JP2019052292A - Polypropylene resin composition, polypropylene resin molded body, and method for producing polypropylene resin molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polypropylene resin composition, a polypropylene resin molded article and a method for producing a polypropylene resin molded article which can be dyed with a dye. SOLUTION: The graft modification rate of maleic anhydride in the maleic anhydride-modified polypropylene is 150,000 to 2.50% by mass, which contains a non-modified polypropylene and a maleic anhydride-modified polypropylene compatible with the non-modified polypropylene. A polypropylene resin composition, characterized in that it is. [Selection diagram] Fig. 1

Description

  The present invention relates to a polypropylene resin composition that can be dyed with a dye, a polypropylene resin molded body, and a method for producing a polypropylene resin molded body.

  Polypropylene (PP) is a lightweight material with a specific gravity of 0.91 that is lighter than other chemical fibers and natural fibers, and floats on water. For example, the specific gravity of the chemical fiber is 1.38 for polyester, 1.14 for nylon, 1.14 for acrylic, 1.30 for acetate, and 1.50 for rayon. The specific gravity of the natural fiber is 1.54 for cotton, 1.32 for wool, 1.40 for silk, and 1.50 for hemp. Furthermore, since polypropylene is hydrophobic, it has high quick-drying properties and heat retention properties, and is excellent in chemical resistance and strength.

  In order to effectively utilize such properties, polypropylene is colored into fibers and used for industrial purposes such as curing blue sheets and building mesh sheets. For example, a polymer alloy fiber having a sea-island structure formed by blending polypropylene and a cationic dyeable polymer has been proposed as a dyeable polypropylene fiber (Patent Document 1).

  Further, as a modified polypropylene yarn that can be dyed by an aqueous dye bath, a reaction product of CR-polypropylene having a hydroxyl group and a predetermined molecular weight and a bifunctional carboxylic acid or a corresponding carboxylic acid derivative has been proposed (patent) Reference 2).

Japanese Patent Laying-Open No. 2015-148027 Japanese Patent No. 4188557

  However, polypropylene is not sufficiently dyeable. For example, when it is dyed with a disperse dye, it is dyed only to the extent that it is contaminated. For this reason, since clothing products using polypropylene fibers are inferior in color developability compared to clothing made of other fibers, the current situation is that polypropylene is hardly distributed for general clothing applications.

  Therefore, fibers other than polypropylene, such as polyester having good dyeability, are used for clothing, but in this case, the specific gravity of the fibers is large, so that weight reduction of the product becomes an issue.

  Therefore, if polypropylene can be applied as a fiber for clothing, the specific gravity is lighter than other materials such as polyester, so that a lightweight product can be manufactured. Furthermore, compared with other fibers, since the apparent density is increased as much as the yarn is not made finer, the amount of dye used can be reduced, and it can be expected that dyeing fastness is satisfied.

  In view of the above problems, an object of the present invention is to provide a polypropylene resin composition that can be dyed with a dye, a polypropylene resin molded body, and a method for producing a polypropylene resin molded body.

  In order to solve the above problems, a polypropylene resin composition which is one embodiment of the present invention includes unmodified polypropylene and maleic anhydride-modified polypropylene compatible with the unmodified polypropylene, and the maleic anhydride modified The graft modification rate of maleic anhydride in polypropylene is 1.50 to 2.50% by mass.

  The mass ratio of the unmodified polypropylene and the maleic anhydride-modified polypropylene may be 50:50 to 97: 3.

  The maleic anhydride-modified polypropylene may have a Z average molecular weight of 50,000 to 100,000.

  The unmodified polypropylene may have a Z average molecular weight of 50,000 to 100,000.

  The polypropylene resin composition may have a melt flow rate of 10 to 40 g / 10 min under conditions of a temperature of 230 ° C. and a load of 2.16 kg.

  In addition, the polypropylene resin molded product according to one embodiment of the present invention includes a compatible solution of unmodified polypropylene and maleic anhydride-modified polypropylene, and the maleic anhydride-modified polypropylene has a graft modification rate of 1.50. It is -2.50 mass%, It is characterized by the above-mentioned.

  The mass ratio of the unmodified polypropylene and the maleic anhydride-modified polypropylene may be 50:50 to 97: 3.

  The maleic anhydride-modified polypropylene may have a Z average molecular weight of 50,000 to 100,000.

  The unmodified polypropylene may have a Z average molecular weight of 50,000 to 100,000.

  The compatible material may be a dyed product dyed with a disperse dye.

