JP2009144147A - Propylene resin composition for 1 piece resin cap - Google Patents

Abstract

A 1P resin that satisfies the basic properties of a cap, such as good wrapping properties, sealing properties, unplugging properties, rigidity, and impact resistance, and that does not impair the appearance of the cap such as color unevenness or impair the flavor of the contents. A propylene-based resin composition for 1P resin cap that can provide a cap and a 1P resin cap obtained by molding the same are provided.
A propylene resin composition for a 1P resin cap is obtained by polymerizing a crystalline propylene polymer component and then successively polymerizing a propylene / α-olefin random copolymer component. A propylene-based block copolymer satisfying a content of 1 to 24% by weight, a flexural modulus (X) of 900 to 1600 MPa, an MFR of 0.5 to 100 g / 10 min, and a weight average molecular weight of the copolymer component (Y) ≦ −1670X + 2804000 Shall be used.
[Selection figure] None

Description

  The present invention relates to a propylene-based resin composition for a one-piece resin cap and a one-piece resin cap obtained by molding the same, and more specifically, good wrapping property, sealing property, opening property, rigidity, impact resistance. Propylene resin composition for one-piece resin caps that can provide a one-piece resin cap that satisfies the basic characteristics of the cap such as fragility and that is difficult to cause appearance defects such as color unevenness and flavor of the contents, and A one-piece resin cap obtained by molding is provided.

In recent years, caps used for beverage bottles and the like have become mainstream in place of metal lids such as aluminum from the viewpoint of cost reduction. The type of resin cap is mainly a two-piece cap (hereinafter also referred to as 2P) with a sealing material (liner) affixed to the inside of the cap, or a one-piece seal (hereinafter also referred to as 1P) without using a liner. .) There is a cap. As the resin, polypropylene (PP) or polyethylene (HDPE, LDPE, LLDPE) is preferably used.
Until now, 2P resin caps have been the mainstream, but at present, there is no need for a process such as attaching a sealing material, and there is a shift to 1P resin caps that have the advantage of being manufactured at low cost. FIG. 1 shows a schematic cross-sectional view of an example of a typical 1P resin cap. The 1P resin cap is sealed by inserting the bottle body opening between the inner ring and the outer ring of the cap. At this time, since the sealing cannot be guaranteed unless the top of the main body is in close contact with the seal part on the inner surface of the cap, it is necessary to increase the opening torque when the cap is tightened into the bottle main body for materials with poor winding properties. There was a problem that it was difficult to open. In order to improve this, it is the actual situation that an appropriate amount of lubricant is generally added.

Up to now, as resin caps and related resins and polymers, heat-sterilizable resin caps (for example, see Patent Document 1), propylene polymers for container lids (for example, see Patent Document 2), propylene resin compositions (See, for example, Patent Documents 3 and 4).
In such a conventional technique, for example, as shown in Patent Document 4, in the case of a 1P resin cap, if polyethylene is not added, appropriate tightening property, sealing property, openability, rigidity, impact resistance, etc. The basic characteristics of the cap could not be satisfied. However, when polyethylene is added, the dispersibility of polyethylene in polypropylene is not good, so if the appearance of the cap such as color unevenness due to the addition of polyethylene is impaired or the molding cycle is poor There is a need for improvement. In addition, the lubricant is an additive that easily bleeds, but in the case of a 1P resin cap, since it comes into direct contact with the content liquid, there is a possibility of bleeding and damaging the flavor of the content, and it is required to reduce it as much as possible. Yes.

JP 2002-68282 A JP 7-316229 A JP 2004-182955 A JP 2005-314474 A

  Under these circumstances, the present invention satisfies the basic characteristics of the cap such as good tightening performance, sealing performance, openability, rigidity, and impact resistance, and causes the appearance and content of the cap such as color unevenness. It is an object of the present invention to provide a one-piece resin cap for a one-piece resin cap that can provide a one-piece resin cap that hardly impairs the flavor of a product, and a one-piece resin cap obtained by molding the same.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a desired problem can be obtained by using a specific propylene-based block copolymer for a one-piece resin cap propylene-based resin composition. The present invention has been found out, and the present invention has been made based on this finding.

That is, according to the first invention of the present invention, after polymerizing the crystalline propylene polymer component, it is obtained by continuously polymerizing the propylene / α-olefin random copolymer component, and the following characteristics (1) to A propylene-based resin composition for a one-piece resin cap containing a propylene-based block copolymer satisfying (4) is provided.
(1) The content of α-olefin is 1 to 24% by weight
(2) The flexural modulus measured based on JIS K6921 is 900 to 1600 MPa.
(3) Melt flow rate measured based on JIS K7210 (230 ° C., 2.16 kg load) is 0.5 to 100 g / 10 min. (4) Weight average molecular weight of propylene / α-olefin random copolymer component ( The relationship between Y) and the flexural modulus (X) measured based on JIS K6921 is a range represented by the following mathematical formula (A).
[Equation 1]
Y ≦ −1670X + 2804000 (A)
(However, Y ≧ 100000)

（式中、Ｒ^１は直接結合、硫黄又は炭素数１〜９のアルキレン基又はアルキリデン基であり、Ｒ^２及びＲ^３は水素原子又は炭素数１〜８のアルキル基であり、Ｍはアルカリ金属またはアルカリ土類金属であり、ｎはＭの価数である。）

（式中、Ｒ^１は水素原子又は炭素数１〜４のアルキル基を示し、Ｒ^２及びＲ^３は水素原子又は炭素数１〜１２のアルキル基を示し、Ｍは周期律表第ＩＩＩ族または第ＩＶ族の金属原子を示し、ＸはＭが周期律表第ＩＩＩ族の金属原子を示す場合には、ＨＯ−を示し、Ｍが周期律表第ＩＶ族の金属原子を示す場合には、Ｏ＝又は（ＨＯ）_２−を示す。）

［式中、Ｍ_１およびＭ_２は、同一または異なって、カルシウム、ストロンチウム、リチウムおよび一塩基性アルミニウムから選択される少なくとも１種の金属カチオンであり、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_９およびＲ_１０は、同一または異なって、水素、炭素数１〜９のアルキル基（ここで、いずれか２つのビシナルまたはジェミナルアルキル基は、一緒になって６個までの炭素原子を有する炭化水素環を形成してもよい）、ヒドロキシ基、炭素数１〜９のアルコキシ基、炭素数１〜９のヒドロキシアルキル基、アミノ基、炭素数１〜９のアルキルアミノ基、ハロゲン及びフェニル基から選択される少なくとも１種の置換基を示す。］ According to the second invention of the present invention, in the first invention, 0.01 to 0.4% by weight of at least one nucleating agent represented by the following formulas (1) to (3): A propylene-based resin composition for a one-piece resin cap, which is blended, is provided.

(In the formula, R ¹ is a direct bond, sulfur, a C 1-9 alkylene group or an alkylidene group, R ² and R ³ are a hydrogen atom or a C 1-8 alkyl group, and M is an alkali metal. Or an alkaline earth metal, where n is the valence of M.)

(Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² and R ³ represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and M represents group III of the periodic table or Represents a group IV metal atom, X represents HO— when M represents a group III metal atom of the periodic table, and M represents a group IV metal atom of the periodic table, O = or (HO) ₂ − is indicated.)

[Wherein, M ₁ and M ₂ are the same or different and are at least one metal cation selected from calcium, strontium, lithium and monobasic aluminum, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same or different and each represents hydrogen, an alkyl group having 1 to 9 carbon atoms (wherein any two vicinal or geminal alkyl groups are Together, a hydrocarbon ring having up to 6 carbon atoms may be formed), a hydroxy group, an alkoxy group having 1 to 9 carbon atoms, a hydroxyalkyl group having 1 to 9 carbon atoms, an amino group, carbon The at least 1 sort (s) of substituent selected from the alkylamino group of number 1-9, a halogen, and a phenyl group is shown. ]

  According to the third invention of the present invention, in the first or second invention, the propylene-based resin composition for a one-piece resin cap is characterized in that the lubricant is further blended in a range of 1% by weight or less. Things are provided.

  According to a fourth aspect of the present invention, in any one of the first to third aspects, the polyethylene is further blended in an amount of less than 5 parts by weight based on 100 parts by weight of the propylene-based block copolymer. A propylene-based resin composition for a one-piece resin cap is provided.

  According to a fifth aspect of the present invention, there is provided a one-piece resin cap obtained by molding a propylene-based resin composition for a one-piece resin cap in any one of the first to fourth aspects. Provided.

  According to a sixth aspect of the present invention, there is provided the one-piece resin cap according to the fifth aspect, wherein the molding is compression molding.

  According to a seventh aspect of the present invention, there is provided the one-piece resin cap according to the fifth aspect, wherein the molding is injection molding.

According to the propylene-based resin composition for a one-piece resin cap of the present invention, the basic properties of the cap such as good wrapping properties, sealing properties, unplugging properties, rigidity, and impact resistance are satisfied. There is an advantage that it is possible to provide a one-piece resin cap that hardly deteriorates the appearance and the flavor of the contents.
Further, since the one-piece resin cap of the present invention is obtained by molding the above resin composition, it satisfies the basic properties of the cap such as good winding properties, sealing properties, unplugging properties, rigidity, impact resistance, It has an advantage that the appearance of the cap such as color unevenness is hardly generated and the flavor of the contents is hardly impaired.

