TWI794291B - Polypropylene resin composition, polypropylene resin molded article, and method for producing polypropylene resin molded article - Google Patents

Abstract

The present invention provides a polypropylene resin composition dyeable with a dye, a polypropylene resin molded article, and a method for producing a polypropylene resin molded article. The polypropylene resin composition of the present invention is characterized in that it contains unmodified polypropylene and maleic anhydride-modified polypropylene compatible with unmodified polypropylene, and maleic anhydride in maleic anhydride-modified polypropylene The graft modification rate of 1.50% by mass to 2.50% by mass.

Description

Polypropylene resin composition, polypropylene resin molded article, and method for producing polypropylene resin molded article

The present invention relates to a polypropylene resin composition dyeable with a dye, a polypropylene resin molded article, and a method for producing a polypropylene resin molded article.

Compared with other chemical fibers and natural fibers, polypropylene (PP) is a lightweight material with a specific gravity as light as 0.91 and floats on water. For example, the specific gravity of chemical fibers is 1.38 for polyester, 1.14 for nylon, 1.14 for acrylic, 1.30 for acetate, and 1.50 for rayon. Also, the specific gravity of natural fibers 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, and is also excellent in chemical resistance and strength.

In order to make effective use of the above-mentioned characteristics of polypropylene, polypropylene is fiberized and colored, and it is used in industrial applications such as blue steel skins for maintenance and mesh sheets for construction engineering. For example, a polymer alloy fiber having a sea-island structure in which polypropylene is mixed with a cationic dyeable polymer has been proposed as a dyeable polypropylene fiber (Patent Document 1).

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

[Prior technical literature] 【Patent Literature】

[Patent Document 1] Japanese Patent Laid-Open No. 2015-148027

[Patent Document 2] Japanese Patent No. 4188557

However, the dyeability of polypropylene is insufficient, for example, in the case of dyeing treatment with a disperse dye, it can only be dyed to the extent of staining. Therefore, clothing products and the like using polypropylene fibers are inferior in color development compared to clothing made of other fibers, and thus polypropylene is hardly distributed as a general clothing application at present.

Therefore, fibers other than polypropylene such as polyester with good dyeability are used for clothing applications, but in this case, since the specific gravity of the fiber is large, weight reduction of the product becomes a problem.

Therefore, if polypropylene can be used as a fiber for clothing, the specific gravity will be lighter than other materials such as polyester, so lightweight products can be produced. In addition, compared with other fibers, the filaments are not extremely thin, and the apparent concentration is increased correspondingly, so the amount of dye used can be reduced, and satisfactory color fastness can be expected.

In view of the above-mentioned problems, an object of the present invention is to provide a polypropylene resin composition dyeable with a dye, a polypropylene resin molded article, and a method for producing a polypropylene resin molded article.

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

Alternatively, the mass ratio of the above-mentioned unmodified polypropylene to the above-mentioned maleic anhydride-modified polypropylene may be 50:50-97:3.

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

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

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

Moreover, the polypropylene resin molded article which is one aspect of the present invention is characterized in that it contains a compatibilizer of unmodified polypropylene and maleic anhydride-modified polypropylene, and the maleic anhydride-modified polypropylene in the above-mentioned maleic anhydride-modified polypropylene is characterized in that The graft modification rate of toic anhydride is 1.50% by mass to 2.50% by mass.

Alternatively, the mass ratio of the above-mentioned unmodified polypropylene to the above-mentioned maleic anhydride-modified polypropylene may be 50:50-97:3.

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

Alternatively, the above-mentioned unmodified polypropylene may have a Z-average molecular weight of 50,000 to 100,000.

The above-mentioned compatibilizer may be a dyed product dyed with a disperse dye.

In addition, a method for producing a polypropylene resin molded article according to an aspect of the present invention is characterized in that it includes: a melt production step of obtaining a melt of the polypropylene resin composition; molding the melt to form a preliminary a molding step of a molded body; and a cooling and solidification step of cooling and solidifying the preliminary molded body to obtain a molded body.

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

As described above, according to the present invention, a polypropylene resin composition dyed with a dye, a polypropylene resin molded article, and a method for producing a polypropylene resin molded article can be provided.