  In addition, a method for producing a polypropylene resin molded body according to an aspect of the present invention includes a melt production process for obtaining a melt of the polypropylene resin composition, a molding process for molding the melt into a preform, And a cooling and solidifying step of cooling and solidifying the preform to obtain a shaped body.

  The method for producing a polypropylene resin molded body may include a dyeing step of dyeing the molded body after the cooling and solidifying step with a disperse dye.

  As described above, according to the present invention, it is possible to provide a polypropylene resin composition that can be dyed with a dye, a polypropylene resin molded body, and a method for producing a polypropylene resin molded body.

It is a side view which represents typically the multifilament manufacturing apparatus used for spinning.

  Hereinafter, one embodiment of the polypropylene resin composition, the polypropylene resin molded body, and the method for producing the polypropylene resin molded body of the present invention will be described in detail.

[Polypropylene resin composition]
The polypropylene resin composition contains unmodified polypropylene and maleic anhydride-modified polypropylene that is compatible with the unmodified polypropylene. Unmodified polypropylene (hereinafter sometimes referred to as “unmodified PP”) is a thermoplastic resin obtained by polymerizing propylene, and no modifier is used during polycondensation, and it is modified. Not a polymer. Since such non-modified PP has a low specific gravity, for example, it is possible to reduce the amount of dye used even if the surface area of fibers, yarns, etc. is increased, providing a lightweight product with high dyeing fastness. can do. Moreover, quick drying, heat retention, chemical resistance and strength, which are the characteristics of polypropylene, can be imparted to products such as fibers.

  As the maleic anhydride-modified polypropylene (hereinafter sometimes referred to as “modified PP”), those compatible with the unmodified polypropylene are used. Polypropylene modified by modification with maleic anhydride is superior in dyeability compared to unmodified PP. In particular, the dyeability with disperse dyes is equivalent to that of polyesters commonly used for clothing. When such a modified PP is compatible with the unmodified PP, the dyeing fastness is high and the weight is light, and while satisfying quick drying properties, heat retaining properties, chemical resistance, strength, etc., uniform dyeing properties are achieved. It can be demonstrated.

  For example, if a modified PP that is incompatible with the unmodified PP is used, the distribution of the unmodified PP and the modified PP is not uniform when the product is made of yarn or fiber, and the unmodified PP and the modified PP have a sea-island structure. May form. In this case, since the dyeability is different between the unmodified PP and the modified PP, the uniform dyeability may not be satisfied as a whole product.

  In the maleic anhydride-modified polypropylene, the graft modification rate of maleic anhydride is 1.50 to 2.50% by mass. The graft modification rate of maleic anhydride is the content of maleic anhydride in the maleic anhydride-modified polypropylene. When the graft modification rate is within this range, excellent dyeability can be exhibited while satisfying the properties as polypropylene. If the maleic anhydride modification rate is small, the dyeability may not be satisfied. Further, when the modification rate is large, there is a possibility that it is not compatible with unmodified PP. When the graft modification rate is 1.75 to 2.15% by mass, the compatibility with the unmodified PP is satisfied, and even when various color dyes are used, the dyeing property is stably exhibited. be able to.

  Specific examples of the polypropylene resin composition having the above-described characteristics include a mixture of solid unmodified PP and modified PP such as powder, granules, pellets, and flakes. When any PP is a pellet-like mixture, or when one PP is flaky and the other PP is a pellet-like mixture, one PP is powdery and pellety, and the other PP is flaky And the like. Further, the unmodified PP and the modified PP are melted, compatibilized and integrated to form a solid, such as powder, granules, pellets, and flakes, and the unmodified PP and modified PP as a polymer alloy. Those obtained by dissolving a non-modified PP and a modified PP in a solvent to form a liquid may also correspond to the polypropylene resin composition. However, the polypropylene resin composition in the present invention is not limited to these.

  The mass ratio of the unmodified polypropylene and the maleic anhydride-modified polypropylene is preferably 50:50 to 97: 3. When the mass ratio is within this range, excellent dyeability can be exhibited while satisfying the properties as polypropylene. If the ratio of unmodified PP is large, the dyeability may not be satisfied. Further, increasing the ratio of the modified PP does not improve the dyeability. The mass ratio of 70:30 to 95: 5 is more preferable because it satisfies the properties and dyeability as polypropylene and is excellent in processability to products such as yarns, fibers and films.

