JP5076421B2 - Polypropylene resin composition, and sheet and container comprising the same - Google Patents

Description

  The present invention relates to a polypropylene resin composition, and a sheet and a container comprising the same. More specifically, the present invention relates to a polypropylene-based resin composition capable of suppressing deformation of a container when molded into a container, and a sheet and a container made thereof.

Conventionally, it is known that a polypropylene resin is used as various molded articles.
For example, in JP-A-8-311253, as a means for improving the transparency of a molded product, a phosphate compound having a specific structure, a lithium aluminum composite hydroxide salt, and a specific amount of each are added to crystalline polyolefin. A crystalline polyolefin composition is described.

  Japanese Patent Application Laid-Open No. 2002-348421 discloses polypropylene (A) having a crystalline melting point within a specific temperature range as a means for improving the transparency, impact resistance, heat resistance and rigidity of a sheet, and 5 A resin composition is described in which a cyclic organic phosphate basic polyvalent metal salt is blended as a crystal nucleating agent with a resin component composed of polypropylene (B) having a crystalline melting point in a range of ˜50 ° C.

JP-A-8-311253 JP 2002-348421 A

However, when the polyolefin resin composition described in the above publication is used for a container, the container may be deformed, and thus it has been required to suppress the deformation of the container.
Under such circumstances, an object of the present invention is to provide a polypropylene-based resin composition capable of suppressing deformation of a container when molded into a container, and a sheet and a container comprising the same.

式（Ｉ）
（式中、Ｒ¹は水素原子又は炭素原子数１〜４のアルキル基を表し、Ｒ²およびＲ³はそれぞれ独立に水素原子、炭素原子数１〜１２のアルキル基、シクロアルキル基、アリール基またはアラルキル基を表し、Ｍ¹はアルカリ金属原子、アルカリ土類金属原子、またはアルミニウム原子であり、Ｍ¹がアルカリ金属原子の場合、ｐは１であり、且つｑは０であり、Ｍ¹がアルカリ土類金属原子の場合、ｐは２であり、且つｑは０であり、Ｍ¹がアルミニウム原子の場合、ｐは１または２であり、且つｑは３−ｐである。） As a result of intensive studies, the present inventors have found that the present invention can solve the above problems, and have completed the present invention.
That is, the present invention
A resin component containing 50 to 99.5% by weight of the following propylene polymer (A) and 0.05 to 50% by weight of the following propylene polymer (B) (however, the polymer (A) and the heavy The total amount of the union (B) is 100% by weight), and 0.01 to 1 part by weight of an aromatic phosphate compound represented by the following formula (I) with respect to 100 parts by weight of the resin component. The present invention relates to a polypropylene resin composition, and a sheet and a container made thereof.
Propylene polymer (A): A propylene polymer having a melting point (Tm) of 100 to 149 ° C. and a melt flow rate (MFR) of 1 to 10 g / 10 min.
Propylene polymer (B): A propylene homopolymer or a propylene-ethylene copolymer having a propylene content of 99.6 to 99.99% by weight and an ethylene content of 0.01 to 0.4% by weight. A polymer (provided that the total of propylene content and ethylene content is 100% by weight), melting point (Tm) is 150 to 165 ° C., and melt flow rate (MFR) is 1 to 10 g / 10 min. This relates to a propylene polymer.

Formula (I)
(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, and an aryl group. Or an aralkyl group, M ¹ is an alkali metal atom, an alkaline earth metal atom, or an aluminum atom; when M ¹ is an alkali metal atom, p is 1, q is 0, and M ¹ is (In the case of an alkaline earth metal atom, p is 2, and q is 0. When M ¹ is an aluminum atom, p is 1 or 2, and q is 3-p.)

  ADVANTAGE OF THE INVENTION According to this invention, when shape | molded in a container, the polypropylene resin composition which can suppress a deformation | transformation of a container, and the sheet | seat and container consisting thereof can be obtained.

The polypropylene resin composition of the present invention contains 50 to 99.5% by weight of the propylene polymer (A) and 0.05 to 50% by weight of the propylene polymer (B). The total of the combination (A) and the polymer (B) is 100% by weight).
From the viewpoint of suppressing deformation of the container when molded into a container, the content of the polymer (A) and the polymer (B) is preferably 55 to 99% by weight of the polymer (A), A polymer (B) is 1-45 weight%. More preferably, the polymer (A) is 60 to 95% by weight and the polymer (B) is 5 to 40% by weight.

  The propylene polymer (A) used in the present invention is at least one polymer selected from the group consisting of a propylene homopolymer and a propylene copolymer. From the viewpoint of enhancing transparency, a propylene-based copolymer is preferable.