The propylene-based resin composition for a one-piece resin cap of the present invention (hereinafter also referred to as a propylene-based resin composition for a 1P resin cap) is obtained by polymerizing a crystalline propylene polymer component and then continuously propylene / α-olefin random A propylene-based block copolymer obtained by polymerizing a copolymer component and satisfying the following characteristics (1) to (4) is used.
(1) The content of α-olefin is 1 to 24% by weight
(2) The flexural modulus measured based on JIS K6921 is 900 to 1600 MPa.
(3) Melt flow rate measured based on JIS K7210 (230 ° C., 2.16 kg load) is 0.5 to 100 g / 10 min. (4) Weight average molecular weight of propylene / α-olefin random copolymer component ( The relationship between Y) and the flexural modulus (X) measured based on JIS K6921 is a range represented by the following mathematical formula (A).
[Equation 1]
Y ≦ −1670X + 2804000 (A)
(However, Y ≧ 100000)
Hereinafter, the components constituting the propylene-based resin composition for 1P resin cap of the present invention (this may be abbreviated as the present propylene-based resin composition), the production method thereof, and the like will be described in detail.

1. Propylene-based block copolymer The propylene-based block copolymer used in the present propylene-based resin composition is obtained by polymerizing a crystalline propylene polymer component and then continuously polymerizing a propylene / α-olefin random copolymer component. Obtained. The crystalline propylene polymer component and the propylene / α-olefin random copolymer component may be polymerized in a single stage or in multiple stages.
Such a propylene-based block copolymer is composed of two or more crystalline propylene polymer components and two or more propylene / α-olefin random copolymer components as long as the effects of the present invention are not impaired. May be.

(Crystalline propylene polymer component)
The crystalline propylene polymer component is obtained by homopolymerizing propylene, and is selected from a very small amount such as 2 or less and 4 to 20 carbon atoms of 0.5 wt% or less, so long as the crystallinity is not lost. One or more comonomers may be copolymerized.
The proportion of the crystalline propylene polymer component in the propylene-based block copolymer is not particularly limited, but is preferably 70 to 95% by weight, more preferably 75 to 93% by weight, and particularly preferably 80 to 90% by weight. If it is less than 70% by weight, sufficient rigidity cannot be obtained. Conversely, if it exceeds 95% by weight, sufficient impact resistance may not be obtained.
Further, the crystalline propylene polymer component is not particularly limited, but the isotactic pentad fraction ([mmmm]), which is a measure of crystallinity, is 90% or more, preferably 95% or more, more preferably 96% or more. However, if it is significantly lower than 90%, the balance between rigidity and impact resistance is deteriorated, and the basic characteristics of the cap may not be satisfied.

(Propylene / α-olefin random copolymer component)
Examples of the α-olefin used in the propylene / α-olefin random copolymer component include α-olefins having 2 to 20 carbon atoms excluding propylene, such as ethylene, butene-1, hexene-1, and octene-1. It can be illustrated. One or more α-olefins may be used. Of these, ethylene and butene-1 are preferable, and ethylene is more preferable.
The content of α-olefin in the propylene / α-olefin random copolymer component is preferably 15 to 85% by weight, more preferably 15 to 45% by weight or 55 to 85% by weight, particularly preferably 55 to 75% by weight. It is. If it is less than 15% by weight, sufficient impact resistance cannot be obtained, and if it exceeds 45% by weight and less than 55% by weight, the force for opening the plug (opening torque) becomes too low, which is problematic in actual use. Occurs. On the other hand, if it exceeds 85% by weight, impact resistance cannot be obtained. Therefore, 55 to 75% by weight considering all balances is particularly preferable. When the α-olefin content is more than 45% by weight and less than 55% by weight, the opening force (opening torque) at the time of high temperature use at 40 to 60 ° C. becomes low, which may cause a problem in actual use. The reason why the opening torque decreases when it exceeds 45% by weight and less than 55% by weight is that the propylene / α-olefin random copolymer component in this region is the softest and its physical properties are highly dependent on heat. As a countermeasure, it is conceivable to adjust the α-olefin content. This value is less likely to be affected by heat as it becomes 50% by weight as a starting point. Further, as a measure other than adjusting the content of α-olefin used in the propylene / α-olefin random copolymer component, addition of high-density polyethylene can be mentioned. When high-density polyethylene is added, the propylene / α-olefin random copolymer component is selectively incorporated into the propylene / α-olefin random copolymer component, and the decrease in rigidity due to heat of the propylene / α-olefin random copolymer component is reduced. Reduction is suppressed. In addition, by adding high-density polyethylene, the 1P cap can be tightened and opened easily, but this is also selectively incorporated into the propylene / α-olefin random copolymer component. It is considered that the apparent MFR of this component is changed, thereby reducing the surface hardness of the molded product cap. However, the addition amount of the high-density polyethylene is preferably less than 5 parts by weight with respect to 100 parts by weight of the propylene-based block copolymer from the viewpoint of uneven color of the molded product cap.
Further, the weight average molecular weight of the propylene / α-olefin random copolymer component (hereinafter sometimes referred to as “CopyMw”) is 100,000 or more, and if it is less than 100,000, there is a possibility that a cap having sufficient impact resistance cannot be obtained. is there. The CopolyMw is preferably 250,000 or more, and if it is less than 250,000, there is a possibility that the band part for preventing tampering of the cap will be stretched at the time of opening and the cutting performance will be deteriorated.

(Propylene block copolymer)
The propylene-based block copolymer has an α-olefin content of 1 to 24% by weight, preferably 4 to 20% by weight, more preferably 8 to 12% by weight.
When the α-olefin content is less than 1% by weight, the impact resistance is lowered, and when it exceeds 24% by weight, the rigidity is lowered.
The content of α-olefin is measured by ¹³ C-NMR.
The propylene block copolymer has a melt flow rate measured based on JIS K7210 (230 ° C., 2.16 kg load) of 0.5 to 100 g / 10 minutes, preferably 2.0 to 50 g / 10. In terms of the balance between moldability and physical properties, more preferably in the range of 2.0-30 g / 10 min, even more preferably 3-20 g / 10 min, especially 8-15 g / 10 min. Good at.
If the melt flow rate is less than 0.5 g / 10 min, molding processability may be deteriorated and it may be difficult to obtain a satisfactory product, and if it exceeds 100 g / 10 min, impact resistance is reduced. The physical property balance becomes worse.

The propylene block copolymer has a flexural modulus measured based on JIS K6921 of 900 to 1600 MPa, preferably 1000 to 1500 MPa, more preferably 1100 to 1500 MPa.
When the flexural modulus is significantly below 900 MPa, when the internal pressure in the bottle rises due to a decrease in rigidity, a phenomenon called blow-off in which the cap comes off occurs, which is not suitable as a cap. When the elastic modulus greatly exceeds 1600 MPa, not only the cap tightening property is deteriorated, but also the impact resistance is lowered.
The propylene-based block copolymer has a relationship between the flexural modulus (X) and CopyMw (Y) in the range represented by the following formula (A).
[Equation 1]
Y ≦ −1670X + 2804000 (A)
(However, Y ≧ 100000)

The 1P resin cap is required to have performances such as a tightening property, a sealing property, and an opening property. If these performances are high, a 1P resin cap that is good as a product can be obtained. And it is understood that these performances can be judged as good or bad by the relationship between CopyMw and flexural modulus. The relationship between the PolyMw and the flexural modulus of the propylene-based block copolymer used in the examples described later is plotted in FIG. 3, and the 1P resin cap obtained by the copolymer has a tightness, a sealing property and an opening property. A sample having a good overall evaluation was rated as ◯, and a sample having a poor evaluation as ×. And from the result, when CopolMw is (Y) and bending elastic modulus (X),
Y = −1670X + 2804000
From the relational expression, it was found that the comprehensive evaluation of the tightening property, the sealing property, and the plugging property can be clearly separated from the good range and the poor range. In general, it was thought that the cap closed tightly when the bending elastic modulus (rigidity) is lowered, that is, the tightening property is improved. However, the goodness of the tightening property is not only a problem of the bending elastic modulus. It can be seen that it is important to make appropriate adjustments in relation to In other words, if a propylene-based block copolymer is used in which CopolyMw (Y) deviates from the range of the formula (A), a defect occurs in the tightening property as a 1P resin cap, and defective products that are not completely sealed It may occur or the openability may deteriorate.

  Further, the copy Mw (Y) is preferably 100,000 or more, more preferably 200,000 or more, and more preferably 250,000 or more. If the copy Mw (Y) is less than 100,000, there is a possibility that sufficient impact resistance cannot be obtained for the obtained cap.

(Propylene block copolymer production method)
The propylene-based block copolymer can be obtained by polymerizing a propylene homopolymer which is a crystalline propylene polymer portion (previous stage) and then polymerizing a propylene / α-olefin random copolymer portion (post stage). it can.

  The catalyst used for the polymerization is not particularly limited, and a known catalyst can be used. For example, a so-called Ziegler-Natta catalyst or a metallocene catalyst (for example, JP-A-5-295022) in which a titanium compound and organic aluminum are combined can be used. Since a propylene block copolymer having a good balance between rigidity and impact resistance is good, a Ziegler-Natta catalyst having high stereoregularity is generally more preferable. The Ziegler-Natta catalyst is a titanium trichloride or titanium trichloride composition obtained by reduction with organoaluminum as a titanium compound, which is further activated by treatment with an electron donating compound (for example, JP-A-47-34478, JP-A-58-23806, JP-A-63-146906), a so-called supported catalyst obtained by supporting titanium tetrachloride on a carrier such as magnesium chloride (for example, JP-A-58-157808, JP-A-58-58). 83006, JP 58-5310, JP 61-218606) and the like. As these catalysts, known catalysts can be used without any particular limitation.

  An organoaluminum compound is used as a cocatalyst. For example, trialkylaluminum such as trimethylaluminum, triethylaluminum and triisobutylaluminum, alkylaluminum halide such as diethylaluminum chloride and diisobutylaluminum chloride, alkylaluminum hydride such as diethylaluminum hydride, alkylaluminum alkoxide such as diethylaluminum ethoxide, methyl Examples include alumoxanes such as alumoxane and tetrabutylalumoxane, and complex organoaluminum compounds such as dibutyl methylboronate and lithium aluminum tetraethyl. It is also possible to use a mixture of two or more of these.