10‧‧‧Feed Hopper

11‧‧‧opening

20‧‧‧Cylinder

21, 22, 23, 24‧‧‧The part in the cylinder 20

30‧‧‧Nozzle

31‧‧‧Head

40‧‧‧Heating cylinder

50‧‧‧cooling cylinder

60‧‧‧oiling roller

70‧‧‧Pretensioning roller

80, 81, 82, 83‧‧‧Extending roller

90‧‧‧Spool

100‧‧‧multifilament manufacturing equipment

A‧‧‧air

P‧‧‧pressure

Y‧‧‧Silk

[ Fig. 1 ] A side view showing a multifilament manufacturing apparatus used for spinning.

One aspect of the polypropylene resin composition, the polypropylene resin molded article, and the method for producing the polypropylene resin molded article of the present invention will be described in detail below.

[Polypropylene resin composition]

The polypropylene resin composition includes unmodified polypropylene and maleic anhydride-modified polypropylene compatible with the aforementioned unmodified polypropylene. Unmodified polypropylene (hereinafter also referred to as "unmodified PP") is a thermoplastic resin obtained by polymerizing propylene, and is an unmodified polymer without using any modifier during polycondensation. If such unmodified PP is used, since the specific gravity is light, even if the surface area of fibers, silk, etc. is increased, the amount of dye used can be reduced, and light-weight products with high color fastness can be provided. In addition, it is possible to impart quick-drying properties, heat retention, chemical resistance, and strength, which are characteristics of polypropylene, to products such as fibers.

As the above-mentioned maleic anhydride-modified polypropylene (hereinafter, also referred to as "modified PP"), a material compatible with the above-mentioned unmodified polypropylene was used. Polypropylene modified by modification with maleic anhydride has excellent dyeability compared to unmodified PP. In particular, the dyeability of disperse dyes is equivalent to that of polyester generally used for clothing. Such modified PP is compatible with unmodified PP, and thus has high color fastness, is lightweight, and can exhibit uniform dyeability while satisfying quick-drying properties, heat retention, chemical resistance, strength, and the like.

For example, when using modified PP that is incompatible with unmodified PP, in the case of forming products such as silk and fiber, the distribution of unmodified PP and modified PP becomes uneven, and unmodified PP and modified PP become uneven. Sexual PP may form a sea-island structure. Then, since unmodified PP and modified PP differ in dyeability, uniform dyeability may not be satisfied as a whole product.

In the above-mentioned maleic anhydride-modified polypropylene, the graft modification rate of maleic anhydride is 1.50% by mass to 2.50% by mass. The graft modification ratio of maleic anhydride is the content of maleic anhydride in the above-mentioned maleic anhydride-modified polypropylene. When the graft modification rate is within this range, excellent dyeability can be exhibited while satisfying the characteristics as polypropylene. When the modification rate of maleic anhydride is small, dyeability may not be satisfied. Also, when the modification rate is large, there is a possibility that it is incompatible with unmodified PP. When the graft modification rate is 1.75% by mass to 2.15% by mass, the compatibility with unmodified PP can be satisfied, and the dyeability can be stably exhibited even when dyes of various colors are used.

Specific forms of the polypropylene resin composition having the above characteristics include, for example, a mixture of solid unmodified PP and modified PP in powder form, granular form, pellet form, and flake form. Examples include a mixture in which arbitrary PP is in the form of pellets, a mixture in which one PP is flake-shaped and the other PP is in the form of pellets, and one PP is in the form of powder or pellets and the other is in the form of pellets. PP is in the form of flakes, etc. In addition, unmodified PP and modified PP are melted and compatibilized to form a solid state such as powder, granular, pellet, and flake, and unmodified PP and modified PP are formed into a polymer Both the form of an alloy and the form in which unmodified PP and modified PP are dissolved in a solvent to form a liquid can be suitably used as the polypropylene resin composition. However, in the present invention, the polypropylene resin composition is not limited to the above forms.

The mass ratio of the above-mentioned unmodified polypropylene to the above-mentioned maleic anhydride-modified polypropylene is ideally 50:50-97:3. By setting the mass ratio within this range, excellent dyeability can be exhibited while satisfying the characteristics as polypropylene. When the ratio of unmodified PP is large, dyeability may not be satisfied. Also, even if the ratio of the modified PP is increased, the dyeability does not improve. If the above mass ratio is 70:30 to 95:5, it is more preferable because it satisfies the characteristics and dyeability as polypropylene, and has excellent processability when processed into products such as yarn, fiber, and film.

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 the melt viscosity changes, which also affects the processability. By setting the Z average molecular weight of the modified PP within this range, compatibility with 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 PP may increase, and the dyeability may improve, but the compatibility with unmodified PP may decrease. Also, when the Z-average molecular weight of the modified PP is large, the influence of maleic anhydride on the modification of PP may be reduced, and the dyeability may decrease. If the above-mentioned Z average molecular weight is 70,000 to 90,000, compatibility with unmodified PP and processability can be satisfied, and quick-drying, heat retention, chemical resistance, and strength can be imparted to the product, so it is more desirable.

