JP7092606B2 - Polypropylene resin composition, polypropylene resin molded product and method for producing polypropylene resin molded product - Google Patents

Description

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

Polypropylene (PP) has a lighter specific gravity of 0.91 than other chemical fibers and natural fibers, and is a lightweight material that floats on water. For example, the specific densities of chemical fibers are 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 natural fibers is 1.54 for cotton, 1.32 for wool, 1.40 for silk, and 1.50 for hemp. Further, since polypropylene is hydrophobic, it dries quickly and has high heat retention, and is also excellent in chemical resistance and strength.

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

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

Japanese Unexamined Patent Publication No. 2015-148027 Japanese Patent No. 4188557

However, polypropylene is not sufficiently dyeable, and when dyed with a disperse dye, for example, polypropylene is dyed only to the extent that it is contaminated. Therefore, since clothing products using polypropylene fibers are inferior in color development to clothing made of other fibers, polypropylene is rarely distributed as a general clothing application.

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

Therefore, if polypropylene can be applied as a fiber for clothing, it is possible to manufacture a lightweight product because the specific gravity is lighter than that of other materials such as polyester. Further, as compared with other fibers, the apparent concentration is increased because the yarn is not made extremely fine, so that the amount of dye used can be reduced, and it can be expected that the dyeing fastness is satisfied.

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

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

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

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

The Z average molecular weight of the unmodified polypropylene may be 50,000 to 100,000.

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

Further, the polypropylene resin molded body according to one aspect of the present invention contains a compatible mixture of unmodified polypropylene and maleic anhydride-modified polypropylene, and the graft modification rate of maleic anhydride in the maleic anhydride-modified polypropylene is 1.50. It is characterized in that it is about 2.50% by mass.

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

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

The Z average molecular weight of the unmodified polypropylene may be 50,000 to 100,000.

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

Further, the method for producing a polypropylene resin molded product according to one aspect of the present invention includes a melt manufacturing step for obtaining a melt of the polypropylene resin composition, a molding step for molding the melt into a preformed body, and a molding step. It is characterized by including a cooling and solidifying step of cooling and solidifying the preformed body to obtain a molded body.

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

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

It is a side view schematically showing the multifilament manufacturing apparatus used for spinning.

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

[Polypropylene resin composition]
The polypropylene resin composition contains unmodified polypropylene and maleic anhydride-modified polypropylene compatible with the unmodified polypropylene. Unmodified polypropylene (hereinafter, may be referred to as "unmodified PP") is a thermoplastic resin obtained by polymerizing propylene, and is modified without using any modifying agent during polycondensation. Not a polymer. Since such non-modified PP has a light specific gravity, it is possible to reduce the amount of dye used even if the surface area of fibers, threads, etc. is increased, and a lightweight product with high dyeing fastness is provided. can do. In addition, the quick-drying property, heat retention property, chemical resistance and strength characteristic of polypropylene can be imparted to products such as fibers.

As the maleic anhydride-modified polypropylene (hereinafter, may be referred to as "modified PP"), a polypropylene that is compatible with the non-modified polypropylene is used. Polypropylene modified by modification with maleic anhydride is superior in dyeability as compared with unmodified PP. In particular, the dyeability with disperse dyes is equivalent to that of polyester, which is generally used for clothing. By dissolving such modified PP with non-modified PP, dyeing fastness is high and light weight is achieved, and uniform dyeing property is achieved while satisfying quick-drying property, heat retention property, chemical resistance, strength and the like. Can be demonstrated.

For example, if a modified PP that is incompatible with the non-modified PP is used, the distribution of the non-modified PP and the modified PP will not be uniform when the product is made of yarn, fiber, etc., and the non-modified PP and the modified PP will have a sea-island structure. May form. Then, since the dyeability of the non-modified PP and the modified PP are different, it may not be possible to satisfy the uniform dyeability of the product as a whole.

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 denaturation rate is within this range, excellent dyeability can be exhibited while satisfying the characteristics as polypropylene. If the denaturation rate of maleic anhydride is small, the dyeability may not be satisfied. Further, when the modification rate is large, it may not be compatible with the non-modified PP. When the graft modification rate is 1.75 to 2.15% by mass, the dyeability is stably exhibited even when dyes of various colors are used while satisfying the compatibility with the unmodified PP. be able to.

