide, daylight fluorescent pigments, bronze powder, aluminum powder, also carbon black, graphite, and iron black may be exemplified as a black pigment.

  When an inorganic pigment is used, the surface treatment may be performed using various surface treatment agents. As such a surface treatment agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, a surface graft polymer, or the like can be used. 01 to 10% by weight, preferably 0.1 to 7% by weight can be used. In the case of organic pigments, the molecular weight is preferably 300 to 2,000. If it is less than 300, the pigment may move to the fiber surface and color transfer may occur. On the other hand, when the molecular weight exceeds 2,000, aggregation tends to occur. A preferred molecular weight is 350-700.

  In addition, as an average particle diameter of a pigment, it is preferable that it is 0.001-2 micrometer, Most preferably, it is 0.005-1 micrometer. When the average particle size is less than 0.001 μm, it is difficult to obtain practically. On the other hand, when the particle size exceeds 2 μm, the filter in the spinner pack is likely to be clogged. The holes become prone to contamination and the spinning surface must often be cleaned. The particle size distribution of the pigment to be used is not particularly limited, but the particle size component of 1 μm or more is preferably 20% by weight or less of the whole pigment, and particularly preferably 10% by weight or less suppresses the rise in the pack pack pressure. It is preferable from the viewpoint.

(Method for producing polybutylene terephthalate composition)
There is no restriction | limiting in particular in the manufacturing method of the polybutylene terephthalate composition (masterbatch) comprised from the polybutylene terephthalate and pigment in this invention, A well-known method is employable. That is, it is possible to employ either a method in which polybutylene terephthalate and a pigment are separately supplied to a kneading extruder or supplied to a kneading extruder after preliminary mixing. As the kneading extruder, a screw-type biaxial same-direction or different-direction kneading extruder is preferably used, but a single-screw kneading extruder may be used.
In addition, the temperature at the time of melt-kneading is usually performed at a melting point or higher of polybutylene terephthalate. The melt kneading temperature is preferably 230 to 290 ° C.

  The resulting polybutylene terephthalate composition of the present invention has a pigment concentration of 1 to 60% by weight, preferably 5 to 55% by weight. If it is less than 1% by weight, the amount of mixing for coloring increases and the production efficiency decreases. On the other hand, if the amount exceeds 60% by weight, the dispersion state of the pigment is deteriorated, and problems such as the occurrence of yarn breakage in the yarn making process and acceleration of the pack pressure increase are not preferable.

<Pigment-containing polytrimethylene terephthalate polyester>
In the present invention, the polybutylene terephthalate composition (masterbatch) containing the above pigment is mixed with polytrimethylene terephthalate to obtain a pigment-containing polytrimethylene terephthalate-based polyester.

(PTT)
The PTT used in the present invention is a polyester having trimethylene terephthalate as a main repeating unit. This polyester may be a copolymerized polytrimethylene terephthalate obtained by copolymerizing a third component other than the component constituting the trimethylene terephthalate unit. The third component (copolymerization component) may be either a dicarboxylic acid component or a glycol component. Here, “main” means 90 mol% or more in all repeating units.

  As the component preferably used as the third component, as the dicarboxylic acid component, aromatic dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, isophthalic acid or phthalic acid, adipic acid, azelaic acid, sebacic acid or decanedicarboxylic acid, etc. Aliphatic dicarboxylic acids such as aliphatic dicarboxylic acids and cyclohexanedicarboxylic acids, and the glycol component include ethylene glycol, tetramethylene glycol, diethylene glycol, polyethylene glycol, hexamethylene glycol, cyclohexanedimethanol or 2,2-bis [4 -(2-hydroxyethoxy) phenyl] propane and the like are exemplified, and these can be used alone or in combination of two or more.

  The method for producing PTT used in the present invention is not particularly limited. A method in which terephthalic acid is directly esterified with trimethylene glycol and then polymerized, and an ester-forming derivative of terephthalic acid is transesterified with trimethylene glycol. Thereafter, any of the polymerization methods may be employed.

  The PTT polymerization catalyst used in the present invention is not particularly limited, but it is preferable to use a titanium compound as the polymerization catalyst. Here, the titanium compound used as a catalyst is preferably an organic titanium compound soluble in a polymer. Although there is no restriction | limiting in particular as content of the said titanium compound, From a polycondensation reactivity, the hue of the polyester obtained, and a heat resistant viewpoint, about 2-150 millimol% is contained as a titanium metal element with respect to all the dicarboxylic acid components. It is preferable that

  Here, when a method of polymerizing an ester-forming derivative of terephthalic acid after undergoing a transesterification reaction with trimethylene glycol and adopting a polymerization method, as a transesterification reaction catalyst, usually a calcium compound, a magnesium compound, a manganese compound, a zinc compound, etc. A catalyst used as a transesterification catalyst for polyester may be used in combination. However, usually, a method in which the above-described titanium compound is used as both a transesterification catalyst and a polymerization catalyst is preferably employed.