When the propylene polymer (A) is a propylene copolymer, a propylene random copolymer may be mentioned.
Examples of the propylene random copolymer include a propylene-ethylene copolymer obtained by copolymerizing propylene and ethylene, and a copolymer of propylene and at least one α-olefin having 4 to 20 carbon atoms. Examples include propylene-α-olefin copolymers obtained, propylene-ethylene-α-olefin copolymers obtained by copolymerizing propylene, ethylene, and at least one α-olefin having 4 to 20 carbon atoms. It is done.

  Examples of the α-olefin having 4 to 20 carbon atoms used in the propylene-ethylene-α-olefin copolymer include 1-butene, 2-methyl-1-propene, 1-pentene, and 2-methyl-1. -Butene, 3-methyl-1-butene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4 -Methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1- Butene, 1-octene, methyl-1-pentene, ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1 Pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, and the like. 1-butene, 1-hexene, 1-hexene and 1-octene are preferable, and 1-butene and 1-hexene are more preferable from the viewpoint of transparency and rigidity.

  Examples of the propylene-α-olefin copolymer include propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, and propylene-ethylene-α-. Examples of the olefin copolymer include a propylene-ethylene-1-butene copolymer, a propylene-ethylene-1-hexene copolymer, and a propylene-ethylene-1-octene copolymer.

The propylene random copolymer is preferably a propylene-ethylene copolymer, a propylene-1-butene copolymer, a propylene-1-hexene copolymer, a propylene-ethylene-1-butene copolymer, or propylene-ethylene. -1-hexene copolymer.
More preferred are a propylene-ethylene copolymer, a propylene-1-butene copolymer, and a propylene-ethylene-1-butene copolymer from the viewpoints of transparency and rigidity.

  The melting point (Tm) of the propylene polymer (A) is 100 to 149 ° C., preferably 105 to 148 ° C., more preferably 110 to 147 ° C. If the melting point (Tm) of the propylene polymer (A) is below the lower limit, the rigidity of the sheet or the container that is the secondary molded body may deteriorate. When the upper limit is exceeded, the amount of heat required for thermoforming a sheet or a container that is a secondary molded body thereof may increase.

  The melting point (Tm) of the propylene polymer (A) is selected by selecting a polymerization catalyst used for the production of the propylene polymer (A) and adjusting the stereoregularity of the propylene polymer (A). Can be adjusted within range. Moreover, it can adjust within the said range by adjusting ethylene and / or alpha-olefin content contained in a propylene polymer (A).

  Usually, when the stereoregularity of the propylene polymer (A) increases, the melting point (Tm) increases, and when the stereoregularity decreases, the melting point (Tm) decreases. Further, when the content of ethylene and / or α-olefin contained in the propylene-based polymer (A) increases, the melting point (Tm) decreases, and when the content of ethylene and / or α-olefin decreases, the melting point (Tm). ) Will be higher.

  The melt flow rate (MFR) measured at a temperature of 230 ° C. and a load of 21.18 N of the propylene polymer (A) is 1 to 10 g / 10 minutes, preferably 2 to 9 g / 10 minutes, more preferably 2 ~ 8 g / 10 min.

  When the MFR of the propylene-based polymer (A) used in the present invention is below the lower limit, the extrusion load during extrusion may increase. On the other hand, if the upper limit is exceeded, the fluidity of the resin during extrusion may deteriorate, or the formability of the sheet or container may deteriorate.

  The propylene polymer (B) used in the present invention is a propylene homopolymer or a propylene-ethylene copolymer having an ethylene content of 0.01 to 0.4% by weight. In addition, when a polymer (B) is a propylene-ethylene copolymer, the sum total of propylene content and ethylene content shall be 100 weight%.

  When the propylene polymer (B) is a propylene-ethylene copolymer, the ethylene content is preferably 0.02 to 0.38% by weight, more preferably 0.04 to 0.35% by weight. is there.

The melting point (Tm) of the propylene-based polymer (B) is 150 to 165 ° C, preferably 151 to 164 ° C, more preferably 152 to 163 ° C.
When the melting point (Tm) of the propylene polymer (B) used in the present invention is below the above lower limit, the rigidity of the sheet or container may be deteriorated. On the other hand, if the upper limit is exceeded, the amount of heat required for thermoforming the sheet or the secondary molded body thereof may increase.

  The melting point (Tm) of the propylene polymer (B) is determined by selecting a polymerization catalyst used for the production of the propylene polymer (B) and adjusting the stereoregularity of the propylene polymer (B). (Tm) can be adjusted within the above range. Moreover, it can adjust within the said range by adjusting ethylene content of a propylene polymer (B).