  In addition, various polymerization additives for the purpose of improving stereoregularity, controlling particle properties, controlling soluble components, controlling molecular weight distribution, and the like can be used for the above-described catalyst. For example, organic silicon compounds such as diphenyldimethoxysilane and tert-butylmethyldimethoxysilane, esters such as ethyl acetate, butyl benzoate, methyl p-toluate and dibutyl phthalate, ketones such as acetone and methyl isobutyl ketone, diethyl ether And electron donating compounds such as ethers such as benzoic acid and propionic acid, and alcohols such as ethanol and butanol.

  As polymerization methods, slurry polymerization using an inert hydrocarbon such as hexane, heptane, octane, benzene or toluene as a polymerization solvent, bulk polymerization using propylene itself as a polymerization solvent, or polymerization of propylene as a raw material in a gas phase state. Gas phase polymerization is possible. Moreover, it can also carry out combining any polymerization form. For example, a method in which a crystalline propylene polymer is bulk-polymerized and a propylene / α-olefin random copolymer is vapor-phase polymerized, or a crystalline propylene polymer is bulk-polymerized, followed by gas-phase polymerization, Examples of the α-olefin random copolymer include a method performed by gas phase polymerization. Since the propylene block copolymer requires the weight average molecular weight of the propylene / α-olefin random copolymer component to satisfy Formula (A), the propylene / α-olefin random copolymer portion is propylene as a polymerization solvent. -It is preferable to carry out by vapor phase polymerization in which the α-olefin random copolymer is difficult to dissolve.

Further, the polymerization mode may be any of batch type, continuous type and semi-batch type. The polymerization reactor is not particularly limited in shape and structure, but a tank with a stirrer generally used in slurry polymerization and bulk polymerization, a tube reactor, a fluidized bed reactor generally used in gas phase polymerization, and a stirring blade A horizontal reactor having
In the gas phase polymerization, the polymerization step of the propylene homopolymer portion supplies propylene and hydrogen as a chain transfer agent, and the temperature is 50 to 150 ° C., preferably 50 to 90 ° C., and the partial pressure of propylene in the presence of the catalyst. The residence time is 2 to 10 hours, preferably 2 to 5 hours under the condition of 0.5 to 4.5 MPa, preferably 1.0 to 3.0 MPa. The crystalline propylene polymer portion may be copolymerized with an α-olefin other than propylene as long as the effects of the present invention are not impaired.

  Subsequently, in the subsequent polymerization step, propylene, α-olefin and hydrogen are supplied, and in the presence of the catalyst (the catalyst used in the polymerization step of the propylene homopolymer portion), a temperature of 50 to 150 ° C., preferably Propylene and α-olefin are randomly copolymerized under conditions of 50 to 80 ° C., partial pressure of propylene and α-olefin of 0.5 to 4.5 MPa, preferably 1.0 to 3.0 MPa. -An olefin random copolymer part is manufactured and a propylene block copolymer is obtained as a final product. The propylene / α-olefin random copolymer portion may be copolymerized with olefin other than propylene and α-olefin within a range not impairing the effects of the present invention.

The propylene-based resin composition is mainly composed of the propylene-based block copolymer, but preferably contains a nucleating agent and a lubricant, and further within the range not impairing the effects of the present invention. Other resins such as polyethylene and olefin-based elastomers and other various additives may be appropriately blended.
2. Nucleating Agent As the nucleating agent, those represented by the following formulas (1) to (3) are desirable. By blending such a nucleating agent in the present propylene-based resin composition, the composition and the cap formed from the composition are increased in crystallization temperature to further improve the molding cycle property, and excellent in the cap. It gives rigidity, improves sink marks and warpage of the cap, and makes it possible to extremely reduce odor and elution from the cap. Examples of such a nucleating agent include commercially available products such as nucleating agents NA11 and NA21 manufactured by ADEKA Corporation, and nucleating agent HPN68L manufactured by Milliken.
The blending amount of the nucleating agent is 0.01 to 0.4% by weight, preferably 0.03 to 0.2% by weight, more preferably 0.05 to 0% with respect to the propylene resin composition for 1P resin cap. .15% by weight is selected, and if it is less than 0.01% by weight, it is difficult to obtain a sufficient effect, and if it exceeds 0.4% by weight, further improvement in performance cannot be expected. It may become incompatible with the PL standard.

（式中、Ｒ^１は直接結合、硫黄又は炭素数１〜９のアルキレン基又はアルキリデン基であり、Ｒ^２及びＲ^３は水素原子又は炭素数１〜８のアルキル基であり、Ｍはアルカリ金属またはアルカリ土類金属であり、ｎはＭの価数である。）

(In the formula, R ¹ is a direct bond, sulfur, a C 1-9 alkylene group or an alkylidene group, R ² and R ³ are a hydrogen atom or a C 1-8 alkyl group, and M is an alkali metal. Or an alkaline earth metal, where n is the valence of M.)

In the organophosphate metal salt compound represented by the formula (1), M is preferably Na, K, Li, Ca, Mg, Sr, Zn, Cd or the like, and particularly preferably Na or K.
Specific examples of the organophosphate metal salt compound include sodium-2,2′-methylene-bis- (4,6-di-t-butylphenyl) phosphate, sodium-2,2′-ethylidene-bis- (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis- (4-i-propyl-6-t-butylphenyl) phosphate, sodium-2,2'- Butylidene-bis- (4,6-dimethylphenyl) phosphate, sodium-2,2'-butylidene-bis- (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-t- Octylmethylene-bis- (4,6-methylphenyl) phosphate, sodium-2,2′-t-octylmethylene-bis- (4,6-di-t-butylphenyl) phosphate Sulfate, sodium-2,2′-methylene-bis- (4-methyl-6-tert-butylphenyl) phosphate, sodium-2,2′-methylene-bis- (4-ethyl-6-tert-butylphenyl) ) Phosphate, sodium (4,4′-dimethyl-6,6′-di-t-butyl-2,2′-biphenyl) phosphate, sodium-2,2′-ethylidene-bis- (4-s-) Butyl-6-tert-butylphenyl) phosphate, sodium-2,2′-methylene-bis- (4,6-di-methylphenyl) phosphate, sodium-2,2′-methylene-bis- (4 6-di-ethylphenyl) phosphate, and mixtures of two or more thereof. Of these, sodium-2,2′-methylene-bis- (4,6-di-t-butylphenyl) phosphate is particularly preferable.
A commercially available product can be used as such a nucleating agent. Specifically, NA-11 manufactured by ADEKA Corporation can be mentioned.

（式中、Ｒ^１は水素原子又は炭素数１〜４のアルキル基を示し、Ｒ^２及びＲ^３は水素原子又は炭素数１〜１２のアルキル基を示し、Ｍは周期律表第ＩＩＩ族または第ＩＶ族の金属原子を示し、ＸはＭが周期律表第ＩＩＩ族の金属原子を示す場合には、ＨＯ−を示し、Ｍが周期律表第ＩＶ族の金属原子を示す場合には、Ｏ＝又は（ＨＯ）_２−を示す。）

(Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² and R ³ represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and M represents group III of the periodic table or Represents a group IV metal atom, X represents HO— when M represents a group III metal atom of the periodic table, and M represents a group IV metal atom of the periodic table, O = or (HO) ₂ − is indicated.)

In the aromatic phosphates represented by the formula (2), M is preferably Al, Sn, Pb, Ti, Zr, etc., and particularly preferably Al.
Specific examples of the aromatic phosphate esters include, for example, 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-di-t-butylphenyl) phosphate], and hydroxyaluminum-bis [2 , 2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], Droxyaluminum-bis [2,2′-methylene-bis (4-methyl-6-tert-butylphenyl) phosphate], hydroxyaluminum-bis [2,2′-ethylidene-bis (4-methyl-6- t-butylphenyl) phosphate], hydroxyaluminum-bis [2,2′-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate], hydroxyaluminum-bis [2,2′-ethylidene- Bis (4-ethyl-6-tert-butylphenyl) phosphate], hydroxyaluminum-bis [2,2′-methylene-bis (4-i-propyl-6-tert-butylphenyl) phosphate], hydroxyaluminum -Bis [2,2'-ethylidene-bis (4-i-propyl-6-t-butylphenyl) phosphate Preferably, hydroxyaluminum-bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], and hydroxyaluminum-bis [2,2′-ethylidene- Bis (4,6-di-t-butylphenyl) phosphate], and a mixture of two or more of these.

It is effective to use the aromatic phosphates represented by the formula (2) together with an organic alkali metal salt.
Examples of the organic alkali metal salt include at least one selected from the group consisting of alkali metal carboxylates, alkali metal β-diketonates, and alkali metal β-keto acid ester salts.
Examples of the alkali metal constituting the organic alkali metal salt include lithium, sodium, and potassium.