Z average molecular weight can be measured by GPC (gel permeation chromatography), for example, and can be calculated|required by following formula (1).

Z average molecular weight = Σ(Mi‧Mi‧Hi)/Σ(Mi‧Hi). ． ． Formula 1)

Here, Mi is the i-th molecular weight from the peak start point, and Hi is the i-th peak height from the base line from the peak start point.

The above-mentioned unmodified polypropylene preferably has a Z-average molecular weight of 50,000 to 100,000. By setting the Z average molecular weight of unmodified PP within this range, compatibility with modified PP and processability can be satisfied. When the Z-average molecular weight of the unmodified PP is large, processability may decrease due to an increase in melt viscosity or the like. In addition, if the Z average molecular weight of the unmodified PP is small, the strength may be impaired when forming products such as filaments and fibers. 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 g/10 minutes 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 processability when the polypropylene resin composition is heated and melted and processed into filaments, fibers, etc. can be satisfied. When the value of the melt flow rate is large or when the value of the melt flow rate is small, the processability may decrease. In consideration of applicability to various production devices used for melt spinning, the melt flow rate is more preferably 20 g/10 minutes to 30 g/10 minutes. In addition, the melt flow rate can be measured in accordance with JIS K 7210 (1999), for example.

The polypropylene resin composition may contain other components in addition to unmodified polypropylene and maleic anhydride-modified polypropylene. For example, polymers compatible with unmodified PP and modified PP, additives, etc. may be included for the purpose of modifying polypropylene, etc., and solvents, etc. may also be included from the viewpoint of ease of processing.

[Polypropylene resin molding]

Next, the polypropylene resin molded article will be described. The polypropylene resin molded article contains a compatibilizer of unmodified polypropylene and maleic anhydride-modified polypropylene. Unmodified PP is a thermoplastic resin obtained by polymerizing propylene, and is an unmodified polymer without using any modifier during polycondensation. If such unmodified PP is used, since the specific gravity is light, even if the surface area of fibers and threads is increased, the amount of dye used can be reduced, and a lightweight polypropylene resin molded body with high color fastness can be formed. In addition, quick-drying properties, heat retention, chemical resistance, and strength, which are characteristics of polypropylene, can be imparted to the polypropylene resin molded article.

Modified PP is polypropylene modified by modification with maleic anhydride, and has excellent dyeability compared to unmodified PP. In particular, the dyeability of disperse dyes is equivalent to that of polyester generally used for clothing. By containing such a compatibilizer of modified PP and unmodified PP, the polypropylene resin molding has high color fastness and light weight, and can meet the requirements of quick drying, heat retention, chemical resistance and strength, etc. At the same time, it exhibits uniform dyeability. Compatible body is a solution or mixture formed by various substances having affinity with each other. In the polypropylene resin molded article, the compatibilizer is a mixture obtained by uniformly melting and mixing unmodified PP and modified PP without uneven distribution such as sea-island structure.

In the above-mentioned maleic anhydride-modified polypropylene, the graft modification rate of maleic anhydride is 1.50% by mass to 2.50% by mass. The graft modification ratio of maleic anhydride is the content of maleic anhydride in the above-mentioned maleic anhydride-modified polypropylene. When the graft modification rate is within this range, excellent dyeability can be exhibited while satisfying the characteristics as polypropylene. When the modification rate of maleic anhydride is small, dyeability may not be satisfied. Also, when the modification rate is large, there is a possibility that it is incompatible with unmodified PP. When the graft modification rate is 1.75% by mass to 2.15% by mass, the compatibility with unmodified PP is satisfied, and the dyeability can be stably exhibited even when dyes of various colors are used.

The polypropylene resin molded article having the above-mentioned characteristics is obtained by processing a polypropylene resin composition, and examples thereof include filaments, fibers, woven fabrics, braided fabrics, non-woven fabrics, clothing, films, sheets, containers, and caps. , syringes and other medical equipment. However, in the present invention, the polypropylene resin molded article is not limited to these.