  Usually, when the stereoregularity of the propylene polymer (B) increases, the melting point (Tm) increases, and when the stereoregularity decreases, the melting point (Tm) decreases. Further, the melting point (Tm) decreases as the ethylene content in the propylene polymer (B) increases, and the melting point (Tm) increases as the ethylene content decreases.

  The melt flow rate (MFR) measured at a temperature of 230 ° C. and a load of 21.18 N of the propylene polymer (B) is 1 to 10 g / 10 minutes, preferably 2 to 9 g / 10 minutes, more preferably 2 ~ 8 g / 10 min.

  If the MFR of the propylene-based polymer (B) used in the present invention is below the lower limit, the extrusion load during extrusion may increase. Moreover, when it exceeds the said upper limit, the fluidity | liquidity of resin at the time of an extrusion process may deteriorate, and the moldability of a sheet | seat or a container may deteriorate.

As a manufacturing method of propylene-type polymer (A) and (B), the method of manufacturing with a well-known polymerization method using a well-known polymerization catalyst is mentioned.
As a known polymerization catalyst, for example,
(1) a catalyst system comprising a solid catalyst component essentially containing magnesium, titanium and halogen, an organoaluminum compound, and a third component such as an electron donating compound used as necessary;
(2) a catalyst system comprising a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring and an alkylaluminoxane,
(3) A catalyst system composed of a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring and a compound that reacts with it to form an ionic complex, and an organoaluminum compound.
Preferred is a catalyst system comprising a solid catalyst component essentially containing magnesium, titanium and halogen, an organoaluminum compound, and an electron donating compound. For example, JP-A-61-218606, JP-A-61-287904 JP-A-1-319508, JP-A-7-216017, and the like.

  Known polymerization methods include, for example, a slurry polymerization method using an inert hydrocarbon solvent, a solvent polymerization method, a solventless liquid phase polymerization method and a gas phase polymerization method, and preferably a gas phase polymerization method. . Furthermore, a method of combining the above-described polymerization methods and continuously performing them, for example, a liquid phase-gas phase polymerization method and the like can be mentioned. For example, polymerization methods described in JP-A-7-216017 and the like can be mentioned.

（式中、Ｒ¹は水素原子又は炭素原子数１〜４のアルキル基を表し、Ｒ²およびＲ³はそれぞれ独立に水素原子、炭素原子数１〜１２のアルキル基、シクロアルキル基、アリール基またはアラルキル基を表し、Ｍ¹はアルカリ金属原子、アルカリ土類金属原子、またはアルミニウム原子であり、Ｍ¹がアルカリ金属原子の場合、ｐは１であり、且つｑは０であり、Ｍ¹がアルカリ土類金属原子の場合、ｐは２であり、且つｑは０であり、Ｍ¹がアルミニウム原子の場合、ｐは１または２であり、且つｑは３−ｐである。） The aromatic phosphate ester compounds used in the present invention are compounds represented by the following formula (I).

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, and an aryl group. Or an aralkyl group, M ¹ is an alkali metal atom, an alkaline earth metal atom, or an aluminum atom; when M ¹ is an alkali metal atom, p is 1, q is 0, and M ¹ is (In the case of an alkaline earth metal atom, p is 2, and q is 0. When M ¹ is an aluminum atom, p is 1 or 2, and q is 3-p.)

In the aromatic phosphate ester compounds represented by the above formula (I) used in the present invention, examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹ include a methyl group, an ethyl group, a propyl group, i- A propyl group, an n-butyl group, a sec-butyl group, an i-butyl group and the like. Examples of the alkyl group having 1 to 12 carbon atoms represented by R ² and R ³ include a methyl group, an ethyl group, and a propyl group. I-propyl group, n-butyl group, sec-butyl group, t-butyl group, amyl group, t-amyl group, hexyl group, heptyl group, octyl group, i-octyl group, t-octyl group, 2- Examples include ethylhexyl group, nonyl group, i-nonyl group, decyl group, i-decyl group, undecyl group, dodecyl group, t-dodecyl group and the like.

Examples of the alkali metal atom represented by M ¹ in the above formula (I) used in the present invention include lithium, sodium, and potassium. Examples of the alkaline earth metal atom include beryllium, calcium, magnesium, Examples include strontium and barium.

M ¹ in the above formula (I) used in the present invention is preferably lithium or aluminum, and more preferably lithium.