  The maleic anhydride-modified polypropylene preferably has a Z average molecular weight (Mz) of 50,000 to 100,000. The molecular weight of the polymer affects the compatibility with other polymers, and also affects the processability because the melt viscosity and the like change. When the Z average molecular weight of the modified PP is within this range, compatibility with the unmodified PP and processability can be satisfied. If the Z-average molecular weight of the modified PP is small, the influence of the maleic anhydride on the modification of the PP may be increased, and the dyeability may be increased, but the compatibility with the unmodified PP may be decreased. In addition, when the Z average molecular weight of the modified PP is large, the influence of the maleic anhydride on the modification of the PP may be small, and the dyeability may be reduced. The Z average molecular weight of 70,000 to 90,000 is more preferable because it satisfies compatibility with unmodified PP and processability, and can impart quick drying, heat retention, chemical resistance and strength to the product. .

The Z average molecular weight can be measured, for example, by GPC (gel permeation chromatography), and can be determined by the following formula (1).
Z average molecular weight = Σ (Mi · Mi · Hi) / Σ (Mi · Hi) (1)
Here, Mi means the molecular weight at the i-th from the peak start point, and Hi means the peak height from the baseline at the i-th from the peak start point.

  The Z-average molecular weight of the unmodified polypropylene is preferably 50,000 to 100,000. When the Z-average molecular weight of the unmodified PP is within this range, compatibility with the modified PP and processability can be satisfied. When the Z average molecular weight of the unmodified PP is large, the workability may be lowered due to an increase in the melt viscosity. Further, if the Z-average molecular weight of the unmodified PP is small, the strength may be impaired when a product such as yarn or fiber is used. In consideration of processability and product strength, the Z average molecular weight is more preferably 85,000 to 95,000.

  The melt flow rate (MFR) of the polypropylene resin composition is preferably 10 to 40 g / 10 min under conditions of a temperature of 230 ° C. and a load of 2.16 kg. When the melt flow rate is within this range, it is possible to satisfy the processability when the polypropylene resin composition is heated and melted to be processed into a thread or fiber. When the value of the melt flow rate is large or small, workability may be reduced. Considering applicability to various production apparatuses used for melt spinning, the melt flow rate is more preferably 20 to 30 g / 10 minutes. The melt flow rate can be measured according to, for example, JIS K 7210 (1999).

  The polypropylene resin composition may contain other components in addition to unmodified polypropylene and maleic anhydride modified polypropylene. For example, unmodified PP and polymers compatible with modified PP, additives, and the like may be included for the purpose of modifying polypropylene, and a solvent may be included from the viewpoint of facilitating processing.

[Polypropylene resin molded product]
Next, the polypropylene resin molded body will be described. The polypropylene resin molding includes a compatible solution of unmodified polypropylene and maleic anhydride-modified polypropylene. Unmodified PP is a thermoplastic resin obtained by polymerizing propylene, and is a polymer that is not modified without any modifier used during polycondensation. Since such non-modified PP has a low specific gravity, for example, it is possible to reduce the amount of dye used even if the surface area of fibers, threads, etc. is increased, and a lightweight polypropylene resin molding with high dyeing fastness. It can be a body. Moreover, the quick-drying property, heat retention, chemical resistance, and strength which are the characteristics of polypropylene can be imparted to the polypropylene resin molded body.

  Modified PP is a polypropylene modified by modification with maleic anhydride, and is excellent in dyeability as compared with unmodified PP. In particular, the dyeability with disperse dyes is equivalent to that of polyesters commonly used for clothing. By including such a compatible solution of modified PP and unmodified PP, the polypropylene resin molded body has high dyeing fastness and light weight, and also satisfies quick drying, heat retention, chemical resistance, strength and the like. In addition, uniform dyeability can be exhibited. A compatible solution is a solution or mixture formed by a plurality of substances having affinity for each other. In the polypropylene resin molded product, the compatible solution is an admixture in which the unmodified PP and the modified PP are uniformly melted and mixed without any uneven distribution of the sea-island structure or the like.

  In the maleic anhydride-modified polypropylene, the graft modification rate of maleic anhydride is 1.50 to 2.50% by mass. The graft modification rate of maleic anhydride is the content of maleic anhydride in the maleic anhydride-modified polypropylene. When the graft modification rate is within this range, excellent dyeability can be exhibited while satisfying the properties as polypropylene. If the maleic anhydride modification rate is small, the dyeability may not be satisfied. Further, when the modification rate is large, there is a possibility that it is not compatible with unmodified PP. When the graft modification rate is 1.75 to 2.15% by mass, the compatibility with the unmodified PP is satisfied, and even when various color dyes are used, the dyeing property is stably exhibited. be able to.