The mass ratio of the above-mentioned unmodified polypropylene to the above-mentioned maleic anhydride-modified polypropylene is ideally 50:50-97:3. By setting the mass ratio within this range, excellent dyeability can be exhibited while satisfying the characteristics as polypropylene. When the ratio of unmodified PP is large, dyeability may not be satisfied. Also, even if the ratio of the modified PP is increased, the dyeability does not improve. If the above mass ratio is 70:30 to 95:5, it is more preferable because it satisfies the characteristics and dyeability as polypropylene, and has excellent processability when processed into products such as yarn, fiber, and film.

The above-mentioned 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 changes the melt viscosity, etc., which also affects the processability. By setting the Z average molecular weight of the modified PP within this range, compatibility with unmodified PP and processability can be satisfied. When the Z-average molecular weight of the modified PP is small, the influence of modification by maleic anhydride may increase, and the compatibility and dyeability with unmodified PP may decrease. Also, when the Z-average molecular weight of the modified PP is large, processability may decrease due to an increase in melt viscosity or the like. If the above-mentioned Z average molecular weight is 70,000 to 90,000, compatibility with unmodified PP and processability can be satisfied, and quick-drying, heat retention, chemical resistance, and strength can be imparted to the product, so it is more desirable.

The above-mentioned unmodified polypropylene preferably has a Z-average molecular weight of 50,000 to 100,000. By setting the Z average molecular weight of unmodified PP within this range, compatibility with modified PP and processability can be satisfied. When the Z-average molecular weight of the unmodified PP is large, processability may decrease due to increase in melt viscosity or the like. Also, if the Z-average molecular weight of unmodified PP is small, the strength may be impaired when forming products such as filaments and fibers. In consideration of processability and product strength, the above-mentioned Z-average molecular weight is more preferably 85,000-95,000.

The above-mentioned compatibilizer may be a dyed product dyed with a disperse dye. Examples of dyes include disperse dyes, cationic dyes, acid dyes, water-soluble dyes, and the like, and dyeing can be performed with various dyes alone or in combination according to purposes. For clothing applications, especially by using disperse dyes, unevenness can be eliminated and uniform dyeing properties can be satisfied. Dyeing can be performed by a usual dyeing method such as dipping a compatibilizer into a dye.

The polypropylene resin molded article may contain other components in addition to unmodified polypropylene and maleic anhydride-modified polypropylene. For example, polymers compatible with unmodified PP and modified PP, additives, plasticizers, etc. may be contained for the purpose of modification of polypropylene, etc., and the above-mentioned dyes and the like may be contained.

[Manufacturing method of polypropylene resin molding]

Next, a method for producing the above-mentioned polypropylene resin molded article will be described. This production method includes a melt production process, a molding process, and a cooling and solidification process shown below.

(melt production process)

The melt production step 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 pressure, or the like. The melt is a mixture obtained by making unmodified PP and modified PP compatible and uniformly melted and mixed, and is in a liquid state with fluidity. As a method of heating and reducing the pressure of the polypropylene resin composition, a common method can be used. For example, a melt can be obtained by throwing pellets of the polypropylene resin composition into a tank equipped with a heating mechanism, and kneading the pellets with a stirring blade or the like while heating the pellets.

(forming process)

The molding step is a step of molding the molten body to form a preliminary molded body. For example, in the case of producing yarn as a polypropylene resin composition, the above-mentioned tank is provided with an extrusion port capable of extruding the molten body from the tank, such as a spinning nozzle, and by extruding the molten body from the extrusion port, , a preformed body as a fluid body of the thread can be obtained.

Moreover, in the case of producing a film, for example, by sending the molten body in the above-mentioned tank toward a T-die equipped with a manifold, a lip, etc., the molten body is widened in the width direction through the manifold, and the slit-shaped lip is used. By adjusting the thickness of the film, etc., it is possible to obtain a preformed body as a film-like fluid body.

(cooling and solidification process)

The cooling and solidification step is a step of cooling and solidifying the preliminary molded body to obtain a molded body. The preform is a molten fluid that can be solidified by cooling it. For example, in the case of producing yarn as a polypropylene resin composition, the fluid of the yarn can be cured by exposing it to room temperature conditions to become a yarn.

In addition, in the case of producing a film, the film-like fluid can be cooled and solidified to form a thin film by sending the film-like fluid to, for example, a casting device and bringing it into contact with a cooling roll of the casting device.