When M ¹ of the above formula (I) used in the present invention is lithium, examples of the aromatic phosphate compound include lithium-2,2′-methylene-bis (4,6-dimethylphenyl) phosphate. ], Lithium-2,2'-ethylidene-bis (4,6-dimethylphenyl) phosphate, lithium-2,2'-methylene-bis (4,6-diethylphenyl) phosphate, lithium-2,2 ' Ethylidene-bis (4,6-diethylphenyl) phosphate, lithium-2,2′-methylene-bis (4,6-i-propylphenyl) phosphate, lithium-2,2′-ethylidene-bis (4 , 6-i-propylphenyl) phosphate, lithium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, lithium -2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, lithium -2,2'-ethylidene-bis (4-methyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-t-butyl-6-methylphenyl) phosphate, lithium -2,2'-ethylidene-bis (4-t-butyl-6-methylphenyl) phosphate, lithium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, lithium -2,2'-ethylidene-bis (4-ethyl-6-tert-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-i-propyl-6-tert-butyl) Tilphenyl) phosphate, lithium-2,2′-ethylidene-bis (4-i-propyl-6-tert-butylphenyl) phosphate, and the like.

When M ¹ of the above formula (I) used in the present invention is aluminum, examples of the aromatic phosphate compound include hydroxyaluminum-bis [2,2′-methylene-bis (4,6-dimethylphenyl). ) Phosphate], hydroxyaluminum-bis [2,2′-ethylidene-bis (4,6-dimethylphenyl) phosphate], hydroxyaluminum-bis [2,2′-methylene-bis (4,6-diethylphenyl) ) Phosphate], hydroxyaluminum-bis [2,2′-ethylidene-bis (4,6-diethylphenyl) phosphate], hydroxyaluminum-bis [2,2′-methylene-bis (4,6-i-) Propylphenyl) phosphate], hydroxyaluminum-bis [2,2′-ethylidene-bis (4 6-i-propylphenyl) phosphate], hydroxyaluminum-bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], hydroxyaluminum-bis [2,2′- Ethylidene-bis (4,6-di-t-butylphenyl) phosphate], hydroxyaluminum-bis [2,2′-methylene-bis (4-methyl-6-tert-butylphenyl) phosphate], hydroxyaluminum -Bis [2,2′-ethylidene-bis (4-methyl-6-tert-butylphenyl) phosphate], hydroxyaluminum-bis [2,2′-methylene-bis (4-tert-butyl-6-methyl) Phenyl) phosphate], hydroxyaluminum-bis [2,2′-ethylidene-bis (4-tert-butyl-6-methyl) Phenyl) phosphate], hydroxyaluminum-bis [2,2′-methylene-bis (4-ethyl-6-tert-butylphenyl) phosphate], hydroxyaluminum-bis [2,2′-ethylidene-bis (4 -Ethyl-6-t-butylphenyl) phosphate], hydroxyaluminum-bis [2,2′-methylene-bis (4-i-propyl-6-t-butylphenyl) phosphate], hydroxyaluminum-bis [ 2,2′-ethylidene-bis (4-i-propyl-6-tert-butylphenyl) phosphate] and the like.

As the aromatic phosphate ester compounds represented by the formula (I), commercially available products may be used. For example, ADK STAB NA71 (trade name, manufactured by ADEKA Corporation) in which M ^{1 in the} formula (I) is lithium, Adeka Stub NA21 (trade name, manufactured by ADEKA Corporation) in which M ^{1 in} formula (I) is aluminum can be mentioned.

  The content of the aromatic phosphate ester compound used in the present invention is 100 parts by weight of the resin component containing the propylene polymer (A) and the propylene polymer (B) or the propylene polymer (C). On the other hand, it is 0.01-1 weight part, Preferably it is 0.015-0.1 weight part, More preferably, it is 0.020-0.05 weight part.

  When the content of the aromatic phosphate ester compounds used in the present invention is below the lower limit, transparency and rigidity may not be excellent. Further, if the content of the aromatic phosphate ester compounds used in the present invention exceeds the above upper limit, the sheet or the container made thereof may be fuzzy.

  You may add another additive to the polypropylene resin composition of this invention as needed. Examples of other additives include neutralizers, organic peroxides, weather resistance, flame retardancy, antistatic agents, plasticizers, lubricants, copper damage inhibitors, antioxidants, and antiblocking agents. . Other additives may be used alone or in combination of at least two kinds.

  Examples of the neutralizing agent include fatty acid calcium salts and hydrotalcite, and the content thereof is preferably a resin component containing 100% by weight of a propylene polymer (A) and a propylene polymer (B). 0.005 to 0.5 parts by weight with respect to parts.