Specific forms of the polypropylene resin composition having the above-mentioned characteristics include, for example, a mixture of solid non-modified PP and modified PP such as powder, granule, pellet and flake. When both PPs are a pellet-like mixture, or when one PP is in the form of flakes and the other PP is in the form of pellets, one PP is in the form of powder or pellets and the other is in the form of flakes. For example, the case is. Further, the unmodified PP and the modified PP were melted and compatible with each other to be integrated into a solid such as powder, granule, pellet and flake, and the unmodified PP and the modified PP were used as a polymer alloy. A polypropylene resin composition can also be a product obtained by dissolving a non-modified PP and a modified PP in a solvent to make a liquid. However, the polypropylene resin composition in the present invention is not limited to these.

The mass ratio of the unmodified polypropylene to 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 characteristics as polypropylene. If the proportion of non-denatured PP is large, the stainability may not be satisfied. Further, even if the proportion of modified PP is increased, the dyeability is not improved. When the mass ratio is 70:30 to 95: 5, it is more preferable because it is excellent in processability into products such as threads, fibers and films while satisfying the characteristics and dyeability as polypropylene.

The Z average molecular weight (Mz) of the maleic anhydride-modified polypropylene is preferably 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 maleic anhydride on the modification of the PP may be large, and the stainability may be improved, but the compatibility with the unmodified PP may be lowered. Further, when the Z average molecular weight of the modified PP is large, the influence of maleic anhydride on the modification of PP may be small, and the stainability may be deteriorated. When the Z average molecular weight is 70,000 to 90000, it is more preferable because compatibility with unmodified PP and processability can be satisfied, and quick-drying property, heat retention property, chemical resistance and strength can be imparted to the product. ..

The Z average molecular weight can be measured by, for example, 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 position from the peak start point, and Hi means the peak height from the baseline at the i-th point 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. If the Z average molecular weight of the unmodified PP is large, the workability may be deteriorated due to an increase in melt viscosity and the like. Further, if the Z average molecular weight of the unmodified PP is small, the strength may be impaired in the case of a product such as a thread or a fiber. Considering processability and product strength, it is more preferable that the Z average molecular weight is 85,000 to 95,000.

The melt flow rate (MFR) of the polypropylene resin composition is preferably 10 to 40 g / 10 minutes under the conditions of a temperature of 230 ° C. and a load of 2.16 kg. When the melt flow rate is within this range, the workability when processing the polypropylene resin composition into threads, fibers or the like in a state of being heated and melted can be satisfied. If the melt flow rate value is large or small, the workability may deteriorate. Considering the applicability to various manufacturing equipment 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, it may contain a non-modified PP, a polymer or an additive compatible with the modified PP for the purpose of modifying polypropylene, or the like, or may contain a solvent or the like from the viewpoint of facilitating processing.

[Polypropylene resin molded product]
Next, the polypropylene resin molded body will be described. The polypropylene resin molded product contains a compatible product of unmodified polypropylene and maleic anhydride-modified polypropylene. Unmodified PP is a thermoplastic resin obtained by polymerizing propylene, and is a polymer that has not been modified without any modification agent used during polycondensation. Since such a non-modified PP has a light specific gravity, it is possible to reduce the amount of dye used even if the surface area of fibers, threads, etc. is increased, and it is possible to mold a lightweight polypropylene resin having high dyeing fastness. Can be a body. Further, the polypropylene resin molded product can be imparted with the characteristics of polypropylene, such as quick-drying property, heat retention property, chemical resistance and strength.

The modified PP is polypropylene modified by modifying it with maleic anhydride, and is superior in dyeability as compared with unmodified PP. In particular, the dyeability with disperse dyes is equivalent to that of polyester, which is generally used for clothing. By containing such a compatible product of the modified PP and the non-modified PP, the polypropylene resin molded product has high dyeing fastness, is lightweight, and satisfies quick-drying property, heat retention property, chemical resistance, strength and the like. At the same time, uniform dyeability can be exhibited. A compatible substance is a solution or an admixture formed by a plurality of substances having an affinity for each other. In the polypropylene resin molded product, the compatible material is an admixture in which the non-modified PP and the modified PP are uniformly melted and mixed without any bias in the distribution such as the sea-island structure.

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 denaturation rate is within this range, excellent dyeability can be exhibited while satisfying the characteristics as polypropylene. If the denaturation rate of maleic anhydride is small, the dyeability may not be satisfied. Further, when the modification rate is large, it may not be compatible with the non-modified PP. When the graft modification rate is 1.75 to 2.15% by mass, the dyeability is stably exhibited even when dyes of various colors are used while satisfying the compatibility with the unmodified PP. be able to.