  Examples of the carboxylic acid constituting the alkali metal carboxylate include acetic acid, propionic acid, acrylic acid, octylic acid, isooctylic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, Fats such as ricinoleic acid, 12-hydroxystearic acid, behenic acid, montanic acid, melicic acid, dodecylthioacetic acid, β-dodecylthiopropionic acid, β-N-laurylaminopropionic acid, β-N-methyl-lauroylaminopropionic acid Aliphatic polycarboxylic acids such as monocarboxylic acid, malonic acid, succinic acid, adipic acid, maleic acid, azelaic acid, sebacic acid, dodecanedioic acid, citric acid, butanetricarboxylic acid, butanetetracarboxylic acid, naphthenic acid, cyclohexane Pentanecarboxylic acid, 1-methylcyclopentane Rubonic acid, 2-methylcyclopentanecarboxylic acid, cyclopentenecarboxylic acid, cyclohexanecarboxylic acid, 1-methylcyclohexanecarboxylic acid, 4-methylcyclohexanecarboxylic acid, 3,5-dimethylcyclohexanecarboxylic acid, 4-butylcyclohexanecarboxylic acid, 4 -Cyclocyclic mono- or polycarboxylic acids such as octylcyclohexanecarboxylic acid, cyclohexenecarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, benzoic acid, toluic acid, xylic acid, ethylbenzoic acid, 4-t-butylbenzoic acid Examples thereof include aromatic mono- or polycarboxylic acids such as acid, salicylic acid, phthalic acid, trimellitic acid, and pyromellitic acid.

  Examples of the β-diketone compound constituting the alkali metal β-diketonate include acetylacetone, pivaloylacetone, palmitoylacetone, benzoylacetone, pivaloylbenzoylacetone, dibenzoylmethane, and the like.

  Examples of the β-keto acid ester constituting the alkali metal β-keto acid ester salt include ethyl acetoacetate, octyl acetoacetate, lauryl acetoacetate, stearyl acetoacetate, ethyl benzoyl acetate, benzoyl acetate lauryl and the like. It is done.

Alkali metal carboxylate, alkali metal β-diketonate or alkali metal β-keto acid ester salt, which is a component of the organic alkali metal salt, is a combination of the above alkali metal and carboxylic acid, β-diketone compound or β-keto acid ester, respectively. It is a salt and can be produced by a conventionally known method. Among these alkali metal salt compounds, alkali metal aliphatic monocarboxylates, particularly lithium aliphatic monocarboxylates are preferable, and aliphatic monocarboxylates having 8 to 20 carbon atoms are particularly preferable.
A commercially available product can be used as such a nucleating agent. Specifically, NA-21 manufactured by ADEKA Corporation can be mentioned.

（式中、Ｍ_１およびＭ_２は、同一または異なって、カルシウム、ストロンチウム、リチウムおよび一塩基性アルミニウムから選択される少なくとも１種の金属カチオンであり、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_９およびＲ_１０は、同一または異なって、水素、炭素数１〜９のアルキル基［ここで、いずれか２つのビシナルまたはジェミナルアルキル基は、一緒になって６個までの炭素原子を有する炭化水素環を形成してもよい）、ヒドロキシ基、炭素数１〜９のアルコキシ基、炭素数１〜９のヒドロキシアルキル基、アミノ基、炭素数１〜９のアルキルアミノ基、ハロゲン及びフェニル基から選択される少なくとも１種の置換基を示す。］
「一塩基性アルミニウム」なる用語は周知であり、２つのカルボン酸基が結合した単一カチオンとしてアルミニウムヒドロキシド基を含むことを意味している。また、ビシナルは隣接炭素に結合することを、ジェミナルは同一炭素に結合することをそれぞれ意味する。
ハロゲンは特に限定されず、フッ素、塩素、臭素または沃素である。さらに、これら可能な塩のそれぞれにおいて、非対称炭素原子の立体配置は、シスまたはトランスのいずれでもよいが、シスが好ましい。

(Wherein M ₁ and M ₂ are the same or different and are at least one metal cation selected from calcium, strontium, lithium and monobasic aluminum, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same or different and each represents hydrogen, an alkyl group having 1 to 9 carbon atoms [wherein any two vicinal or geminal alkyl groups are Together, a hydrocarbon ring having up to 6 carbon atoms may be formed), a hydroxy group, an alkoxy group having 1 to 9 carbon atoms, a hydroxyalkyl group having 1 to 9 carbon atoms, an amino group, carbon The at least 1 sort (s) of substituent selected from the alkylamino group of number 1-9, a halogen, and a phenyl group is shown. ]
The term “monobasic aluminum” is well known and is meant to include an aluminum hydroxide group as a single cation with two carboxylic acid groups attached. In addition, vicinal means to bond to adjacent carbon, and geminal means to bond to the same carbon.
Halogen is not particularly limited, and is fluorine, chlorine, bromine or iodine. Further, in each of these possible salts, the configuration of the asymmetric carbon atom may be either cis or trans, with cis being preferred.

The nucleating agent represented by the formula (3) may be used in combination with other compounds for the purpose of preventing aggregation and the like.
A commercially available product can be used as such a nucleating agent. Specifically, Hyperform HPN68L manufactured by Meriken Co., which has the following formula (4) can be mentioned.

  In formula (4), Metal refers to a monovalent or trivalent metal, of which monovalent is preferred, and a particularly preferred metal is sodium. In the case of a trivalent metal, an aluminum metal containing a hydroxyl group is also possible.

<Other nucleating agents>
In the present propylene-based resin composition, in addition to the nucleating agent represented by the formulas (1) to (4), another nucleating agent is added in an amount not significantly inhibiting the effect of suppressing odor and elution. It can be used together in the range of ˜0.4% by weight.
Other nucleating agents include known nucleating agents such as sorbitol nucleating agents, carboxylate nucleating agents and talc. 1,3,2,4, dibenzylidene sorbitol, which is a sorbitol-based nucleating agent, has a strong odor and may be eluted and precipitated, which is not preferable for a cap for food use.

3. Lubricant In the present propylene-based resin composition, a lubricant can be blended in order to improve the moldability and roll-fastness of the 1P resin cap. Examples of the lubricant include higher fatty acid amides such as oleic acid amide, stearic acid amide, erucic acid amide, aliphatic alcohol, and wax. The amount of lubricant blended is preferably as small as possible in consideration of the risk of affecting the flavor and the like of the contents, and is preferably 1% by weight or less in the 1P resin cap propylene resin composition.

4). Other resin In this propylene-type resin composition, other resin can be mix | blended. Examples of other resins include polyethylene and olefin-based elastomer, among which polyethylene is used. The amount of other resins, especially polyethylene, is preferably less than 5 parts by weight and more preferably less than 3 parts by weight with respect to 100 parts by weight of the propylene-based block copolymer.
However, when this propylene-based resin composition is colored and used as a propylene-based resin composition for a 1P colored resin cap, if the polyethylene is blended, appearance defects such as color unevenness may occur in the cap, or molding cycles Since the properties may deteriorate, it is desirable that the amount of polyethylene is as small as possible.

5). Other additives In the present propylene-based resin composition, various additives used as additives for polypropylene-based resins in addition to the above-described components are blended as necessary within the range not impairing the effects of the present invention. can do.
Examples of such additives include antioxidants, light stabilizers, ultraviolet absorbers, metal fatty acid salts, neutralizing agents, antistatic agents, fillers, pigments and dyes for coloring purposes, and dispersants. Etc.

  Examples of the antioxidant include bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite, di-stearyl-pentaerythritol-di-phosphite, and bis (2,4- Di-t-butylphenyl) pentaerythritol-di-phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′- Phosphorous antioxidants such as biphenylene-diphosphonite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4′-biphenylene-diphosphonite, Di-t-butyl-p-cresol, tetrakis [methylene (3,5-di-t-butyl-4-hydroxyhydrocinnamate)] methane 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxybenzyl) Phenolic antioxidants such as isocyanurates, di-stearyl-ββ'-thio-di-propionate, di-myristyl-ββ'-thio-di-propionate, di-lauryl-ββ'-thio-di-propionate Thio antioxidants, amine antioxidants represented by the following formula (5) and formula (6), 5,7-di-t-butyl-3- (3,4 di-methyl-phenyl)- Examples include lactone antioxidants such as 3H-benzofuran-2-one, and vitamin E antioxidants represented by the following formula (7).

（式中、Ｒ^１及びＲ^２は炭素数１４〜２２のアルキル基である。）

(In the formula, R ¹ and R ² are alkyl groups having 14 to 22 carbon atoms.)

  Examples of the light stabilizer include n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-butyl-4. '-Hydroxybenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl-2-succinate-2- (4-hydroxy-2,2,6,6-tetramethyl-1- Piperidyl) ethanol condensate, poly {[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4diyl] [(2,2,6,6 -Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]}, N, N′-bis (3-aminopropyl) ethylenediamine-2,4 -Bis [N-butyl- - (1,2,2,6,6-pentamethyl-4-piperidyl) amino] such as 6-chloro-1,3,5-triazine condensate, and the like.

  Examples of the ultraviolet absorber include 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- ( 2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole and the like.

  Examples of the metal fatty acid salt include calcium stearate, zinc stearate, magnesium stearate and the like.

  Examples of the neutralizing agent include hydrotalcite (trade name: magnesium aluminum composite hydroxide salt manufactured by Kyowa Chemical Industry Co., Ltd.), Mizukarak (lithium aluminum composite hydroxide salt), and the like.

6). Method for Producing Propylene Resin Composition for 1P Resin Cap The propylene resin composition for 1P resin cap of the present invention comprises a propylene block copolymer as a main composition component and other subordinate composition components such as the nucleation A composition comprising at least one selected from other resins such as additives, lubricants, polyethylene, and other additives, or a plurality of types of propylene-based block copolymers themselves. After mixing with a Henschel mixer, a super mixer, a ribbon blender, etc., an appropriate temperature, preferably in the range of 190 to 260 ° C., with a normal single screw extruder, twin screw extruder, Banbury mixer, Brabender, roll, etc. It can be obtained by melt-kneading at a temperature.

7). Molding of 1P Resin Cap The 1P resin cap is produced by shaping a propylene-based resin composition for 1P resin cap into a desired form by various conventionally known molding methods. As the molding method, an injection molding method, a compression molding method, and an injection compression molding method are particularly preferable because the effects of the present invention can be obtained satisfactorily. Among them, compression molding is particularly preferable from the viewpoints of versatility and productivity.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
In each Example and Comparative Example, the propylene-based polymer used was the propylene-based block copolymer (BPP1-23) obtained in Production Example 1-23 below.