As the organic peroxide, those that are industrially easy to handle are preferred, and for example, those having a half-life at 150 ° C. of 0.5 minutes or more are preferred. Specific examples of such organic peroxides include 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,1-bis (t-butylperoxy) 3, 3,5. -Trimethylcyclohexane, t-butyl peroxyisopropyl carbonate, t-butyl per-3,3,5-trimethylhexanoate, 1,3 bis (2-t-butylperoxyisopropyl) benzene and the like can be mentioned.
Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like.

  If necessary, the polypropylene resin composition of the present invention may contain a polyethylene resin, an ethylene-α-olefin elastomer, and the like.

  As a method for producing the polypropylene resin composition of the present invention, the propylene polymer (A), the propylene polymer (B), and the aromatic phosphoric acid ester compounds are further added as necessary. The method of melt-kneading various additives is mentioned. For example, the propylene polymer (A), the propylene polymer (B), and the aromatic phosphate ester compounds, and the various additives that are added as necessary, a tumbler mixer, a Henschel mixer, Examples of the method include mixing using a mixer such as a ribbon blender, and then melt-kneading with a single-screw extruder, twin-screw extruder, Banbury mixer, or the like to form a pellet.

  The polypropylene resin sheet of the present invention is a sheet comprising the polypropylene resin composition of the present invention. Examples of a method for molding the polypropylene resin composition of the present invention into a sheet include molding methods used for normal sheet production such as an extrusion molding method, an injection molding method, a press molding method, and a calendar molding method. Among these, the extrusion molding method is preferred, and the extrusion T die molding method is more preferred because of the reason that productivity is good and the reason that transparency is good. As an extrusion T-die molding method, for example, a molten polypropylene resin composition is extruded from a T-die into a sheet using a single screw extruder, a twin screw extruder, a gear extruder, etc., and cooled and solidified with a metal cooling roll. An extruding T-die forming method is used.

  The thickness of the sheet of the present invention is usually 0.1 to 3.0 mm, preferably 0.3 to 2.5 mm, from the viewpoint of obtaining sufficient strength and transparency. The sheet of the present invention may be a single sheet or a multilayer sheet made of different resins. Examples of the method for producing a multilayer sheet include an extrusion laminating method, a heat laminating method, a dry laminating method and the like that are usually used.

  The polypropylene resin sheet of the present invention may be uniaxially or biaxially stretched by, for example, a roll stretching method, a tenter stretching method, a tubular stretching method, or the like. Further, the surface treatment may be performed by a corona discharge treatment, a flame treatment, a plasma treatment, an ozone treatment or the like that is usually used.

Examples of a method for thermoforming the polypropylene resin sheet of the present invention into a polypropylene resin container which is a secondary molded body include known thermoforming methods such as vacuum forming, pressure forming, and vacuum / pressure forming.
As a heating method at the time of thermoforming, methods such as direct heating by a hot plate and indirect heating by a far infrared heater can be mentioned. The method of thermoforming is preferably a method of thermoforming at a relatively high pressure pressure in order to ensure good mold transferability, more preferably air leakage from the mold mating surface and the life of the mold. In this method, thermoforming is performed in a range in which the reduction hardly occurs, for example, in the range of 0.2 to 0.5 MPa.

  As a shape of the polypropylene resin container of the present invention, any shape can be selected according to the purpose. For example, a shape according to food packaging applications such as a lunch box type, bowl type, drink cup type, jelly cup type, etc., and a shape according to industrial applications such as a tray for storing precision parts can be selected.

  Hereinafter, the present invention will be described in detail by way of examples and comparative examples. Measurement of physical properties and preparation of samples used in Examples and Comparative Examples were performed according to the following methods.

[Measurement method of physical properties]
(1) Melt flow rate (MFR, unit: g / 10 minutes)
It was measured at a temperature of 230 ° C. and a load of 21.18 N according to the method of condition 14 (Condition Number 14) of JIS K7210.

(2) Ethylene and 1-butene content (unit: wt%)
Measurement was performed in accordance with a quantitative method by IR spectrum described in pages 616 to 619 of Polymer Handbook (1995, published by Kinokuniya Shoten).

(3) Melting point (Tm, unit: ° C)
The resin was hot-pressed (preheated at 230 ° C for 5 minutes, pressured up to 50 kgf / cm ² G over 3 minutes, held for 2 minutes, then cooled at 30 ° C and 30 kgf / cm ² G for 5 minutes) A 0.5 mm sheet was prepared, and a 10 mg sheet was heat-treated at 220 ° C. for 5 minutes in a nitrogen atmosphere using a differential scanning calorimeter (manufactured by PerkinElmer, Inc., model DSC-7). Cool to 150 ° C., hold at 150 ° C. for 1 minute, further cool to 50 ° C. at a cooling rate of 50 ° C./minute, hold at 50 ° C. for 1 minute, and then increase the temperature from 50 ° C. to 180 ° C. to 5 ° C./minute In the melting curve obtained when heated at 1, the temperature showing the maximum peak was measured.