[dyeing process]

The method for producing a polypropylene resin molded article may further include a dyeing step. Examples of dyes used in the dyeing step include disperse dyes, cationic dyes, acid dyes, water-soluble dyes, and the like, and dyeing can be performed with various dyes alone or in combination according to the purpose. For clothing applications, especially by using disperse dyes, unevenness can be eliminated and uniform dyeing properties can be satisfied. The dyeing process is not particularly limited, and may include, for example, immersing the compatibilizer in a dispersion solution in which a disperse dye is dissolved, heating to 130° C. for about 30 minutes of dyeing treatment, and then using a soaping agent to remove excess on the surface of the compatibilizer. Dye is washed, dehydrated, dried and other usual dyeing methods. The dyeing process may be performed after the cooling and solidification process, or may be performed between each of the above-mentioned processes, or may be performed together with each of the above-mentioned processes. For example, after obtaining a melt of the polypropylene resin composition, dyeing may be added to the melt, and then the melt may be molded.

The method for producing a polypropylene resin molded article may further include other steps in addition to the above-mentioned melt production step, molding step, cooling and solidification step, and dyeing step. For example, a processing step of processing a molded body into a predetermined shape may be included after the cooling and solidification step.

Specifically, in the case of producing yarn as a polypropylene resin composition, the drawing process of reheating and extending the yarn after the above-mentioned cooling and solidification process, the heat treatment process of obtaining the strain of the yarn by heat treatment, and the A cutting process of cutting to a predetermined length, a winding process of winding the yarn on a bobbin or the like, and the like.

In addition, in the case of producing a film, a stretching step of stretching the film after the cooling and solidification step in the longitudinal direction and a transverse direction, a corona treatment step for improving the adhesion of ink and adhesive, a flame treatment step, chemical Handling process, winding process of winding with a winding machine, etc.

As described above, according to the present invention, since it can be dyed with a dye, 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.

[Example]

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 at all.

[choice of dye as clothing use]

Using the black dyes 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 the polyester used for comparison of dyeability, polyethylene terephthalate (MFR (280°C, 2.16kg): 30g/10min, melting point: 250°C, specific gravity: 1.38 , Z average molecular weight: 160000).

(dyeing method)

As each polymer, a pellet-shaped masterbatch was used, and each pellet-shaped polymer was dyed under the following conditions.

‧Disperse dyes: Immerse the polymer in disperse dyes heated to 130°C for 30 minutes.

‧Cationic dye: Immerse the polymer in cationic dye heated to 120°C for 30 minutes.

‧Acid dye: Dip the polymer in acid dye heated to 100°C for 30 minutes.

‧Direct Dyes: Immerse the polymer in direct dyes heated to 90°C for 30 minutes.

After the above-mentioned dyeing, each spherical polymer was allowed to dry naturally at room temperature, and the dyeability was evaluated. The results are shown in Table 3. In Table 3, polymers with a lightness (L*) of less than 20 using a spectrophotometer were evaluated as being excellent in dyeability and marked as ○, polymers with a lightness of 20 to 60 were evaluated as dyeable and marked as △, and those with lightness greater than A polymer of 60 was evaluated as being insufficiently dyed and marked with x.

Modified PP exhibits the same dyeability as polyester used for clothing products when dyed with disperse dyes. In addition, modified PP can also be dyed with cationic dyes, but cannot be sufficiently dyed with acid dyes or direct dyes.

Also, unmodified PP can be dyed with disperse dyes, but cannot satisfy the dyeability for clothing use.

From the above results, it can be seen that the modified PP has excellent dyeability with disperse dyes. However, since the value of MFR is high, it is difficult to process into filaments and fibers. On the other hand, although unmodified PP is not as good as modified PP in terms of dyeability, its MFR value is low and it is easy to process into silk and fiber. In contrast, in order to find a polypropylene that satisfies dyeability and processability, a compatibilizer of unmodified PP and modified PP was prepared as follows, and the dyeability and processability were evaluated.

[Evaluation of Dyeability of Polypropylene Resin Composition]

A compatibile obtained by mixing unmodified PP and modified PP in a predetermined ratio was produced, and the MFR of the compatibilizer was measured, and the dyeability using the above-mentioned disperse dye was evaluated. The results are shown in Table 4. In Table 4, the evaluation method of dyeability is the same as that in Table 3.

In order to be processed into filaments and fibers, the MFR of the polymer is ideally 10g/10 minutes to 40g/10 minutes. According to the results in Table 4, it can be seen that if the mass ratio of unmodified PP to modified PP is 95:5~67:33, the processability and dyeability can be satisfied.

In addition, in the above, the processability was evaluated on the assumption of yarn and fiber, but in the case of producing a sheet or film, it can be produced by adjusting the MFR suitable for the production equipment regardless of the results in Table 4. .