  The intrinsic viscosity of PTT used in the present invention (measured in an orthochlorophenol solution at 35 ° C.) is 0.80 to 1.40 dL / g, preferably 0.90 to 1.20 dL / g. If it is less than 0.80 dL / g, the physical properties of the resulting pigment-containing polytrimethylene terephthalate-based polyester may be deteriorated. On the other hand, if it exceeds 1.40 dL / g, melt kneading becomes difficult and the melt viscosity is too high. Yarn breakage is likely to occur during spinning and drawing.

(Mixture of polybutylene terephthalate composition and PTT)
There is no restriction | limiting in particular in the blending method of the polybutylene terephthalate composition and PTT in this invention, The well-known method similar to this composition is employable. That is, any of a method of supplying the polybutylene terephthalate composition and PTT separately to the kneading extruder, or supplying them to the kneading extruder after preliminary mixing can be employed. As the kneading extruder, a screw-type biaxial same-direction or different-direction kneading extruder is preferably used, but a single-screw kneading extruder may be used. Moreover, the polybutylene terephthalate composition (masterbatch) mixed with PTT can use multiple types together. By combining master batches containing basic pigments at an appropriate ratio, polytrimethylene terephthalate-based polyester fibers having various types of hues can be obtained from a small number of types of master batches.
In addition, the temperature at the time of melt-kneading is usually performed at a melting point or higher of the polybutylene terephthalate composition and PTT.

(Concentration of polybutylene terephthalate composition after mixing with PTT)
In the present invention, the concentration of the polybutylene terephthalate composition after mixing the polybutylene terephthalate composition (masterbatch) and the polytrimethylene terephthalate is 0 with respect to the total amount of the polytrimethylene terephthalate and the polybutylene terephthalate composition. .5 to 8.0% by weight, preferably 1.0 to 7.5% by weight. Here, in order to make it less than 0.5% by weight, since a high pigment concentration is required for the composition (master batch) containing the chromatic pigment or black pigment to be used, problems such as non-uniform dispersion of the pigment, etc. Is likely to occur. On the other hand, when the content exceeds 8.0% by weight, the composition containing a chromatic pigment or black pigment (masterbatch) and the polytrimethylene terephthalate contained a chromatic pigment or black pigment due to a difference in fluidity during melting. The influence of the non-uniform dispersion of the composition becomes remarkable, causing problems such as yarn breakage during spinning and non-uniform product fiber diameter. In addition, when using together multiple types of polybutylene terephthalate composition (masterbatch), the density | concentration of a polybutylene terephthalate composition is calculated based on the total weight of the polybutylene terephthalate composition used together.

(Other)
The PBT, PTT, polybutylene terephthalate composition (masterbatch), and polytrimethylene terephthalate-based polyester (polybutylene terephthalate composition + TPP) used in the present invention may contain a small amount of additives such as a lubricant, if necessary. Antioxidants, solid phase polycondensation accelerators, fluorescent brighteners, antistatic agents, antibacterial agents, ultraviolet absorbers, light stabilizers, heat stabilizers, and the like may be included.

<Manufacture of original polytrimethylene terephthalate-based polyester fiber>
The original polytrimethylene terephthalate-based polyester fiber of the present invention is melt-spun at a spinning speed of 1,200 m / min or less by mixing the polybutylene terephthalate composition with polytrimethylene terephthalate. This melt spinning can be produced in a manner similar to that usually applied to known polyester fibers and composite fibers, but is particularly preferred for the base polytrimethylene terephthalate pellets with the desired pigment. A method is preferably employed in which the composition (master batch) pellets composed of a pigment and polybutylene terephthalate are weighed and supplied to an extruder for spinning so as to obtain a concentration.
At this time, the melting temperature in the die is preferably about 235 ° C. to 285 ° C., more preferably about 240 ° C. to 260 ° C.
In this melt spinning, the spinning speed is 1,200 m / min or less, preferably 100 to 1,100 m / min. When it exceeds 1,200 m / min, the difference in deformation speed between spinning of polybutylene terephthalate composition containing a chromatic pigment or black pigment and polytrimethylene terephthalate containing substantially no chromatic pigment or black pigment is remarkable. Therefore, there are problems such as non-uniformity of the diameter of the obtained original fiber and yarn breakage during spinning.