(4) Transparency of sheet (haze, unit:%)
It measured according to JIS K7105.

(5) Sheet rigidity (Young's modulus, unit: MPa)
It measured according to JIS K7113.

(6) Transparency of container (haze, unit:%)
It measured according to JISK7105 using the test piece cut out from the trunk | drum center of the polypropylene resin container obtained by pressure forming.

(7) Rigidity of container (Young's modulus, unit: MPa)
It measured according to JISK7113 using the test piece cut out from the trunk | drum center of the polypropylene resin container obtained by pressure forming.

(8) Deformation amount of container (unit: mm)
For the amount of deformation of the container, measure the maximum and minimum diameters of the opening of the polypropylene resin container obtained by pressure forming, and obtain the difference (maximum diameter of the container opening-minimum diameter, unit: mm) It was. If the amount of deformation of the container is large, the design of the container may deteriorate.

(Producing method of propylene polymer (A))
Using the catalyst system obtained by the method described in Example 1 of JP-A-7-216017, as the catalyst conditions, the Al / Ti molar ratio is 600, the cyclohexylethyldimethoxysilane (Z) / Ti molar ratio is 40, As polymerization conditions, the polymerization temperature was 84 ° C., the polymerization pressure was 1.8 MPa, the feed amount of ethylene (unit: Kg) to the total feed amount (unit: Ton) of propylene, ethylene and 1-butene was 8 kg / Ton, The feed amount of 1-butene relative to the feed amount is 36 kg / Ton, the hydrogen concentration is 1.25 vol% (volume%), the ethylene concentration is 0.6 vol% (volume%), and the 1-butene concentration is 4.3 vol% (volume) Propylene, ethylene, 1-butene and hydrogen to feed propylene, ethylene and 1-butene. The by copolymerizing at gas phase polymerization, propylene below - to obtain ethylene-1-butene copolymer (A-1).
(A-1) Propylene-ethylene-1-butene copolymer MFR is 7.0 g / 10 min, Tm is 148 ° C., ethylene content is 1.0% by weight, and 1-butene content is It was 4.2% by weight.

[Producing method of propylene polymer (B)]
Using the catalyst system obtained by the method described in Example 1 of JP-A-7-216017, as the catalyst conditions, the Al / Ti molar ratio is 140, and the cyclohexylethyldimethoxysilane (Z) / Ti molar ratio is 0.4. As polymerization conditions, the polymerization temperature is 84 ° C., the polymerization pressure is 2.1 MPa, the feed amount of ethylene (unit: Kg) to the total feed amount of propylene and ethylene (unit: Ton) is 5.3 kg / Ton, hydrogen Propylene, ethylene and hydrogen are fed so that the concentration becomes 0.06 vol% (volume%) and the ethylene concentration becomes 0.29 vol% (volume%), and propylene and ethylene are copolymerized by gas phase polymerization. The following propylene-ethylene copolymer (B-1) was obtained.
(B-1) Propylene-ethylene copolymer MFR was 1.5 g / 10 min, Tm was 162 ° C., and the ethylene content was 0.3% by weight.

[Aromatic phosphoric acid ester compounds]
Adeka stub NA71 (trade name) manufactured by ADEKA Corporation, where M ^{1 of} formula (I) is lithium, or ADEKA stub NA21 (trade name) manufactured by ADEKA, where M ^{1 of} formula (I) is aluminum is used. It was.

Comparative Example A
From propylene-ethylene-1-butene copolymer (A-1) 90 parts by weight as propylene-based polymer, ethylene content 0.3 parts by weight propylene-ethylene copolymer (B-1) 10 parts by weight 100 parts by weight of the resin component, aromatic phosphate ester compounds made by ADEKA Corporation, Adeka Stub NA21 (trade name) 0.20 parts by weight, calcium stearate as a chlorine supplement, 0.05 parts by weight, oxidized 3/1 mixture of tris (2,4-t-butylphenyl) phosphite / tetrakis [methylene-3 (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane) as inhibitor 0.255 parts by weight, and after mixing for 3 minutes with a Henschel mixer in a nitrogen atmosphere, using an extrusion granulator with a screw diameter of 65 mmφ, Pellets were obtained by melt-kneading at 250 ° C. The MFR of the obtained pellet was 6.8 g / 10 minutes.
Using a T-die sheet processing machine (die width 450 mm), the pellets obtained above were extruded under the conditions of a screw diameter of 65 mmφ, a cylinder temperature of 250 ° C., a die temperature of 250 ° C., a take-off speed of 1.8 m / min, and a cooling roll temperature of 60 ° C. Then, an extruded sheet (thickness: 1.65 mm, width: 45 cm) was molded and the physical properties were measured. The results are shown in Table 1.
Using a drink cup-shaped female mold with an opening diameter of 93 mmφ, a depth of 116 mm, and a bottom diameter of 55.1 mm, the pressure was obtained under the conditions of 0.3 MPa and far-infrared heater temperature of 350 ° C. The extruded sheet thus obtained was subjected to pressure forming to obtain a polypropylene resin container as a secondary molded body. The physical properties of the polypropylene resin container were measured using a test piece cut from the center of the trunk of the polypropylene resin container, which was the obtained secondary molded body. The maximum diameter and the minimum diameter of the opening of the container were measured, and the difference (maximum diameter of the opening of the container−minimum diameter, unit: mm) was determined as the deformation amount of the container. The results are shown in Table 1.