The polypropylene resin molded body having the above characteristics is a processed polypropylene resin composition, and is, for example, medical instruments such as threads, fibers, woven fabrics, knitted fabrics, non-woven fabrics, clothing, films, sheets, containers, caps, and injectors. Can be mentioned. However, the polypropylene resin molded product in the present invention is not limited to these.

The mass ratio of the unmodified polypropylene to 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 characteristics as polypropylene. If the proportion of non-denatured PP is large, the stainability may not be satisfied. Further, even if the proportion of modified PP is increased, the dyeability is not improved. When the mass ratio is 70:30 to 95: 5, it is more preferable because it is excellent in processability into products such as threads, fibers and films while satisfying the characteristics and dyeability as polypropylene.

The Z average molecular weight of the maleic anhydride-modified polypropylene is preferably 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 large, and the compatibility with the unmodified PP and the stainability may be deteriorated. Further, when the Z average molecular weight of the modified PP is large, the workability may be deteriorated due to an increase in melt viscosity or the like. When the Z average molecular weight is 70,000 to 90000, it is more preferable because compatibility with unmodified PP and processability can be satisfied, and quick-drying property, heat retention property, chemical resistance and strength can be imparted 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. If the Z average molecular weight of the unmodified PP is large, the workability may be deteriorated due to an increase in melt viscosity and the like. Further, if the Z average molecular weight of the unmodified PP is small, the strength may be impaired in the case of a product such as a thread or a fiber. Considering processability and product strength, it is more preferable that the Z average molecular weight is 85,000 to 95,000.

The compatible product may be a dyed product dyed with a disperse dye. Examples of the dye include a disperse dye, a cationic dye, an acid dye, a water-soluble dye, and the like, and various dyes can be dyed individually or in combination depending on the purpose. For clothing applications, particularly by using a disperse dye, uniform dyeability is satisfied without unevenness. Dyeing can be performed by using a usual dyeing method such as immersing a compatible solution in a dye.

The polypropylene resin molded product may contain other components in addition to unmodified polypropylene and maleic anhydride-modified polypropylene. For example, for the purpose of modifying polypropylene or the like, a polymer, an additive, a plasticizer or the like compatible with the non-modified PP and the modified PP may be contained, or the above-mentioned dye or the like may be contained.

[Manufacturing method of polypropylene resin molded product]
Next, the method for manufacturing the above-mentioned polypropylene resin molded product will be described. The manufacturing method includes a melt manufacturing step, a molding step, and a cooling solidification step shown below.

(Melting material manufacturing 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, reducing the pressure, or the like. The melt is a mixture in which the non-modified PP and the modified PP are compatiblely melted and uniformly melted and mixed, and is a liquid having fluidity. As a method for heating or reducing the pressure of the polypropylene resin composition, a usual method can be adopted. For example, a melt can be obtained by putting pellets of a polypropylene resin composition into a tank provided with a heating means and kneading the pellets with a stirring blade or the like while heating the pellets.

(Molding process)
This is a step of molding the molten material into a preformed body. For example, in the case of producing a yarn as a polypropylene resin composition, the tank is provided with an extrusion port capable of extruding a melt such as a spinneret from the tank, and the yarn is extruded from the extrusion port. A preformed body as a fluid can be obtained.

When producing a film, for example, the melt in the tank is sent to a T-die provided with a manifold, a lip, etc., the melt is spread in the width direction by a manifold, and the thickness of the film is formed by a slit-shaped lip. By adjusting the slits and the like, a preformed body as a film-like fluid can be obtained.

(Cooling solidification process)
This is a step of cooling and solidifying the preformed body to obtain a molded body. The preformed body is a molten fluid, and can be solidified by cooling the preformed body. For example, when a yarn is produced as a polypropylene resin composition, the fluid of the yarn can be solidified into a yarn by exposing it to room temperature conditions.

Further, in the case of producing a film, a film-like fluid can be sent to, for example, a casting device and brought into contact with a cooling roll of the casting device to be cooled and solidified to form a film.

[Dyeing process]
The method for producing a polypropylene resin molded product 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 individually or in combination depending on the purpose. For clothing applications, particularly by using a disperse dye, uniform dyeability is satisfied without unevenness. The dyeing step is not particularly limited, but for example, the compatible dye is immersed in a dispersion liquid in which a dispersion dye is dissolved, heated to 130 ° C., dyed for about 30 minutes, and then the excess dye on the surface of the compatible dye is removed with a soaping agent. It can include ordinary dyeing methods such as washing with water, dehydration, and drying. The dyeing step can be performed after the cooling solidification step, can be performed during each of the above-mentioned steps, or can be performed together with each of the above-mentioned steps. For example, after obtaining a melt of a polypropylene resin composition, a dye can be added to the melt to dye it, and then the melt can be formed.