[Evaluation of Spinnability and Spinning]

Next, on the basis of the evaluation results of the above-mentioned [selection of dyestuffs for clothing applications], Examples 1 to 4 and Comparative Example 1 shown below were carried out, and the polypropylene resin composition was spun and knitted. Dyeing was carried out after cylindrical shape, and the spinnability, the dyeability of spinning, and the fastness of dyeing were evaluated.

〈Spinning〉

As the spinning machine, a multifilament manufacturing device (manufactured by Musashino-kikai Co., Ltd.) was used. A side view schematically showing a multifilament production apparatus 100 for spinning is shown in FIG. 1 .

(Multifilament Manufacturing Equipment)

The multifilament manufacturing apparatus 100 includes a hopper 10 for feeding raw materials, a cylinder 20 for heating and melting the raw materials sent from the hopper 10, and a cylinder 20 for extruding the molten material extruded from the cylinder 20 at a pressure P indicated by an arrow. The nozzle 30 that extrudes the raw material from the circular hole to form a filament, the heating cylinder 40 that heats the filament Y extruded from the nozzle from the surrounding, the cooling cylinder 50 that cools the filament sent from the heating cylinder 40 from the surrounding, Oiling roller 60 for oiling the yarn sent from the cooling cylinder 50, pre-tensioning roller 70 for removing the initial elongation by applying a certain load to the oiled yarn for a certain period of time, and stretching roller 80 for drawing the yarn , and a bobbin 90 around which the stretched wire is wound.

(spinning treatment)

A spherical polypropylene resin composition is used as a raw material, and the raw material is put into the multifilament manufacturing apparatus 100 from the opening 11 of the hopper 10, melted in the cylinder 20, and sent to the nozzle 30. The pressure applied by the gear pump shown to the head 31 extrudes the material from the circular hole to form a plurality of filaments. Then, the filament Y is solidified by passing through the heating cylinder 40 and the cooling cylinder 50 while bundling a plurality of filaments into one filament Y. In the cooling cylinder 50, the air A shown by the arrow is sent, and the yarn Y is cooled. Thereafter, oiling treatment and drawing treatment are performed, and the yarn is wound around the bobbin 90, thereby completing the spinning treatment.

As the spinning conditions, the temperatures of the portions of reference numerals 21 to 24 in the cylinder 20 were set to 180° C., 190° C., 200° C., and 200° C., respectively, and the circular hole metal opening of the nozzle was set to a 24-filament nozzle. Also, the temperature of the resin in the nozzle 30 was set at 220°C, and the extrusion rate from the circular hole was set at 7.5 g/min. As stretching conditions, the linear velocity of the oiling roll was set to 150 m/min, the linear velocity of the pre-tensioning roll 70 was set to 200 m/min, the linear velocity of the stretching roll 81 was set to 210 m/min, and the The linear speed of the stretching roll 82 was set to 250 m/min (drawing ratio 1.2 times), and the linear speed of the stretching roll 83 was set to 240 m/min at a temperature of 40°C and the temperature was set to 40°C. The case where stable spinning was possible for one hour or longer was evaluated as good spinnability.

〈Cylinder weaving〉

In order to knit the spinning test produced above into a tube shape, a tube knitting machine (manufactured by Koike Machine Co., Ltd.) for testing was used for tube knitting.

〈Refining〉

In order to refine the dirt and oil adhering to the obtained tubular braid, the tubular braid was thrown into a cleaning solution to which a surfactant (Score roll E13 manufactured by Kitahiro Chemical Co., Ltd.) was added at a ratio of 1 g/L. , wash at 60 °C for 10 min. Thereafter, water washing is performed to remove stains, oil content, and surfactants from the tubular knitted fabric.

〈Dyeing〉

The tubular knitted fabrics after refining were dipped in disperse dyes heated to 130° C. for 30 minutes, using the disperse dyes shown in Table 1, and dyed in the same manner as the usual polyester dyeing method. After dyeing, the tubular knitted fabric was allowed to dry naturally at room temperature, and the measurement of brightness and the evaluation of color fastness were performed.

<Measurement of Brightness>

After confirming that the dyed tubular knitted fabric is uniformly dyed by visual observation, the lightness (L*) was measured at three positions of the tubular knitted fabric with a spectrophotometer, and the average of the lightness at the three positions was When the value was less than 20, it was judged that it was dyed black without any problem, and the evaluation was good. Moreover, when the average value was 20 or more, the dyeing|staining to black was insufficient, and it evaluated as defective.