Comparative Example B
Except for changing ADEKA STAB NA21 of aromatic phosphate ester compounds to 0.10 parts by weight, pelletizing was performed in the same manner as in Comparative Example A (MFR = 6.6 g / 10 min), and a sheet and a container were molded, and physical properties were measured. did. The results are shown in Table 1.

Comparative Example C
The propylene-ethylene-1-butene copolymer (A-1) was changed to 70 parts by weight and the propylene-ethylene copolymer (B-1) was changed to 30 parts by weight, and the copolymer (A-1) and the copolymer ( B-1) 0.10 parts by weight of an aromatic phosphate ester compound ADK STAB NA21 and 2,5-dimethyl-2,5-di ( Except that t-butylperoxy) hexane was changed to 0.08 parts by weight, it was pelletized in the same manner as in Comparative Example A (MFR = 6.5 g / 10 min), a sheet and a container were molded, and physical properties were measured. The results are shown in Table 1.

Comparative Example D
Propylene-ethylene-1-butene copolymer (A-1) 50 parts by weight, propylene-ethylene copolymer (B-1) 50 parts by weight, copolymer (A-1) and copolymer ( B-1) 0.10 parts by weight of an aromatic phosphate ester compound ADK STAB NA21 and 2,5-dimethyl-2,5-di ( Except that t-butylperoxy) hexane was changed to 0.13 parts by weight, it was pelletized in the same manner as in Comparative Example A (MFR = 6.3 g / 10 min), a sheet and a container were molded, and physical properties were measured. The results are shown in Table 1.

Example 5
The propylene-ethylene-1-butene copolymer (A-1) was changed to 70 parts by weight and the propylene-ethylene copolymer (B-1) was changed to 30 parts by weight, and the copolymer (A-1) and the copolymer ( B-1) 0.10 parts by weight of an aromatic phosphate ester compound ADK STAB NA71 and 2,5-dimethyl-2,5-di ( Except that t-butylperoxy) hexane was changed to 0.08 parts by weight, it was pelletized in the same manner as in Comparative Example A (MFR = 6.3 g / 10 min), a sheet and a container were molded, and physical properties were measured. The results are shown in Table 1.

Example 6
The propylene-ethylene-1-butene copolymer (A-1) was changed to 70 parts by weight and the propylene-ethylene copolymer (B-1) was changed to 30 parts by weight, and the copolymer (A-1) and the copolymer ( B-1) 0.02 parts by weight of Adekastab NA71, an aromatic phosphate ester compound, and 2,5-dimethyl-2,5-di (2) as an organic peroxide with respect to 100 parts by weight of the total weight of each. Except that t-butylperoxy) hexane was changed to 0.08 parts by weight, it was pelletized in the same manner as in Comparative Example A (MFR = 6.4 g / 10 min), a sheet and a container were molded, and physical properties were measured. The results are shown in Table 2.

Example 7
The propylene-ethylene-1-butene copolymer (A-1) was changed to 70 parts by weight and the propylene-ethylene copolymer (B-1) was changed to 30 parts by weight, and the copolymer (A-1) and the copolymer ( B-1) 0.04 parts by weight of an aromatic phosphate ester compound ADK STAB NA71 and 2,5-dimethyl-2,5-di (2) as an organic peroxide with respect to 100 parts by weight of the total weight of each. Except that t-butylperoxy) hexane was changed to 0.08 parts by weight, it was pelletized in the same manner as in Comparative Example A (MFR = 6.3 g / 10 min), a sheet and a container were molded, and physical properties were measured. The results are shown in Table 2.