  The polypropylene resin molded body having the above characteristics is obtained by processing a polypropylene resin composition, for example, medical devices such as yarns, fibers, woven fabrics, knitted fabrics, non-woven fabrics, clothing, films, sheets, containers, caps, syringes, etc. Is mentioned. However, in this invention, a polypropylene resin molded object is not limited to these.

  The mass ratio of the unmodified polypropylene and the maleic anhydride-modified polypropylene is preferably 50:50 to 97: 3. When the mass ratio is within this range, excellent dyeability can be exhibited while satisfying the properties as polypropylene. If the ratio of unmodified PP is large, the dyeability may not be satisfied. Further, increasing the ratio of the modified PP does not improve the dyeability. The mass ratio of 70:30 to 95: 5 is more preferable because it satisfies the properties and dyeability as polypropylene and is excellent in processability to products such as yarns, fibers and films.

  The maleic anhydride-modified polypropylene preferably has a Z average molecular weight of 50,000 to 100,000. The molecular weight of the polymer affects the compatibility with other polymers, and also affects the processability because the melt viscosity and the like change. When the Z average molecular weight of the modified PP is within this range, compatibility with the unmodified PP and processability can be satisfied. If the Z-average molecular weight of the modified PP is small, the effect of modification by maleic anhydride may be increased, and the compatibility with the unmodified PP and the dyeability may be reduced. Further, when the Z average molecular weight of the modified PP is large, the workability may be lowered due to an increase in the melt viscosity. The Z average molecular weight of 70,000 to 90,000 is more preferable because it satisfies compatibility with unmodified PP and processability, and can impart quick drying, heat retention, chemical resistance and strength to the product. .

  The Z-average molecular weight of the unmodified polypropylene is preferably 50,000 to 100,000. When the Z-average molecular weight of the unmodified PP is within this range, compatibility with the modified PP and processability can be satisfied. When the Z average molecular weight of the unmodified PP is large, the workability may be lowered due to an increase in the melt viscosity. Further, if the Z-average molecular weight of the unmodified PP is small, the strength may be impaired when a product such as yarn or fiber is used. In consideration of processability and product strength, the Z average molecular weight is more preferably 85,000 to 95,000.

  The compatible material may be a dyed product dyed with a disperse dye. Examples of the dye include disperse dyes, cationic dyes, acid dyes, water-soluble dyes, and the like, and various dyes can be dyed alone or in combination depending on the purpose. For apparel use, disperse dyes are used to satisfy the uniform dyeability without unevenness. Dyeing can be performed using a normal dyeing technique such as immersing a compatible solution in the dye.

  As a polypropylene resin molding, in addition to unmodified polypropylene and maleic anhydride-modified polypropylene, other components may be included. For example, unmodified PP and polymers compatible with modified PP, additives, plasticizers, and the like may be included for the purpose of modifying polypropylene and the like, and the dyes described above may be included.

[Production method of polypropylene resin molding]
Next, a method for producing the above-described polypropylene resin molded body will be described. The manufacturing method includes a melt manufacturing process, a molding process, and a cooling and solidifying process described below.

(Melt production process)
This is a step of obtaining a melt of the polypropylene resin composition of the present invention. For example, the polypropylene resin composition can be melted by heating or reducing pressure. The melt is an admixture in which the unmodified PP and the modified PP are mixed and uniformly melted and mixed, and is a liquid having fluidity. A usual method can be adopted as a method of heating or depressurizing the polypropylene resin composition. For example, a melt can be obtained by putting pellets of a polypropylene resin composition into a tank equipped with heating means and kneading the pellets with a stirring blade or the like while heating.

(Molding process)
This is a step of forming the melt into a preform. For example, in the case of producing a yarn as a polypropylene resin composition, the tank is provided with an extrusion port through which a melt such as a spinneret can be extruded from the tank, and the melt is extruded from the extrusion port. A preform as a fluid can be obtained.

  In the case of producing a film, for example, the melt in the tank is sent to a T die having a manifold, a lip, etc., the melt is spread in the width direction by the manifold, and the thickness of the film is increased by a slit-like lip. By adjusting the thickness or the like, a preform as a film-like fluid can be obtained.

(Cooling solidification process)
In this step, the preform is cooled and solidified to obtain a compact. The preform is a molten fluid, which can be solidified by cooling. For example, when a yarn is produced as a polypropylene resin composition, the yarn fluid can be solidified into a yarn by exposing the yarn fluid to room temperature conditions.