(A) Propylene-based block copolymer Ethylene / propylene block copolymer 1 (BPP1):
(MFR 10 g / 10 min, ethylene concentration 8.5% by weight)
Crystalline propylene polymer component 80.3% by weight
(96% stereoregularity in homo part)
Propylene / α-olefin random copolymer component 19.7% by weight
(Ethylene content: 43.4% by weight, PolyMw: 334000)

Ethylene / propylene block copolymer 2 (BPP2):
(MFR 10 g / 10 min, ethylene concentration 9.9% by weight)
Crystalline propylene polymer component 77.7% by weight
(Homo part stereoregularity 97%)
Propylene / α-olefin random copolymer component 22.3% by weight
(Ethylene content: 44.7% by weight, PolyMw: 290000)

Ethylene / propylene block copolymer 3 (BPP3):
(MFR 10 g / 10 min, ethylene concentration 10.8% by weight)
Crystalline propylene polymer component 75.8% by weight
(Homo part stereoregularity 97%)
Propylene / α-olefin random copolymer component 24.2% by weight
(Ethylene content: 44.7% by weight, PolyMw: 286000)

Ethylene / propylene block copolymer 4 (BPP4):
(MFR 10 g / 10 min, ethylene concentration 6.6% by weight)
Crystalline propylene polymer component 85.0% by weight
(96% stereoregularity in homo part)
Propylene / α-olefin random copolymer component 15.0% by weight
(Ethylene content: 44.0% by weight, PolyMw: 513000)

Ethylene / propylene block copolymer 5 (BPP5):
(MFR 10 g / 10 min, ethylene concentration 7.1% by weight)
Crystalline propylene polymer component 83.9% by weight
(96% stereoregularity in homo part)
Propylene / α-olefin random copolymer component 16.1% by weight
(Ethylene content: 43.8% by weight, PolyMw: 660000)

Ethylene / propylene block copolymer 6 (BPP6):
(MFR 9 g / 10 min, ethylene concentration 5.9% by weight)
Crystalline propylene polymer component 83.1% by weight
(Homo part stereoregularity 94%)
Propylene / α-olefin random copolymer component 16.9% by weight
(Ethylene content: 34.8% by weight, PolyMw: 902000)

Ethylene / propylene block copolymer 7 (BPP7):
(MFR 10 g / 10 min, ethylene concentration 12.7% by weight)
Crystalline propylene polymer component 71.5% by weight
(96% stereoregularity in homo part)
Propylene / α-olefin random copolymer component 28.5% by weight
(Ethylene content: 44.7% by weight, PolyMw: 300000)

Ethylene / propylene block copolymer 8 (BPP8):
(MFR 10 g / 10 min, ethylene concentration 4.2 wt%)
Crystalline propylene polymer component 91.9% by weight
(Stereoregularity of homo part 98%)
Propylene / α-olefin random copolymer component 8.1% by weight
(Ethylene content: 51.8% by weight, PolyMw: 1500000)

Ethylene / propylene block copolymer 9 (BPP9):
(MFR 10 g / 10 min, ethylene concentration 5.8% by weight)
Crystalline propylene polymer component 86.6% by weight
(96% stereoregularity in homo part)
Propylene / α-olefin random copolymer component 13.4% by weight
(Ethylene content: 43.6% by weight, PolyMw: 297000)

Ethylene / propylene block copolymer 10 (BPP10):
(MFR 10 g / 10 min, ethylene concentration 7.2% by weight)
Crystalline propylene polymer component 84.2% by weight
(96% stereoregularity in homo part)
Propylene / α-olefin random copolymer component 15.8% by weight
(Ethylene content: 45.5 wt%, PolyMw: 281400)

Ethylene / propylene block copolymer 11 (BPP11):
(MFR 10 g / 10 min, ethylene concentration 13.4% by weight)
Crystalline propylene polymer component 81.5% by weight
(96% stereoregularity in homo part)
Propylene / α-olefin random copolymer component 18.5% by weight
(Ethylene content: 72.7% by weight, PolyMw: 183000)

Ethylene / propylene block copolymer 12 (BPP12):
(MFR 10 g / 10 min, ethylene concentration 10.4% by weight)
Crystalline propylene polymer component 76.0% by weight
(96% stereoregularity in homo part)
Propylene / α-olefin random copolymer component 24.0% by weight
(Ethylene content: 43.2% by weight, PolyMw: 207000)

Ethylene / propylene block copolymer 13 (BPP13):
(MFR 10 g / 10 min, ethylene concentration 4.6% by weight)
Crystalline propylene polymer component 83.2% by weight
(96% stereoregularity in homo part)
Propylene / α-olefin random copolymer component 16.8% by weight
(Ethylene content: 27.4% by weight, PolyMw: 200000)

Ethylene / propylene block copolymer 14 (BPP14):
(MFR 10 g / 10 min, ethylene concentration 11.6 wt%)
Crystalline propylene polymer component 73.8% by weight
(96% stereoregularity in homo part)
Propylene / α-olefin random copolymer component 26.2% by weight
(Ethylene content: 44.2% by weight, PolyMw: 835000)

Ethylene / propylene block copolymer 15 (BPP15):
(MFR 10 g / 10 min, ethylene concentration 11.8% by weight)
Crystalline propylene polymer component 74.4% by weight
(96% stereoregularity in homo part)
Propylene / α-olefin random copolymer component 25.6% by weight
(Ethylene content: 46.0 wt%, PolyMw: 497000)

Ethylene / propylene block copolymer 16 (BPP16):
(MFR 10 g / 10 min, ethylene concentration 10.3% by weight)
Crystalline propylene polymer component 77.0% by weight
(96% stereoregularity in homo part)
Propylene / α-olefin random copolymer component 23.0% by weight
(Ethylene content: 44.8% by weight, PolyMw: 464000)

Ethylene / propylene block copolymer 17 (BPP17):
(MFR 10 g / 10 min, ethylene concentration 11.8% by weight)
Crystalline propylene polymer component 73.2% by weight
(96% stereoregularity in homo part)
Propylene / α-olefin random copolymer component 26.8% by weight
(Ethylene content: 44.1% by weight, PolyMw: 664000)

Ethylene / propylene block copolymer 18 (BPP18):
(MFR 10 g / 10 min, ethylene concentration 11.7% by weight)
Crystalline propylene polymer component 73.0% by weight
(96% stereoregularity in homo part)
Propylene / α-olefin random copolymer component 27.0% by weight
(Ethylene content: 43.5% by weight, PolyMw: 281000)

Ethylene / propylene block copolymer 19 (BPP19):
(MFR 10 g / 10 min, ethylene concentration 12.6% by weight)
Crystalline propylene polymer component 71.3% by weight
(96% stereoregularity in homo part)
Propylene / α-olefin random copolymer component 28.7% by weight
(Ethylene content: 44.0 wt%, CopyMw: 283000)

Ethylene / propylene block copolymer 20 (BPP20):
(MFR 10 g / 10 min, ethylene concentration 11.9% by weight)
Crystalline propylene polymer component 72.8% by weight
(96% stereoregularity in homo part)
Propylene / α-olefin random copolymer component 27.2% by weight
(Ethylene content: 43.8% by weight, PolyMw: 502000)

Ethylene / propylene block copolymer 21 (BPP21):
(MFR 10 g / 10 min, ethylene concentration 12.7% by weight)
Crystalline propylene polymer component 71.4% by weight
(96% stereoregularity in homo part)
Propylene / α-olefin random copolymer component 28.6% by weight
(Ethylene content: 44.5% by weight, PolyMw: 910000)

Ethylene / propylene block copolymer 22 (BPP22):
(MFR 10 g / 10 min, ethylene concentration 12.5% by weight)
Crystalline propylene polymer component 71.5% by weight
(96% stereoregularity in homo part)
Propylene / α-olefin random copolymer component 28.5% by weight
(Ethylene content: 44.0% by weight, PolyMw: 915000)

Ethylene / propylene block copolymer 23 (BPP23):
(MFR 10 g / 10 min, ethylene concentration 11.9% by weight)
Crystalline propylene polymer component 73.0% by weight
(96% stereoregularity in homo part)
Propylene / α-olefin random copolymer component 27.0% by weight
(Ethylene content: 44.0% by weight, PolyMw: 130000)