Moreover, the single yarn fineness of the obtained fiber is 1.5 dtex or more, preferably 2.0 to 10 dtex. When trying to obtain a fiber having a single yarn fineness of less than 1.5 dtex, the particle size of the pigment is relatively large with respect to the fiber diameter, and there is an influence such as yarn breakage occurring at the time of spinning, and the yield decreases. Therefore, it is not preferable.
The cross-sectional shape of the fiber is not particularly limited, and may be an elliptical cross section, a triangular cross section, or a star cross section in addition to a circular cross section. In addition, any known method can be employed for the composite fiber, and any of a core-sheath structure, a sea-island structure, a side-by-side structure, and the like can be employed. There is no particular limitation on the spinning method, and any method of long fiber, short fiber, spunbond, and melt blow spinning can be employed. The spinning speed is not particularly limited, and stretching and false twisting may be performed following spinning.

Examples In order to make the configuration and effects of the present invention more specific, examples will be given below, but the present invention is not limited to these examples. In addition, each value in an Example was calculated | required according to the following method.
1) Intrinsic viscosity:
TPP was measured at 35 ° C. in orthochlorophenol. PBT was measured at 35 ° C. in a mixed solvent of 40% by weight of 1,1,2,2-tetrachloroethane and 60% by weight of phenol.
2) Fineness Measured according to the method described in JIS-L1015.
3) Spinning yarn breakage Spinning was performed under the conditions shown in Table 1, and the number of yarn breakage occurring in 24 hours per spindle was measured.
4) Number of fiber diameter fluctuations The spun raw yarn was observed with a magnifying glass, and the number of times that a portion having a diameter more than three times the normal fiber diameter per spindle was measured.

[Example 1]
Polytrimethylene terephthalate (abbreviated as PTT) (intrinsic viscosity 0.92 dL / g, melting point 228 ° C.) was melted at 252 ° C. using a screw-type melt extruder, and the inherent viscosity of 0. 85 dL / g polybutylene terephthalate (abbreviated as PBT: DURANEX (grade TRE-DE2) manufactured by Wintech Polymer Co., Ltd.) based black pigment (primary particle size of pigment measured by electron microscope: 0.03 μm ) Was kneaded in 7% by weight, and cooling air of 25 to 30 ° C. was placed at a position 4 cm below the die surface onto the yarn discharged at a discharge rate of 600 g / min from a known solid round cross-section spinneret (420 holes). Undrawn yarn was obtained at a winding speed of 1,000 m / min. The number of yarn breaks that occurred continuously during 24 hours was measured. Further, the obtained undrawn yarn was observed with a magnifying glass at 1,000 m, and the number of occurrences of a very thick portion having a diameter of 3 times or more the normal fiber diameter was measured as the number of fiber diameter fluctuations. Next, the undrawn yarn obtained is drawn to 1.7 to 2.5 times by a two-stage hot water drawing method of 50 ° C. × 90 ° C. so that the tow of 500,000 dtex is drawn after drawing, did.

[Example 2] to [Example 8], [Comparative Example 1] to [Comparative Example 9]
The same operation as in Example 1 was performed except for the intrinsic viscosity of PTT, the intrinsic viscosity of PBT, the pigment content concentration of the master batch, the pigment hue, the master batch addition rate, the discharge amount, the spinning speed, and the number of nozzle holes of the melt spinning. . The results are shown in Table 1.

  The original polytrimethylene terephthalate-based polyester fiber obtained by the present invention is useful for applications such as vehicular interior materials and carpets as well as clothing fibers.

Claims (2)

  A method for producing an original polytrimethylene terephthalate-based polyester fiber having a fineness of 1.5 dtex or more, wherein a polybutylene terephthalate composition containing a pigment and polytrimethylene terephthalate are mixed and melt-spun, and the intrinsic viscosity (1,1 , 2,2-tetrachloroethane in a mixed solvent of 40% by weight of phenol and 60% by weight of phenol, measured at 35 ° C.) with respect to polybutylene terephthalate having 0.75 to 1.30 dL / g. A polytrimethylene terephthalate composition containing 60% by weight of polytrimethylene terephthalate having an intrinsic viscosity (measured in an orthochlorophenol solution at 35 ° C.) of 0.80 to 1.40 dL / g and the polybutylene terephthalate composition 0.5 to 8.0 of the polybutylene terephthalate composition relative to the total weight Were mixed so that the amounts%, spinning speed 1,200m / min method for producing dyed polytrimethylene terephthalate polyester fiber characterized by melt-spinning below.   The method for producing an original polytrimethylene terephthalate-based polyester fiber according to claim 1, wherein the pigment is a chromatic or black pigment.