  Moreover, when manufacturing a film, a film-like fluid can be cooled, solidified, and can be formed into a film by sending out a film-like fluid to a casting apparatus, for example, and making it contact with the cooling roll of a casting apparatus.

[Dyeing process]
The method for producing a polypropylene resin molded body can further include a dyeing step. Examples of the dye used in the dyeing step include disperse dyes, cationic dyes, acid dyes, water-soluble dyes, and the like, and various dyes can be dyed alone or in combination depending on the purpose. For apparel use, disperse dyes are used to satisfy the uniform dyeability without unevenness. The dyeing process is not particularly limited. For example, the solution is immersed in a dispersion in which a disperse dye is dissolved, heated to 130 ° C. and dyed for about 30 minutes, and then the excess dye on the surface of the solution is removed with a soaping agent. Ordinary dyeing methods such as washing with water, dehydration, and drying can be included. A dyeing process can be performed after a cooling solidification process, and can be performed between each above-mentioned process, and can be performed with each above-mentioned process. For example, after obtaining a melt of a polypropylene resin composition, a dye can be added to the melt and dyed to form the melt.

  As a manufacturing method of a polypropylene resin molding, in addition to the melt manufacturing process, the molding process, the cooling and solidifying process, and the dyeing process, other processes may be included. For example, the process etc. which process a molded object into a predetermined shape after a cooling hardening process can be included.

  Specifically, when a yarn is produced as a polypropylene resin composition, the yarn after the cooling and solidifying step is heated again to be stretched, a heat treatment step for removing strain of the yarn by heat treatment, and a yarn having a predetermined length. And a winding process for winding the yarn around a bobbin or the like.

  In the case of producing a film, a stretching process for stretching the film after the cooling and solidification process vertically and horizontally, a corona treatment process for improving the adhesion of ink and adhesive, a flame treatment process, a chemical treatment process The winding process etc. which wind up with a winder etc. are mentioned.

  As described above, according to the present invention, it is possible to provide a polypropylene resin composition, a polypropylene resin molded article, and a method for producing a polypropylene resin molded article that are particularly suitable for general clothing applications by being dyeable with a dye. Can do.

  Hereinafter, based on an Example and a comparative example, this invention is demonstrated more concretely. However, the present invention is not limited to the following examples.

[Selection of dyes for clothing use]
Using the black dye shown in Table 1, the dyeability of unmodified polypropylene, maleic anhydride-modified polypropylene and polyester was evaluated. Table 2 shows the physical properties of unmodified polypropylene and maleic anhydride-modified polypropylene. In addition, as polyester used for the comparison of dyeability, polyethylene terephthalate (MFR (280 ° C., 2.16 kg): 30 g / 10 min, melting point: 250 ° C., specific gravity: 1.38, Z, which is general for apparel use. Average molecular weight: 160,000) was used.

(Dyeing method)
As each polymer, a pellet master batch was used, and each pellet polymer was dyed under the following conditions.
Disperse dye: The polymer was immersed in a disperse dye heated to 130 ° C. for 30 minutes.
Cationic dye: The polymer is immersed in a cationic dye heated to 120 ° C. for 30 minutes.
Acid dye: The polymer is immersed in an acid dye heated to 100 ° C. for 30 minutes.
Direct dye: The polymer is immersed in a direct dye heated to 90 ° C. for 30 minutes.

  After the above dyeing, each pellet polymer was naturally dried at room temperature to evaluate the dyeability. The results are shown in Table 3. In Table 3, a lightness (L *) using a spectrophotometer of less than 20 indicates that the dyeability is excellent, and a lightness of 20 to 60 indicates that it can be dyed, and the lightness is 60. Larger ones were rated as x for poorly stained.

  The modified PP exhibited the same dyeability as the polyester used in clothing products when dyed with disperse dyes. The modified PP can also be dyed with a cationic dye, but was not sufficiently dyed with an acid dye or a direct dye.

  Non-modified PP can be dyed with disperse dyes, but does not satisfy dyeability for clothing.

  From the above results, it was found that the modified PP was excellent in dyeability with a disperse dye. However, since the MFR value is high, it is difficult to process the yarn or fiber. On the other hand, unmodified PP is inferior to modified PP in terms of dyeability, but has a low MFR value and can be easily processed into yarns and fibers. Therefore, in order to find a polypropylene that can satisfy dyeability and processability, as shown below, a compatible solution of unmodified PP and modified PP was prepared, and dyeability and processability were evaluated.