〈Dye fastness〉

(Friction firmness)

Friction firmness was evaluated using a friction tester in accordance with JIS L0849. The case where the dry rubbing is 3-4 or higher and the wet rubbing is 3-4 or higher was evaluated as good rubbing fastness.

(wash fastness)

Fastness to washing was measured in accordance with JIS L0844 (A-2 method). Cotton and nylon were used as the added cloth, and when the added cloth with a high degree of contamination was grade 3-4 or higher, it was evaluated that the fastness to washing was good.

[Example 1]

The pellets of unmodified PP (Novatec SA3A manufactured by Nippon Polypropylene Co., Ltd.) and the pellets of modified PP (Kayabrid 006P manufactured by Kayaku Akzo Company) shown in Table 2 were heated at 240°C at a mass ratio of 90:10. The mixture was mixed down to obtain pellets with an MFR of 18.8 (230° C., 2.16 kg) and an average molecular weight (Mz) of 90,000. The pellets were spun to obtain polymer fibers of 300 decitex 24 filaments. Spinnability was good without yarn breakage occurring for more than 1 hour from the start of spinning.

The obtained polymer fiber is carried out cylinder weaving, after refining with the condition of 4% o.w.f (taking polymer fiber as 100g, using 4g dyestuff) by disperse dyeing. The brightness was 18.17, evaluated as good, and the rubbing fastness was graded 3-4 for dry friction, and grade 3-4 for wet friction, evaluated as good. Furthermore, the fastness to washing was also rated as 3-4 grades, which was evaluated as good.

[Example 2]

The pellets of unmodified PP (Novatec SA3A manufactured by Nippon Polypropylene Co., Ltd.) and the pellets of modified PP (Kayabrid 006P manufactured by Kayaku Akzo Corporation) shown in Table 2 were mixed at a mass ratio of 85:15 at 240°C. Mixing gave pellets with an MFR of 22.0 (230° C., 2.16 kg) and an average molecular weight (Mz) of 89,000. The pellets were spun to obtain polymer fibers of 300 decitex 24 filaments. Spinnability was good without yarn breakage for more than one hour from the start of spinning.

The obtained polymer fibers were tube-woven and dyed with disperse dyes at 4% o.w.f after refining. The brightness was 16.87, evaluated as good, and the rubbing fastness was graded 3-4 for dry friction, and grade 3-4 for wet friction, evaluated as good. Furthermore, the fastness to washing was also rated as 3-4 grades, which was evaluated as good.

[Example 3]

The pellets of unmodified PP (Novatec SA3A manufactured by Nippon Polypropylene Co., Ltd.) and the pellets of modified PP (Kayabrid 006P manufactured by Kayaku Akzo Corporation) shown in Table 2 were mixed at 240°C at a mass ratio of 80:20 Mixing gave pellets with an MFR of 24.5 (230° C., 2.16 kg) and an average molecular weight (Mz) of 89,000. The pellets were spun to obtain polymer fibers of 300 decitex 24 filaments. Spinnability was good without yarn breakage for more than one hour from the start of spinning.

The obtained polymer fibers were tube-woven and dyed with disperse dyes at 4% o.w.f after refining. The brightness was 15.76, which was evaluated as good, and the rubbing fastness was rated as 3-4 for dry rubbing and 3-4 for wet rubbing, and was evaluated as good. Furthermore, the fastness to washing was also rated as 3-4 grades, which was evaluated as good.

[Example 4]

The pellets of unmodified PP (Novatec SA3A manufactured by Nippon Polypropylene Co., Ltd.) and the pellets of modified PP (Kayabrid 006P manufactured by Kayaku Akzo Corporation) shown in Table 2 were mixed at 240°C at a mass ratio of 75:25. Mixing gave pellets with an MFR of 27.3 (230° C., 2.16 kg) and an average molecular weight (Mz) of 89,000. The pellets were spun to obtain polymer fibers of 300 decitex 24 filaments. Spinnability was good without yarn breakage for more than one hour from the start of spinning.

The obtained polymer fibers were tube-woven and dyed with disperse dyes at 4% o.w.f after refining. The brightness was 15.68, evaluated as good, and the rubbing fastness was graded 3-4 for dry friction, and grade 3-4 for wet friction, evaluated as good. Furthermore, the fastness to washing was also rated as 3-4 grades, which was evaluated as good.

[Comparative Example 1]

Without using modified PP, pellets of unmodified PP (Novatec SA3A manufactured by Nippon Polypropylene Co., Ltd.) shown in Table 2 were spun to obtain polymer fibers of 300 decitex 24 filaments. Spinnability was good without yarn breakage for more than one hour from the start of spinning.