The method for producing a polypropylene resin molded product may include other steps in addition to the above-mentioned melt manufacturing step, molding step, cooling solidification step, and dyeing step. For example, it can include a processing step of processing the molded product into a predetermined shape after the cooling and curing step.

Specifically, in the case of producing a thread as a polypropylene resin composition, a drawing step of heating and stretching the thread after the cooling and solidifying step again, a heat treatment step of removing strain of the thread by heat treatment, and a predetermined length of the thread. Examples thereof include a cutting step of cutting, a winding step of winding a thread onto a bobbin, and the like.

Further, in the case of producing a film, a stretching step of stretching the film vertically or horizontally after the cooling and solidifying step, a corona treatment step for improving the adhesion of ink and adhesive, a flame treatment step, and a chemical treatment step. , The winding process of winding with a winding machine or the like.

As described above, according to the present invention, it is possible to provide a polypropylene resin composition, a polypropylene resin molded product, and a method for producing a polypropylene resin molded product, which are particularly suitable for general clothing applications because they can be dyed with a dye. Can be done.

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples. However, the present invention is not limited to the following examples.

[Selection of dyes for clothing applications]
The dyeability of unmodified polypropylene, maleic anhydride-modified polypropylene and polyester was evaluated using the black dyes shown in Table 1. Table 2 shows the physical characteristics of unmodified polypropylene and maleic anhydride-modified polypropylene. As the polyester used for dyeing comparison, polyethylene terephthalate (MFR (280 ° C., 2.16 kg): 30 g / 10 min, melting point: 250 ° C., specific gravity: 1.38, Z, which is common for clothing applications. Average molecular weight: 160,000) was used.

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

After performing the above dyeing, each pelletized polymer was naturally dried at room temperature to evaluate the dyeability. The results are shown in Table 3. In Table 3, those having a brightness (L *) of less than 20 using a spectrophotometer are evaluated as having excellent dyeability, and those having a brightness of 20 to 60 are evaluated as being dyeable, and having a brightness of 60. Larger ones were evaluated as x as those with insufficient staining.

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

Further, although the non-modified PP can be dyed with a disperse dye, it does not satisfy the dyeability for clothing use.

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

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

In order to process into yarn or fiber, the MFR of the polymer is preferably 10 to 40 g / 10 minutes. From the results in Table 4, it was found that if the mass ratio of the unmodified PP to the modified PP was 95: 5 to 67:33, the companion was satisfactory in processability and stainability.

In the above, the processability assuming threads and fibers was evaluated, but when manufacturing a sheet or film, regardless of the results in Table 4, the MFR can be adjusted to be suitable for the manufacturing equipment. ..

[Evaluation of spinnability and spinning]
Next, based on the evaluation result of the above-mentioned [Selection of dye for clothing use], Examples 1 to 4 and Comparative Example 1 shown below were carried out, and after spinning the polypropylene resin composition and knitting the cylinder. After dyeing, the spinnability, the dyeability of the spinner, and the dyeing fastness were evaluated.

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

(Multifilament manufacturing equipment)
In the multifilament manufacturing apparatus 100, the hopper 10 into which the raw material is charged, the cylinder 20 that heats and melts the raw material sent from the hopper 10, and the molten raw material extruded from the cylinder 20 are round holes at the pressure P indicated by the arrow. Nozzle 30 extruded from the nozzle 30 to make threads, a heating cylinder 40 that heats the yarn Y extruded from the nozzle from the surroundings, a cooling cylinder 50 that cools the yarn from the surroundings from the heating cylinder 40, and the yarn sent from the cooling cylinder 50. The oiling roll 60 to be oiled, the pretension roll 70 to remove the initial elongation by applying a constant load to the yarn after the oiling treatment for a certain period of time, the drawing roll 80 to draw the yarn, and the bobbin 90 to wind the yarn after drawing. Be prepared.

(Spinning process)
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 the pressure applied to the head 31 from a gear pump (not shown). The raw material was extruded from the round holes to form a plurality of threads. Then, the yarn Y was solidified through the heating cylinder 40 and the cooling cylinder 50 while bundling the 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. After that, an oiling treatment and a drawing treatment were performed to wind the yarn around the bobbin 90, thereby completing the spinning treatment.