(Production Example 1)
(I) Production of solid catalyst component (a) 20 liters of dehydrated and deoxygenated n-heptane was introduced into a tank equipped with a stirrer with an internal volume of 50 liters purged with nitrogen, and then 10 moles of magnesium chloride and 20 moles of tetrabutoxytitanium And then reacting at 95 ° C. for 2 hours, lowering the temperature to 40 ° C., introducing 12 liters of methylhydropolysiloxane (viscosity 20 centistokes) and further reacting for 3 hours, then taking out the reaction solution The resulting solid component was washed with n-heptane.
Subsequently, 5 liters of dehydrated and deoxygenated n-heptane was introduced into the tank using the tank equipped with a stirrer, and then 3 mol of the solid component synthesized above was introduced in terms of magnesium atom. Next, 5 liters of silicon tetrachloride was mixed with 2.5 liters of n-heptane and introduced at 30 ° C. for 30 minutes. The temperature was raised to 70 ° C. and reacted for 3 hours. Then, the reaction solution was taken out, The resulting solid component was washed with n-heptane.
Subsequently, 2.5 liters of dehydrated and deoxygenated n-heptane was introduced into the tank using the tank with a stirrer, and 0.3 mol of phthalic acid chloride was mixed and introduced at 90 ° C. for 30 minutes. And reacted at 95 ° C. for 1 hour. After completion of the reaction, washing with n-heptane was performed. Next, 2 liters of titanium tetrachloride was added at room temperature, and the temperature was raised to 100 ° C., followed by reaction for 2 hours. After completion of the reaction, washing with n-heptane was performed. Further, 0.6 liters of silicon tetrachloride and 8 liters of n-heptane were introduced, reacted at 90 ° C. for 1 hour, and sufficiently washed with n-heptane to obtain a solid component. This solid component contained 1.30% by weight of titanium.
Next, 8 liters of n-heptane, 400 g of the solid component obtained above, 0.27 mol of t-butyl-methyl-dimethoxysilane and 0.27 mol of vinyltrimethylsilane were introduced into the tank equipped with a stirrer substituted with nitrogen. And contacted at 30 ° C. for 1 hour. Next, the mixture was cooled to 15 ° C., 1.5 mol of triethylaluminum diluted in n-heptane was introduced over 15 minutes under 15 ° C., and after the introduction, the temperature was raised to 30 ° C. and reacted for 2 hours. By washing with heptane, 390 g of a solid catalyst component was obtained.
The obtained solid catalyst component contained 1.22% by weight of titanium.
Furthermore, 6 liters of n-heptane and 1 mol of triisobutylaluminum diluted in n-heptane were introduced over 30 minutes at 15 ° C., and then about 0.4 kg / kg of propylene was controlled so as not to exceed 20 ° C. Preliminarily polymerized by introducing for 1 hour. As a result, a polypropylene-containing solid catalyst component (a) in which 0.9 g of propylene was polymerized per 1 g of solid was obtained.

(Ii) Production of propylene-based block copolymer (pre-stage polymerization step: production of crystalline propylene polymer component)
Polymerization was carried out using a continuous reaction apparatus in which two fluidized bed reactors having an internal volume of 230 liters were connected. First, in a first reactor, a polymerization temperature of 75 ° C., a propylene partial pressure of 18 kg / cm ² (absolute pressure), and hydrogen as a molecular weight control agent are continuously fed so that the molar ratio of hydrogen / propylene is 0.015. At the same time, triethylaluminum was supplied at 5.25 g / hr as the solid catalyst component (a) so that the above-described catalyst was supplied at a polymer polymerization rate of 20 kg / hr to produce a crystalline propylene polymer component. The powder polymerized in the first reactor (crystalline propylene polymer component) was continuously withdrawn so that the amount of powder held in the reactor was 60 kg, and continuously transferred to the second reactor.

(Second-stage polymerization process: Propylene / ethylene random copolymer component production)
Subsequently, propylene and ethylene were continuously supplied so that the molar ratio of ethylene / propylene was 0.62 so that the inside of the second reactor had a polymerization temperature of 80 ° C. and a pressure of 2.0 MPa, Hydrogen as a molecular weight control agent is continuously supplied so that the molar ratio of hydrogen / propylene is 0.027, and ethyl alcohol as an active hydrogen compound is 1.7 times mol with respect to triethylaluminum. To produce a propylene / ethylene random copolymer component. The powder that has been polymerized in the second reactor (a propylene-based block copolymer comprising a crystalline propylene polymer component and a propylene / ethylene random copolymer component) has a powder holding amount of 40 kg in the reactor. To the vessel continuously. Nitrogen gas containing water was supplied to stop the reaction to obtain a propylene-based block copolymer. The resulting propylene block copolymer was designated as (BPP1).

(Production Example 2)
Using the catalyst and polymerization method used in Production Example 1, the hydrogen / propylene molar ratio in the preceding polymerization step was 0.015, the hydrogen / propylene molar ratio in the latter polymerization step was 0.034, and ethyl alcohol was changed to triethylaluminum. A propylene-based block copolymer (BPP2) was produced in the same manner as in Production Example 1 except that the amount was changed to 1.5 moles.

(Production Example 3)
Using the catalyst and polymerization method used in Production Example 1, the hydrogen / propylene molar ratio in the preceding polymerization step was 0.016, the hydrogen / propylene molar ratio in the latter polymerization step was 0.036, and ethyl alcohol was triethylaluminum. A propylene-based block copolymer (BPP3) was produced in the same manner as in Production Example 1 except that the amount was changed to 1.3 moles.

(Production Example 4)
Using the catalyst and polymerization method used in Production Example 1, the hydrogen / propylene molar ratio in the preceding polymerization step was 0.015, the hydrogen / propylene molar ratio in the latter polymerization step was 0.020, and ethyl alcohol was triethylaluminum. A propylene-based block copolymer (BPP4) was produced in the same manner as in Production Example 1 except that the amount was changed to 2.2 times the mole.

(Production Example 5)
Using the catalyst and polymerization method used in Production Example 1, the hydrogen / propylene molar ratio in the preceding polymerization step was 0.016, the hydrogen / propylene molar ratio in the latter polymerization step was 0.0052, and ethyl alcohol was triethylaluminum. A propylene-based block copolymer (BPP5) was produced in the same manner as in Production Example 1 except that the amount was changed to 1.9 moles.

(Production Example 6)
(I) Production of solid catalyst component (b) 6 liters of n-hexane, 5.0 mol of diethylaluminum monochloride (DEAC), and 12.0 mol of diisoamyl ether were mixed at 25 ° C. for 5 minutes, and the same temperature for 5 minutes. To obtain a reaction solution (I) (diisoamyl ether / DEAC molar ratio 2.4). 40 moles of titanium tetrachloride was placed in a nitrogen-substituted reactor and heated to 35 ° C., and the entire amount of the reaction solution (I) was added dropwise to the reactor over 180 minutes, then kept at the same temperature for 30 minutes and heated to 75 ° C. The reaction is further allowed to proceed for 1 hour, cooled to room temperature, the supernatant is removed, 30 liters of n-hexane is added, and the supernatant is removed by decantation four times to obtain 1.9 kg of the solid product (II). Obtained. In a state where the whole amount of (II) is suspended in 30 liters of n-hexane, 1.6 kg of diisoamyl ether and 3.5 kg of titanium tetrachloride are added at 20 ° C. over about 5 minutes, and 1 at 60 ° C. Reacted for hours. After completion of the reaction, the mixture was cooled to room temperature (20 ° C.), the supernatant was removed by decantation, 30 liters of n-hexane was added, stirred for 15 minutes, and allowed to stand to remove the supernatant 5 times. After repeating, it was dried under reduced pressure to obtain a Ti-based solid catalyst (b).

(Ii) Production of propylene-based block copolymer (pre-stage polymerization step: production of crystalline propylene polymer component)
A stainless steel autoclave with a stirrer having an internal volume of 400 liters was sufficiently substituted with propylene gas at room temperature, and 120 liters of dehydrated and deoxygenated n-heptane was added as a polymerization solvent. Next, 86 g of diethylaluminum chloride, 50 liters of hydrogen (standard state conversion), 10.5 cc of propionic acid, and 23 g of the catalyst b were added under the condition of a temperature of 65 ° C.
After raising the internal temperature of the autoclave to 70 ° C., propylene was supplied at a rate of 21.7 kg / hour and hydrogen was supplied at a rate of 126 L / hour to initiate polymerization. After 160 minutes, the introduction of propylene was stopped, and the pressure was 0.34 kg / cm ² G at the start of polymerization, increased with time during the supply of propylene, and increased to 7.7 kg / cm ² G when the supply was stopped. Then after the pressure is residual polymerization until 2.0kg / cm ² G, and releasing the unreacted gas in the vessel to 0.3 kg / cm ^2, to produce a crystalline propylene polymer component.

(Second-stage polymerization process: Propylene / ethylene random copolymer component production)
Subsequently, the internal temperature of the autoclave was lowered to 60 ° C., and propylene was supplied at a rate of 5.65 kg / hour and ethylene was supplied at a rate of 2.42 kg / hour. After 120 minutes, the introduction of propylene was stopped, the pressure increased with time during the monomer supply, and increased to 2.8 kg / cm ² G when the supply was stopped. Then after the pressure is residual polymerization until 1.0kg / cm ² G, and releasing the unreacted gas in the vessel to 0.3 kg / cm ^2, to produce a propylene-ethylene random copolymer component.
The obtained solvent (slurry) containing the propylene-based block copolymer is transferred to the next tank with a stirrer, 5 liters of butanol is added, treated at 70 ° C. for 3 hours, further transferred to the next tank with a stirrer, water After adding 100 liters of pure water in which 100 g of sodium oxide was dissolved and treating for 1 hour, the aqueous layer was allowed to stand and then separated to remove the catalyst residue. The slurry is treated with a centrifuge to remove heptane, treated with a dryer at 80 ° C. for 3 hours to completely remove heptane, and from 53.2 kg of a crystalline propylene polymer component and a propylene / ethylene random copolymer component. A propylene-based block copolymer (BPP6) was obtained.

(Production Example 7)
Using the catalyst and polymerization method used in Production Example 1, the hydrogen / propylene molar ratio in the preceding polymerization step was 0.017, the hydrogen / propylene molar ratio in the latter polymerization step was 0.036, and ethyl alcohol was triethylaluminum. A propylene-based block copolymer (BPP7) was produced in the same manner as in Production Example 1 except that the amount was changed to 1.1 moles.