The obtained polymer fibers were tube-woven and dyed with disperse dyes at 4% o.w.f after refining. The lightness was 25.07, and the dyeing to black was insufficient. In addition, the rubbing fastness was rated as good at 3-4 grades for dry friction and 3-4 grades for wet friction. Furthermore, the fastness to washing was also rated as 3-4 grades, which was evaluated as good.

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

For spinning, the MFR of the polymer is ideally 10g/10min~40g/10min. According to Table 4, if the mass ratio of unmodified PP to modified PP is 95:5~67:33 , the result that satisfies processability and dyeability can be obtained. Table 5 shows the results of actually spinning and evaluating spinnability, dyeability, etc., and the results can prove Table 4.

〔Summarize〕

As is clear from the examples, if the polypropylene resin composition of the present invention is used, a polypropylene resin composition excellent in processability and capable of being dyed with a disperse dye or the like can be produced and provided. Therefore, it is suitable as threads and fibers for clothing products, and can also be applied to sheets, films, and the like.

As mentioned above, although the preferred embodiment of this invention was demonstrated in detail, this invention is not limited to these examples. Apparently, a person with ordinary knowledge in the technical field to which the present invention pertains can conceive of various changes or amendments within the scope of the technical ideas described in the scope of the patent application, and it should be understood that such changes and amendments also belong to the present invention technical range.

10‧‧‧Feed Hopper

11‧‧‧opening

20‧‧‧Cylinder

21, 22, 23, 24‧‧‧The part in the cylinder 20

30‧‧‧Nozzle

31‧‧‧Head

40‧‧‧Heating cylinder

50‧‧‧cooling cylinder

60‧‧‧oiling roller

70‧‧‧Pretensioning roller

80, 81, 82, 83‧‧‧Extending roller

90‧‧‧Spool

100‧‧‧multifilament manufacturing equipment

A‧‧‧air

P‧‧‧pressure

Y‧‧‧Silk

Claims (8)

A polypropylene resin composition, characterized in that the aforementioned polypropylene resin composition comprises unmodified polypropylene and maleic anhydride-modified polypropylene compatible with the aforementioned unmodified polypropylene, the aforementioned maleic anhydride-modified polypropylene The graft modification rate of maleic anhydride in polypropylene is 1.50% by mass to 2.50% by mass, the Z-average molecular weight of the aforementioned maleic anhydride-modified polypropylene is 50,000-100,000, and the Z-average molecular weight of the aforementioned unmodified polypropylene is 50000~100000. The polypropylene resin composition as described in item 1 of the scope of application, wherein the mass ratio of the aforementioned unmodified polypropylene to the aforementioned maleic anhydride-modified polypropylene is 50:50~97:3. The polypropylene resin composition as described in item 1 or 2 of the scope of application, wherein the melt flow rate of the aforementioned polypropylene resin composition is 10g/10min at a temperature of 230°C and a load of 2.16kg~ 40g/10 minutes. A polypropylene resin molded body, characterized in that the aforementioned polypropylene resin molded body comprises a compatibilizer of unmodified polypropylene and maleic anhydride-modified polypropylene, and the maleic anhydride in the aforementioned maleic anhydride-modified polypropylene The graft modification rate is 1.50% by mass to 2.50% by mass, the Z-average molecular weight of the aforementioned maleic anhydride-modified polypropylene is 50,000-100,000, and the Z-average molecular weight of the aforementioned unmodified polypropylene is 50,000-100,000. The polypropylene resin molded article described in claim 4 of the patent application, wherein the mass ratio of the aforementioned unmodified polypropylene to the aforementioned maleic anhydride-modified polypropylene is 50:50~97:3. The polypropylene resin molded article described in claim 4 or 5 of the patent application, wherein the compatibilizer is a dyed product dyed with a disperse dye. A method for manufacturing a polypropylene resin molded body, characterized in that the method for manufacturing a polypropylene resin molded body includes: a molten body manufacturing process, in which the melt manufacturing process obtains any one of claims 1 to 3. A melted body of the polypropylene resin composition; a forming step of forming a preformed body by molding the melted body; and a cooling and solidification step of cooling the preformed body in the cooling and solidification step Curing to obtain a shaped body. The method for manufacturing a polypropylene resin molded body as described in claim 7 of the patent claims, wherein the method for manufacturing a polypropylene resin molded body includes a dyeing step, and in the dyeing step, disperse dyes are used to color the molded body after the cooling and solidification step. The aforementioned molded body is dyed.

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