The spinning conditions were such that the temperatures of the portions of the cylinder 20 at reference numerals 21 to 24 were 180 ° C., 190 ° C., 200 ° C., and 200 ° C., respectively, and the round hole cap of the nozzle was a 24-filament nozzle. Further, the resin temperature in the nozzle 30 was set to 220 ° C., and the extrusion rate from the round hole was set to 7.5 g / min. As the 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 stretched roll 81 is 210 m / min, the temperature is 50 ° C., and the peripheral speed of the stretched roll 82 is 250 m. The temperature was 40 ° C., the peripheral speed of the stretching roll 83 was 240 m / min, and the temperature was 40 ° C. When it was possible to spin stably for 1 hour or more, it was evaluated as having good spinnability.

<Cylinder knitting>
In order to test-knit the spinning yarn produced above into a cylinder, a test cylinder knitting machine (manufactured by koikemachine) was used for cylinder knitting.

<Refining>
In order to refine the dirt and oil adhering to the obtained tube knitting, the tube knitting was added to a cleaning solution containing a surfactant (Score Roll E13 manufactured by Kitahiro Chemical Co., Ltd.) at a ratio of 1 g / L, and the tube knitting was added at 60 ° C. for 10 Washed for minutes. Then, it was washed with water to remove dirt, oil and surfactant from the tube knitting.

<staining>
For the tube knitting after refining, the tube knitting was dyed by immersing the tube knitting in the disperse dye heated to 130 ° C. for 30 minutes in the same manner as the general polyester dyeing method using the disperse dye shown in Table 1. After dyeing, the tube knitting 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 tube knitting is uniformly dyed, the brightness (L *) is measured at three points of the tube knitting with a spectrophotometer, and the average value is less than 20. It was judged that it was dyed black without any problem, and it was evaluated as good. Further, those having an average value of 20 or more were evaluated as defective because the dyeing to black was insufficient.

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

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

[Example 1]
The pellets of the non-modified PP (Novatec SA3A manufactured by Japan Polypropylene Corporation) shown in Table 2 and the pellets of the modified PP (Kayabrid 006P manufactured by Kayaku Akzo) were mixed at 240 ° C. with a mass ratio of 90:10 and MFR18.8. (230 ° C., 2.16 kg), pellets having an average molecular weight (Mz) of 90000 were obtained. The pellet was spun to give a polymer fiber of 300 decitex 24 filaments. No yarn breakage occurred for 1 hour or more from the start of spinning, and the spinnability was good.

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

[Example 2]
The pellets of the non-modified PP (Novatec SA3A manufactured by Japan Polypropylene Corporation) shown in Table 2 and the pellets of the modified PP (Kayabrid 006P manufactured by Kayaku Akzo) were mixed at 240 ° C. with a mass ratio of 85:15 and MFR22.0. (230 ° C., 2.16 kg), pellets having an average molecular weight (Mz) of 89000 were obtained. The pellet was spun to give a polymer fiber of 300 decitex 24 filaments. No yarn breakage occurred for 1 hour or more from the start of spinning, and the spinnability was good.

The obtained polymer fibers were tube-knitted, and after scouring, the disperse dye was dyed under the condition of 4% owf. The brightness was good at 16.87, and the friction fastness was good at dry friction grade 3-4 and wet friction grade 3-4. Further, the washing fastness was 3-4 grade, which was good.

[Example 3]
The pellets of the non-modified PP (Novatec SA3A manufactured by Japan Polypropylene Corporation) shown in Table 2 and the pellets of the modified PP (Kayabrid 006P manufactured by Kayaku Akzo) were mixed at 240 ° C. with a mass ratio of 80:20 and MFR24.5. (230 ° C., 2.16 kg), pellets having an average molecular weight (Mz) of 89000 were obtained. The pellet was spun to give a polymer fiber of 300 decitex 24 filaments. No yarn breakage occurred for 1 hour or more from the start of spinning, and the spinnability was good.

The obtained polymer fibers were tube-knitted, and after scouring, the disperse dye was dyed under the condition of 4% owf. The brightness was good at 15.76, and the friction fastness was good at dry friction grade 3-4 and wet friction grade 3-4. Furthermore, the washing fastness was 3-4 grade, which was good.