[Evaluation of dyeability of polypropylene resin composition]
A compatible solution in which unmodified PP and modified PP were confused at a predetermined ratio was prepared, and the MFR of the compatible solution was measured and the dyeability using the disperse dye was evaluated. The results are shown in Table 4. In Table 4, the dyeability evaluation method is the same as in Table 3.

  In order to process the yarn or fiber, the MFR of the polymer is preferably 10 to 40 g / 10 min. From the results in Table 4, it was found that if the mass ratio of unmodified PP and modified PP was a compatible solution of 95: 5 to 67:33, the processability and dyeability were satisfied.

  In the above, the processability assuming yarns and fibers was evaluated. However, when a sheet or film is manufactured, it can be manufactured by adjusting to an MFR suitable for a manufacturing apparatus regardless of the results in Table 4. .

[Evaluation of spinnability and spinning]
Next, based on the evaluation results of the above-mentioned [Selection of dyes for apparel use], Examples 1-4 and Comparative Example 1 shown below are carried out, and after spinning the polypropylene resin composition and knitting the cylinder Dyeing was carried out to evaluate spinnability, dyeability of spinning, and dyeing fastness.

<spinning>
As the spinning machine, a multifilament manufacturing apparatus (manufactured by Musashinokikai Co., Ltd.) was used. FIG. 1 is a side view schematically showing a multifilament manufacturing apparatus 100 used for spinning.

(Multifilament manufacturing equipment)
The multifilament manufacturing apparatus 100 has a hopper 10 into which raw materials are charged, a cylinder 20 that heats and melts the raw materials sent from the hopper 10, and a molten raw material extruded from the cylinders 20 at a hole P at a pressure P indicated by an arrow. A nozzle 30 to be extruded from the nozzle, a heating cylinder 40 for heating the yarn Y extruded from the nozzle from the surroundings, a cooling cylinder 50 for cooling the yarn from the surroundings from the heating cylinder 40, An oiling roll 60 that performs oiling treatment, a pre-tension roll 70 that removes initial elongation over a certain period of time by applying a constant load to the yarn after oiling treatment, a drawing roll 80 that performs yarn drawing treatment, and a bobbin 90 that winds up the yarn after drawing. Prepare.

(Spinning processing)
Using a pellet-shaped polypropylene resin composition as a raw material, the raw material is charged into the multifilament manufacturing apparatus 100 through the opening 11 of the hopper 10, melted by the cylinder 20, sent to the nozzle 30, and pressure applied from the gear pump (not shown) to the head 31. The raw material was extruded from the round hole by a plurality of yarns. The yarn Y was solidified through the heating cylinder 40 and the cooling cylinder 50 while bundling a plurality of yarns into one yarn Y. Air A indicated by an arrow was sent into the cooling cylinder 50 to cool the yarn Y. Then, the spinning process was completed by performing an oiling process and a stretching process and winding the yarn around the bobbin 90.

  The spinning conditions were such that the temperatures of portions 21 to 24 in the cylinder 20 were 180 ° C., 190 ° C., 200 ° C., and 200 ° C., respectively, and the round hole cap of the nozzle was a 24 filament nozzle. Moreover, the resin temperature in the nozzle 30 was 220 degreeC, and the extrusion rate from the round hole was 7.5 g / min. As stretching conditions, the peripheral speed of the oiling roll is 150 m / min, the peripheral speed of the pretension roll 70 is 200 m / min, the peripheral speed of the stretching roll 81 is 210 m / min, the temperature is 50 ° C., and the peripheral speed of the stretching roll 82 is 250 m. / Min (stretching ratio: 1.2 times), a temperature of 40 ° C., a peripheral speed of the stretching roll 83 was 240 m / min, and a temperature was 40 ° C. The case where spinning was possible stably for 1 hour or more was evaluated as having good spinning properties.

<Cylinder knitting>
In order to test-knit the spun yarn produced as described above into a cylindrical shape, a cylindrical knitting machine (manufactured by koikemachine) was used for knitting.

<Scouring>
In order to refine the dirt and oil adhering to the obtained tubular knitting, the tubular knitting was put into a cleaning liquid to which a surfactant (score roll E13 manufactured by Kitahiro Chemical Co., Ltd.) was added at a rate of 1 g / L. Washed minutes. Thereafter, washing with water was performed to remove dirt, oil, and surfactant from the tubular knitting.

<staining>
Using the disperse dyes shown in Table 1, the tube knitting after refining was dyed by immersing the tube knitting in a disperse dye heated to 130 ° C. for 30 minutes in the same manner as in a general polyester dyeing method. After dyeing, the tube braid was naturally dried at room temperature, and the brightness was measured and the dyeing fastness was evaluated.