(Production Example 8)
(Pre-stage polymerization step: production of crystalline propylene polymer component)
A stainless steel autoclave with a stirrer with an internal volume of 200 liters was sufficiently substituted with propylene gas at room temperature, and 60 liters of dehydrated and deoxygenated n-heptane was added as a polymerization solvent. Next, 15 g of triethylaluminum, 50 liters of hydrogen (converted to the standard state), and 6.0 g of the solid catalyst component (a) were added under the conditions of a temperature of 70 ° C.
After the autoclave was heated to an internal temperature of 75 ° C., propylene was supplied at a rate of 9.2 kg / hour and hydrogen was supplied at a rate of 16.2 L / hour to initiate polymerization. After 210 minutes, the introduction of propylene was stopped, the pressure was 0.34 kg / cm ² G at the start of polymerization, increased with time during the supply of propylene, and increased to 4.6 kg / cm ² G when the supply was stopped. Then after the pressure is residual polymerization until 2.5kg / cm ² G, and releasing the unreacted gas in the vessel to 0.3 kg / cm ^2, to produce a crystalline propylene polymer component.

(Second-stage polymerization process: Propylene / ethylene random copolymer component production)
Subsequently, the internal temperature of the autoclave was lowered to 65 ° C., 10 cc of butanol was added, and then propylene was supplied at a rate of 2.45 kg / hour and ethylene at a rate of 1.64 kg / hour. After 55 minutes, the introduction of propylene was stopped, the pressure increased with time during the monomer supply, and increased to 1.0 kg / cm ² G at the time of the supply stop. Thereafter, the unreacted gas in the vessel was discharged to 0.3 kg / cm ² to produce a propylene / ethylene random copolymer component.
The obtained solvent (slurry) containing the propylene block copolymer is transferred to the next tank with a stirrer, 2.5 liters of butanol is added, treated at 70 ° C. for 3 hours, and further transferred to the next tank with a stirrer. Then, 50 liters of pure water in which 50 g of sodium hydroxide was dissolved was added, followed by treatment for 1 hour, and then the aqueous layer was allowed to stand and separated to remove the catalyst residue. The slurry is treated with a centrifuge to remove heptane, and then treated with a dryer at 80 ° C. for 3 hours to completely remove heptane. From 26.5 kg of the crystalline propylene polymer component and the propylene / ethylene random copolymer component A propylene-based block copolymer (BPP8) was obtained.

(Production Example 9)
Using the catalyst and polymerization method used in Production Example 1, the hydrogen / propylene molar ratio in the preceding polymerization step was 0.013, the hydrogen / propylene molar ratio in the latter polymerization step was 0.029, and ethyl alcohol was triethylaluminum. A propylene-based block copolymer (BPP9) was produced in the same manner as in Production Example 1 except that the amount was changed to 2.2 times the mole.

(Production Example 10)
Using the catalyst and polymerization method used in Production Example 1, the hydrogen / propylene molar ratio in the preceding polymerization step was 0.013, the hydrogen / propylene molar ratio in the latter polymerization step was 0.035, and ethyl alcohol was triethylaluminum. A propylene-based block copolymer (BPP10) was produced in the same manner as in Production Example 1 except that the amount was changed to 2.1 times the mol.

(Production Example 11)
Using the catalyst and polymerization method used in Production Example 1, the hydrogen / propylene molar ratio in the preceding polymerization step was 0.011, the ethylene / propylene molar ratio in the latter polymerization step was 2.43, and hydrogen / propylene. A propylene-based block copolymer (BPP11) was produced in the same manner as in Production Example 1 except that the molar ratio was 0.25 and ethyl alcohol was changed to 2.6-fold moles with respect to triethylaluminum.

(Production Example 12)
Using the catalyst and polymerization method used in Production Example 1, the hydrogen / propylene molar ratio in the preceding polymerization step was 0.010, the hydrogen / propylene molar ratio in the latter polymerization step was 0.049, and ethyl alcohol was used. A propylene-based block copolymer (BPP12) was produced in the same manner as in Production Example 1 except that the amount was changed to 1.5 times the mole of triethylaluminum.

(Production Example 13)
Using the catalyst and polymerization method used in Production Example 1, the hydrogen / propylene molar ratio in the preceding polymerization step was 0.0090, the ethylene / propylene molar ratio in the molar polymerization step was 0.23, and hydrogen / propylene. A propylene-based block copolymer (BPP13) was produced in the same manner as in Production Example 1, except that the molar ratio was 0.030 and the ethyl alcohol was changed to 2.1-fold moles with respect to triethylaluminum.

(Production Example 14)
Using the catalyst and polymerization method used in Production Example 1, the hydrogen / propylene molar ratio in the preceding polymerization step was 0.025, the hydrogen / propylene molar ratio in the latter polymerization step was 0.0052, and ethyl alcohol was used. A propylene-based block copolymer (BPP14) was produced in the same manner as in Production Example 1 except that the amount was changed to 1.4 times the mole of triethylaluminum.

(Production Example 15)
Using the catalyst and polymerization method used in Production Example 1, the hydrogen / propylene molar ratio in the preceding polymerization step was 0.022, the hydrogen / propylene molar ratio in the latter polymerization step was 0.012, and ethyl alcohol was used. A propylene-based block copolymer (BPP15) was produced in the same manner as in Production Example 1 except that the molar amount was changed to 1.4 times the amount of triethylaluminum.

(Production Example 16)
Using the catalyst and polymerization method used in Production Example 1, the hydrogen / propylene molar ratio in the preceding polymerization step was 0.017, the hydrogen / propylene molar ratio in the latter polymerization step was 0.013, and ethyl alcohol was used. A propylene-based block copolymer (BPP16) was produced in the same manner as in Production Example 1 except that the amount was changed to 1.5 times the mole of triethylaluminum.

(Production Example 17)
Using the catalyst and polymerization method used in Production Example 1, the hydrogen / propylene molar ratio in the preceding polymerization step was 0.026, the hydrogen / propylene molar ratio in the molar polymerization step was 0.0082, and ethyl alcohol was used. A propylene-based block copolymer (BPP17) was produced in the same manner as in Production Example 1 except that the amount was changed so as to be 1.4 moles relative to triethylaluminum.

(Production Example 18)
Using the catalyst and polymerization method used in Production Example 1, the hydrogen / propylene molar ratio in the preceding polymerization step was 0.014, the hydrogen / propylene molar ratio in the latter polymerization step was 0.036, and ethyl alcohol was used. A propylene-based block copolymer (BPP18) was produced in the same manner as in Production Example 1 except that the amount was changed so as to be 1.4 moles relative to triethylaluminum.

(Production Example 19)
Using the catalyst and polymerization method used in Production Example 1, the hydrogen / propylene molar ratio in the preceding polymerization step was 0.015, the hydrogen / propylene molar ratio in the latter polymerization step was 0.036, and ethyl alcohol was used. A propylene-based block copolymer (BPP19) was produced in the same manner as in Production Example 1 except that the amount was changed to 1.3 times mol with respect to triethylaluminum.

(Production Example 20)
Using the catalyst and polymerization method used in Production Example 1, the hydrogen / propylene molar ratio in the preceding polymerization step was 0.024, the hydrogen / propylene molar ratio in the latter polymerization step was 0.012, and ethyl alcohol was used. A propylene-based block copolymer (BPP20) was produced in the same manner as in Production Example 1 except that the amount was changed so as to be 1.4 moles relative to triethylaluminum.

(Production Example 21)
Using the catalyst and polymerization method used in Production Example 1, the hydrogen / propylene molar ratio in the preceding polymerization step was 0.036, the hydrogen / propylene molar ratio in the latter polymerization step was 0.0050, and ethyl alcohol was used. A propylene-based block copolymer (BPP21) was produced in the same manner as in Production Example 1 except that the amount was changed to 1.3 times the mole of triethylaluminum.

(Production Example 22)
Using the catalyst and polymerization method used in Production Example 1, the hydrogen / propylene molar ratio in the preceding polymerization step was 0.035, the hydrogen / propylene molar ratio in the latter polymerization step was 0.0050, and ethyl alcohol was used. A propylene-based block copolymer (BPP22) was produced in the same manner as in Production Example 1 except that the amount was changed so as to be 1.4 moles relative to triethylaluminum.

(Production Example 23)
Using the catalyst and polymerization method used in Production Example 1, the hydrogen / propylene molar ratio in the preceding polymerization step was 0.039, the hydrogen / propylene molar ratio in the latter polymerization step was 0.0030, and ethyl alcohol was used. A propylene-based block copolymer (BPP23) was produced in the same manner as in Production Example 1 except that the amount was changed to 1.4 moles relative to triethylaluminum.

(B) Nucleating agent NA-11: Organophosphate metal salt compound nucleating agent (manufactured by ADEKA)

(C) Compounding agent for resin IRGANOX 1010: hindered phenol antioxidant (manufactured by Ciba Japan Co., Ltd.)
IRGAFOS 168: Phosphorous antioxidant (manufactured by Ciba Japan Co., Ltd.)
Calcium stearate: neutralizer (manufactured by Sakai Chemical Industry Co., Ltd.)
Erucamide: Lubricant

(D) Pigment master batch (Pigment MB)
(A) Pigment MB1: Pigment MB using polypropylene as a base
Pigment MB containing 3 parts by weight of yellowish green pigment based on 100 parts by weight of the following propylene block copolymer BPP5
(B) Pigment MB2: Pigment MB using high-density polyethylene as a base
Pigment MB containing 3 parts by weight of yellowish green pigment based on 100 parts by weight of high density polyethylene having a melt flow rate at 190 ° C. of 8 g / 10 min and a density of 0.960 g / cm ³

The physical properties were measured by the following method.
I. CopolyMw was measured by the following method.
(1) Analytical device to be used (i) Cross fractionation device CFC T-100 (abbreviated as CFC) manufactured by Dia Instruments Co., Ltd.
GPC column: 3 AD806MS manufactured by Showa Denko Co., Ltd. (2) CFC measurement conditions (i) Solvent: Orthodichlorobenzene (ODCB)
(Ii) Sample concentration: 4 mg / ml
(Iii) Injection volume: 0.4 ml
(Iv) Crystallization: The temperature is lowered from 140 ° C. to 40 ° C. over about 70 minutes.
(V) Sorting method:
The fractionation temperature at the time of temperature-raising elution fractionation is 40, 100, and 140 ° C., and the fraction is separated into three fractions in total.
(Vi) Solvent flow rate during elution: 1 ml / min (3) Post-treatment and analysis of measurement results The molecular weight distribution of components eluted at each temperature is determined using the chromatogram obtained by the detector. Conversion from the retention volume to the molecular weight is performed using a calibration curve prepared in advance with standard polystyrene.
The standard polystyrenes used are the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000.
A calibration curve is prepared by injecting 0.4 ml of a solution dissolved in ODCB (containing 0.5 mg / ml BHT) so that each is 0.5 mg / ml. The calibration curve uses a cubic equation obtained by approximation by the least square method. Conversion to molecular weight uses a general-purpose calibration curve with reference to “Size Exclusion Chromatography” written by Sadao Mori (Kyoritsu Shuppan). The following numerical values are used for the viscosity equation ([η] = K × Mα) used at that time.
(I) When creating a calibration curve using standard polystyrene K = 0.000138, α = 0.70
(Ii) Sample measurement of propylene-based block copolymer K = 0.000103, α = 0.78
The weight average molecular weight of the component (propylene / α-olefin random copolymer component) eluted at 40 ° C. is CopolyMw.