[Example 4]
The pellets of the non-modified PP (Novatec SA3A manufactured by Japan Polypropylene Corporation) shown in Table 2 and the pellets of the modified PP (Kayabrid 006P manufactured by Kayaku Akzo) were mixed at 240 ° C. with a mass ratio of 75:25 and MFR27.3. (230 ° C., 2.16 kg), pellets having an average molecular weight (Mz) of 89000 were obtained. The pellet was spun to give a polymer fiber of 300 decitex 24 filaments. No yarn breakage occurred for 1 hour or more from the start of spinning, and the spinnability was good.

The obtained polymer fibers were tube-knitted, and after scouring, the disperse dye was dyed under the condition of 4% owf. The brightness was good at 15.68, and the friction fastness was good at dry friction grade 3-4 and wet friction grade 3-4. Further, the washing fastness was 3-4 grade, which was good.

[Comparative Example 1]
Without using the modified PP, pellets of the non-modified PP (Novatec SA3A manufactured by Japan Polypropylene Corporation) shown in Table 2 were spun to obtain a polymer fiber of 300 decitex 24 filaments. No yarn breakage occurred for 1 hour or more from the start of spinning, and the spinnability was good.

The obtained polymer fibers were tube-knitted, and after scouring, the disperse dye was dyed under the condition of 4% owf. The brightness was 25.07, and the staining to black was insufficient. Further, the friction fastness was good in the dry friction class 3-4 and the wet friction class 3-4. Further, the washing fastness was 3-4 grade, which was good.

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

In order to spin, the MFR of the polymer is preferably 10 to 40 g / 10 minutes, and from Table 4, if the mass ratio of the unmodified PP to the modified PP is 95: 5 to 67:33, it is a companion. The results satisfying the processability and dyeability have been obtained. Table 5 shows the results of actual spinning and evaluation of spinnability, dyeability, etc., and 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 having excellent 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 a sheet, a film, or the like.

Although the preferred embodiments of the present invention have been described in detail above, the present invention is not limited to such examples. It is clear that a person having ordinary knowledge in the field of the art to which the present invention belongs can come up with various modifications or modifications within the scope of the technical idea described in the claims. , These are also naturally understood to belong to the technical scope of the present invention.

10 Hopper 11 Opening 20 Cylinder 21, 22, 23, 24 Part of cylinder 20 30 Nozzle 31 Head 40 Heating cylinder 50 Cooling cylinder 60 Oiling roll 70 Pretension roll 80, 81, 82, 83 Stretching roll 90 Bobbin 100 Multifilament manufacturing Equipment A Air P Pressure Y Thread

Claims (5)

Containing a companion of unmodified polypropylene and maleic anhydride-modified polypropylene,
The graft modification rate of maleic anhydride in the maleic anhydride-modified polypropylene is 1.50 to 2.50% by mass.
The Z average molecular weight of the maleic anhydride-modified polypropylene is 50,000 to 100,000.
The Z average molecular weight of the unmodified polypropylene is 50,000 to 100,000.
The resin contains only the unmodified polypropylene and the maleic anhydride-modified polypropylene.
The companion is a dyed product dyed with a disperse dye.
Polypropylene resin molded body. The polypropylene resin molded product according to claim 1 , wherein the mass ratio of the unmodified polypropylene to the maleic anhydride-modified polypropylene is 50:50 to 97: 3. A melt manufacturing process for obtaining a melt of a polypropylene resin composition, and
The molding process of molding the molten material into a preformed body, and
A cooling solidification step of cooling and solidifying the preformed body to obtain a molded body, and
A dyeing step of dyeing the molded product after the cooling solidification step with a disperse dye is included .
The polypropylene resin composition contains, as a resin, non-denatured polypropylene and
It contains only a compatible with maleic anhydride-modified polypropylene that is compatible with the non-modified polypropylene.
The graft modification rate of maleic anhydride in the maleic anhydride-modified polypropylene is 1.50 to 2.50% by mass.
The Z average molecular weight of the maleic anhydride-modified polypropylene is 50,000 to 100,000.
The Z average molecular weight of the unmodified polypropylene is 50,000 to 100,000.
A method for manufacturing a polypropylene resin molded product. The method for producing a polypropylene resin molded product according to claim 3, wherein the mass ratio of the unmodified polypropylene to the maleic anhydride-modified polypropylene is 50:50 to 97: 3. The method for producing a polypropylene resin molded product according to claim 3 or 4, wherein the melt flow rate of the polypropylene resin composition is 10 to 40 g / 10 minutes under the conditions of a temperature of 230 ° C. and a load of 2.16 kg.

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