Example 8
Propylene-ethylene-1-butene copolymer (A-1) 50 parts by weight, propylene-ethylene copolymer (B-1) 50 parts by weight, copolymer (A-1) and copolymer ( B-1) 0.04 parts by weight of an aromatic phosphate ester compound ADK STAB NA71 and 2,5-dimethyl-2,5-di (2) as an organic peroxide with respect to 100 parts by weight of the total weight of each. Except that t-butylperoxy) hexane was changed to 0.13 parts by weight, it was pelletized in the same manner as in Comparative Example A (MFR = 5.6 g / 10 min), a sheet and a container were molded, and physical properties were measured. The results are shown in Table 2.

Comparative Example 1
Propylene-ethylene-1-butene copolymer (A-1) 40 parts by weight, propylene-ethylene copolymer (B-1) 60 parts by weight, copolymer (A-1) and copolymer ( B-1) 0.10 parts by weight of an aromatic phosphate ester compound ADK STAB NA21 and 2,5-dimethyl-2,5-di ( Except that t-butylperoxy) hexane was changed to 0.16 parts by weight, it was pelletized in the same manner as in Comparative Example A (MFR = 6.2 g / 10 min), a sheet and a container were molded, and physical properties were measured. The results are shown in Table 3.

Comparative Example 2
Propylene-ethylene-1-butene copolymer (A-1) 30 parts by weight, propylene-ethylene copolymer (B-1) 70 parts by weight, copolymer (A-1) and copolymer ( B-1) 0.10 parts by weight of an aromatic phosphate ester compound ADK STAB NA21 and 2,5-dimethyl-2,5-di ( Except that t-butylperoxy) hexane was changed to 0.18 parts by weight, it was pelletized in the same manner as in Comparative Example A (MFR = 5.9 g / 10 min), a sheet and a container were molded, and physical properties were measured. The results are shown in Table 3.

Comparative Example 3
Propylene-ethylene-1-butene copolymer (A-1) 40 parts by weight, propylene-ethylene copolymer (B-1) 60 parts by weight, copolymer (A-1) and copolymer ( B-1) 0.10 parts by weight of an aromatic phosphate ester compound ADK STAB NA71 and 2,5-dimethyl-2,5-di ( Except that t-butylperoxy) hexane was changed to 0.15 parts by weight, it was pelletized in the same manner as in Comparative Example A (MFR = 5.9 g / 10 min), a sheet and a container were molded, and physical properties were measured. The results are shown in Table 3.

Comparative Example 4
Propylene-ethylene-1-butene copolymer (A-1) 30 parts by weight, propylene-ethylene copolymer (B-1) 70 parts by weight, copolymer (A-1) and copolymer ( B-1) 0.04 parts by weight of an aromatic phosphate ester compound ADK STAB NA71 and 2,5-dimethyl-2,5-di (2) as an organic peroxide with respect to 100 parts by weight of the total weight of each. Except that t-butylperoxy) hexane was changed to 0.19 parts by weight, it was pelletized in the same manner as in Comparative Example A (MFR = 5.2 g / 10 min), a sheet and a container were molded, and physical properties were measured. The results are shown in Table 3.

The polypropylene resin containers of Examples 5 to 8 that satisfy the requirements of the present invention are excellent in rigidity and transparency, and the deformation of the container is suppressed as compared with Comparative Examples 1 to 4 that do not satisfy the requirements of the present invention. You can see that.
Then, when Adegas tub NA71 is used as the aromatic phosphate compound, it can be seen that the amount of deformation of the polypropylene resin container is further reduced when the blending amount is reduced (Examples 6 to 8).

Claims (3)

A resin component containing 50 to 99.5% by weight of the following propylene polymer (A) and 0.05 to 50% by weight of the following propylene polymer (B) (however, the polymer (A) and the heavy 0.01 to 1 part by weight of the aromatic phosphate compound represented by the following formula (I) with respect to 100 parts by weight of the resin component) A polypropylene resin composition.
Propylene polymer (A): A propylene polymer having a melting point (Tm) of 100 to 149 ° C. and a melt flow rate (MFR) of 1 to 10 g / 10 min.
Propylene polymer (B): A propylene homopolymer or a propylene-ethylene copolymer having a propylene content of 99.6 to 99.99% by weight and an ethylene content of 0.01 to 0.4% by weight. A polymer (provided that the total of propylene content and ethylene content is 100% by weight), melting point (Tm) is 150 to 165 ° C., and melt flow rate (MFR) is 1 to 10 g / 10 min. A propylene polymer.

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, and an aryl group. or table to an aralkyl group.) A polypropylene resin sheet comprising the polypropylene resin composition according to claim 1. A polypropylene resin container obtained by thermoforming the polypropylene resin sheet according to claim 2 .