<Measurement of brightness>
After visually confirming that the dyed tubular knitting is uniformly dyed, the lightness (L *) is measured at three locations of the tubular knitting with a spectrophotometer, and the average value is less than 20. Judged that it was dyed black without problems, and evaluated it as good. Moreover, the thing with an average value of 20 or more was insufficiently dye | stained to black, and was evaluated as bad.

<Dyeing fastness>
(Friction fastness)
According to JIS L0849, the friction fastness was evaluated using a friction tester. Those having a dry friction level of 3-4 or higher and a wet friction level of 3-4 or higher were evaluated as having good friction fastness.

(Washing fastness)
Washing fastness was measured according to JIS L0844 (A-2 method). Cotton and nylon were used as the attached fabric, and the attached fabric having a high degree of contamination of grade 3-4 or higher was evaluated as having good fastness to washing.

[Example 1]
Pellets of unmodified PP (Novatech SA3A manufactured by Nippon Polypro Co., Ltd.) and pellets of modified PP (Kayabrid 006P manufactured by Kayaku Akzo Co., Ltd.) shown in Table 2 were mixed at a mass ratio of 90:10 at 240 ° C., and MFR 18.8 was obtained. (230 degreeC, 2.16 kg) and the average molecular weight (Mz) 90000 pellet were obtained. This pellet was spun to obtain a polymer fiber of 300 dtex 24 filaments. The yarn breakage did not occur for more than 1 hour from the start of spinning, and the spinnability was good.

  The obtained polymer fiber was knitted in a cylinder, and after scouring, the disperse dye was dyed under the condition of 4% owf (4 g of dye was used per 100 g of polymer fiber). The brightness was good at 18.17, and the fastness to friction was good at dry friction 3-4 grade and wet friction 3-4 grade. Further, the fastness to washing was 3-4 grade and was good.

[Example 2]
Pellets of unmodified PP (Novatech SA3A manufactured by Nippon Polypro Co., Ltd.) and pellets of modified PP (Kayabrid 006P manufactured by Kayaku Akzo Co., Ltd.) shown in Table 2 were mixed at a mass ratio of 85:15 at 240 ° C., and MFR 22.0 (230 degreeC, 2.16kg) and the average molecular weight (Mz) 89000 pellet were obtained. This pellet was spun to obtain a polymer fiber of 300 dtex 24 filaments. The yarn breakage did not occur for more than 1 hour from the start of spinning, and the spinnability was good.

  The obtained polymer fiber was knitted in a cylinder, and after scouring, the disperse dye was dyed under the condition of 4% owf. The lightness was good at 16.87, and the fastness to friction was good at dry friction 3-4 grade and wet friction 3-4 grade. Further, the fastness to washing was 3-4 grade and was good.

[Example 3]
Pellets of unmodified PP (Novatec SA3A manufactured by Nippon Polypro Co., Ltd.) and pellets of modified PP (Kayabrid 006P manufactured by Kayaku Akzo Co., Ltd.) shown in Table 2 were mixed at a mass ratio of 80:20 at 240 ° C., and MFR24.5 (230 degreeC, 2.16kg) and the average molecular weight (Mz) 89000 pellet were obtained. This pellet was spun to obtain a polymer fiber of 300 dtex 24 filaments. The yarn breakage did not occur for more than 1 hour from the start of spinning, and the spinnability was good.

  The obtained polymer fiber was knitted in a cylinder, and after scouring, the disperse dye was dyed under the condition of 4% owf. The lightness was good at 15.76, and the fastness to friction was good at dry friction 3-4 grade and wet friction 3-4 grade. Further, the fastness to washing was 3-4 grade and was good.

[Example 4]
Pellets of unmodified PP (Novatec SA3A manufactured by Nippon Polypro Co., Ltd.) and pellets of modified PP (Kayabrid 006P manufactured by Kayaku Akzo Co., Ltd.) shown in Table 2 were mixed at a mass ratio of 75:25 at 240 ° C., and MFR27.3 was obtained. (230 degreeC, 2.16kg) and the average molecular weight (Mz) 89000 pellet were obtained. This pellet was spun to obtain a polymer fiber of 300 dtex 24 filaments. The yarn breakage did not occur for more than 1 hour from the start of spinning, and the spinnability was good.

  The obtained polymer fiber was knitted in a cylinder, and after scouring, the disperse dye was dyed under the condition of 4% owf. The brightness was good at 15.68, and the fastness to friction was good at dry friction 3-4 grade and wet friction 3-4 grade. Further, the fastness to washing was 3-4 grade and was good.

[Comparative Example 1]
Without using modified PP, pellets of unmodified PP (Novatech SA3A manufactured by Nippon Polypro Co., Ltd.) shown in Table 2 were spun to obtain polymer fibers of 300 dtex 24 filaments. The yarn breakage did not occur for more than 1 hour from the start of spinning, and the spinnability was good.

  The obtained polymer fiber was knitted in a cylinder, and after scouring, the disperse dye was dyed under the condition of 4% owf. The brightness was 25.07, and dyeing to black was insufficient. The fastness to friction was good in dry friction 3-4 grade and wet friction 3-4 grade. Further, the fastness to washing was 3-4 grade and was good.

  Table 5 shows the evaluation results of the mixing ratio, MFR, average molecular weight, lightness, and dyeability of the unmodified PP and modified PP of the pellets in Examples 1 to 4 and Comparative Example 1.

  For spinning, the MFR of the polymer is preferably 10 to 40 g / 10 min. From Table 4, if the mass ratio of unmodified PP to modified PP is 95: 5 to 67:33, The results satisfying processability and dyeability are obtained. Table 5 shows the results of actual spinning and evaluation of spinnability, dyeability, etc., but this result can support Table 4.

[Summary]
As is clear from the examples, the polypropylene resin composition of the present invention can produce and provide a polypropylene resin composition excellent in processability and dyeable with a disperse dye or the like. Therefore, it is suitable as a thread or fiber for clothing products, and can also be applied to sheets, films and the like.

  As mentioned above, although preferred embodiment of this invention was described in detail, this invention is not limited to this example. It is obvious that a person having ordinary knowledge in the technical field to which the present invention pertains can come up with various changes or modifications within the scope of the technical idea described in the claims. Of course, it is understood that these also belong to the technical scope of the present invention.

10 Hopper 11 Opening 20 Cylinder 21, 22, 23, 24 Parts in Cylinder 20 30 Nozzle 31 Head 40 Heating Tube 50 Cooling Tube 60 Oiling Roll 70 Pretension Roll 80, 81, 82, 83 Stretching Roll 90 Bobbin 100 Multifilament Manufacturing Equipment A Air P Pressure Y Yarn

Claims (12)

Unmodified polypropylene,
Maleic anhydride-modified polypropylene compatible with the unmodified polypropylene,
A polypropylene resin composition, wherein the maleic anhydride-modified polypropylene has a graft modification rate of maleic anhydride of 1.50 to 2.50% by mass.   The polypropylene resin composition according to claim 1, wherein a mass ratio of the unmodified polypropylene and the maleic anhydride-modified polypropylene is 50:50 to 97: 3.   The polypropylene resin composition according to claim 1 or 2, wherein the maleic anhydride-modified polypropylene has a Z-average molecular weight of 50,000 to 100,000.   The polypropylene resin composition according to any one of claims 1 to 3, wherein the unmodified polypropylene has a Z average molecular weight of 50,000 to 100,000.   The polypropylene resin composition according to any one of claims 1 to 4, wherein the melt flow rate is 10 to 40 g / 10 min under conditions of a temperature of 230 ° C and a load of 2.16 kg. Including a compatible solution of unmodified polypropylene and maleic anhydride-modified polypropylene,
A polypropylene resin molded article, wherein the maleic anhydride-modified polypropylene has a graft modification rate of maleic anhydride of 1.50 to 2.50 mass%.   The polypropylene resin molded article according to claim 6, wherein a mass ratio of the unmodified polypropylene and the maleic anhydride-modified polypropylene is 50:50 to 97: 3.   The polypropylene resin molded article according to claim 6 or 7, wherein the maleic anhydride-modified polypropylene has a Z-average molecular weight of 50,000 to 100,000.   The polypropylene resin molded article according to any one of claims 6 to 8, wherein the unmodified polypropylene has a Z average molecular weight of 50,000 to 100,000.   The polypropylene resin molded article according to any one of claims 6 to 9, wherein the compatible solution is a dyed product dyed with a disperse dye. A melt production process for obtaining a melt of the polypropylene resin composition according to any one of claims 1 to 5,
A molding step of molding the melt into a preform,
A cooling and solidifying step of cooling and solidifying the preform to obtain a molded body;
A process for producing a polypropylene resin molded product, comprising:   The manufacturing method of the polypropylene resin molding of Claim 11 including the dyeing | staining process which dye | stains the said molded object after the said cooling solidification process with a disperse dye.

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