II. α-Olefin Content The ethylene / propylene block copolymer was measured by ¹³ C-NMR.

III. Isotactic pentad fraction (stereoregularity of homo part)
Using GSX-270, manufactured by JEOL Ltd., using a solvent of o-dichlorobenzene / heavy benzene, measuring temperature 130 ° C., and performing ¹³ C-NMR measurement by proton decoupling method, in the crystalline propylene polymer component The weight ratio of the mmmm component was determined.

IV. MFR: Compliant with JIS K7210, 230 ° C. 2.16 kg load.

V. Flexural modulus: measured at 23 ° C. according to JIS K6921.

  Caps molded using pellets granulated using the propylene-based block copolymer were evaluated by the following methods. A schematic cross-sectional view of the 1P resin cap used for the evaluation is as shown in FIG.

VI. Cap tightening ability When the cap is set at the bottle mouth and tightened with a tightening torque of 230 Ncm, when reaching the minimum angle at which the top of the bottle body comes into contact with the inner surface of the top of the cap (hereinafter referred to as the top surface contact angle) ○, if not reached, ×, and if the tightening torque is further reduced by 5% or more, ◎ indicates that the top surface contact angle is reached.

VII. Sealing property The 1P cap has a bottle body port inserted between the inner ring and the outer ring up to the inner surface of the top of the cap, so that the sealing property is maintained.
The sealing property was determined as “O” when the tightening torque was 230 Ncm or less and the top surface contact angle was reached, and “X” when it did not.

VIII. Unscrewing Cap that has been tightened until it reaches the top surface contact angle is opened by turning the cap at a speed of 2 seconds per rotation, and the opening torque generated at the time of opening is less than 130 Ncm or more, exceeding 130 Ncm X. In actual use, if this torque is too high, the cap is difficult to open, which is not preferable.

IX. Impact resistance A 1 kg weight was dropped onto a cap from a height of 40 cm. A large or quite (several percent or more) crack was evaluated as x.

X. Blow-off property The cap was tightened until it reached the top surface contact angle, and the internal pressure was increased from the bottle body.

XI. Appearance by visual observation When the obtained cap had uneven color, “X” was given.
XII. Cutting of the band part of the cap The cutting part of the band part (perforation for preventing tampering) of the obtained cap is opened and visually evaluated. When it remained stretched, it was set as "△", and it was marked as "○" when it was cut almost without extending.

Example 1
As a nucleating agent, 0.15% by weight of NA11, 0.05% by weight of IRGANOX1010, 0.05% by weight of IRGAFOS168, erucic acid, based on 98.7% by weight of ethylene / propylene block copolymer 1 (BPP1) After blending and blending 1% by weight of amide and 0.05% by weight of calcium stearate, the mixture was melt-kneaded using an extruder and pelletized. The obtained pellets were injection molded with an injection molding machine at a resin temperature of 220 ° C. and a mold temperature of 40 ° C. to prepare test pieces, and the physical properties were measured from the test pieces. In addition, a cap was obtained by compression molding using a blend of the pigment master batch (pigment MB1) in a ratio of 18.5: 1 to the pellets, and the cap was tightened, sealed, opened, and resisted. Impact properties, blow-off properties, and appearance were confirmed. The results are shown in Table 1.

Example 2
0.09% by weight NA11, 0.05% by weight IRGANOX1010, 0.05% by weight IRGAFOS168, 0.05% by weight of erucic acid, based on 99.06% by weight of ethylene / propylene block copolymer 1 (BPP1) After blending and blending 0.7% by weight of amide and 0.05% by weight of calcium stearate, the mixture was melt-kneaded using an extruder and pelletized. The obtained pellets were injection molded with an injection molding machine at a resin temperature of 220 ° C. and a mold temperature of 40 ° C. to prepare test pieces, and the physical properties were measured from the test pieces. A cap obtained by compression molding using a pellet master batch (pigment MB1) blended at 18.5: 1 to the pellets is obtained, and the cap is tightened, sealed, opened, and impact resistant. Blow-off property and appearance were confirmed. The results are shown in Table 1.

Examples 3, 4, 6, 7, 9-17, Comparative Examples 1-9
Except that the ethylene / propylene block copolymer, the nucleating agent addition amount, and the erucic acid amide addition amount shown in Table 1 were used, test pieces were prepared according to Example 1 and Example 2, and the physical properties were measured. In addition, various performance evaluations were performed. The results are shown in Tables 1 and 2.

Example 5
Except that pigment MB1 used in Example 1 was replaced with pigment MB2, a test piece was prepared according to Example 1, its physical properties were measured, and various performance evaluations were performed. The results are shown in Table 1.

Example 8
4.5% by weight of high density polyethylene having a melt flow rate at 190 ° C. of 8 g / 10 min and a density of 0.960 g / cm ³ with respect to 95.2% by weight of ethylene / propylene block copolymer 12 (BPP12) As a nucleating agent, NA11 0.15 wt%, IRGANOX 1010 0.05 wt%, IRGAFOS 168 0.05 wt%, erucamide 1 wt% and calcium stearate 0.05 wt% were blended. Then, it knead | mixed and pelletized using the extruder. The obtained pellets were injection molded with an injection molding machine at a resin temperature of 220 ° C. and a mold temperature of 40 ° C. to prepare test pieces, and the physical properties were measured from the test pieces. In addition, a cap was obtained by compression molding using a blend of the pigment master batch (pigment MB1) in a ratio of 18.5: 1 to the pellets, and the cap was tightened, sealed, opened, and resisted. Impact properties, blow-off properties, and appearance were confirmed. The results are shown in Table 1.

From Table 1, Examples 1-4 and Examples 10-17 are the propylene-type resin composition for 1P resin caps of this invention, By using this, the winding-tightness which is the basic performance of a cap, and sealing performance It can be seen that the openability, impact resistance, blow-off property and appearance are all good.
In particular, Example 2 is a propylene-based resin composition for 1P resin cap in which erucic acid amide, which is one type of lubricant that has an effect of improving the tightening property with respect to the cap, is reduced. By using a propylene-based block copolymer, it can be seen that even if the lubricant is reduced, the basic performance of the cap can be used without inferiority. Thus, it can be seen that erucic acid amide, which is a component that easily precipitates, and which may adversely affect the contents by precipitation, can be reduced.
In Example 5, since 5 parts by weight of high-density polyethylene was used as the pigment MB per 100 parts by weight of the intended propylene resin composition including the pigment MB, the pigment dispersibility was slightly deteriorated. It can be seen that the basic performance of the cap is almost satisfied, although there is a slight adverse effect on the appearance of the cap.
Examples 6 to 9 are propylene-based resin compositions for a 1P resin cap of the present invention, and the constituent ratio of the propylene / ethylene random copolymer component is a value separated from the central value of 50%, It can be seen that HDPE is added, and the cap opening torque at 23 ° C. and the cap opening torque at 60 ° C. change gradually. As for the performance of the cap, it is preferable that the opening torque, which is easy to open at 23 ° C, is low. At 60 ° C, a certain amount of opening torque is required so that the opening torque is not easily opened. Less is preferable.
Further, Example 6 is less dependent on temperature of the opening torque than Example 9 and has high rigidity and good balance, and the ethylene content in the propylene / ethylene random copolymer component should be higher. I understand.
In addition, since the Copy Mw of Examples 6 to 9 is less than 250,000, it can be seen that the cutting performance of the band part is not so good.
Comparative Examples 1-3, 5-7, and 9 are propylene-based resin compositions for 1P resin caps using a propylene-based block copolymer that does not satisfy the mathematical formula (A) specified in the present invention. It turns out that a defect of property occurs and is not suitable as a 1P resin cap.
Comparative Examples 4 and 8 are propylene block copolymers that satisfy the mathematical formula (A) specified in the present invention, but the rigidity is low because the flexural modulus is below the lower limit specified in the present invention. It can be seen that the 1P resin cap is inferior in blow-off property.
Comparative Example 5 is a propylene-based block copolymer that does not satisfy the mathematical formula (A) specified in the present invention, and its bending elastic modulus exceeds the upper limit specified in the present invention. It can be seen that this is a 1P cap with poor plug and impact resistance.

  The propylene resin composition for 1P cap of the present invention satisfies the basic properties of the cap such as good winding property, sealing property, opening property, rigidity (blow-off property), impact resistance, and appearance of the cap such as uneven color. Since it is possible to provide a 1P resin cap that hardly causes a defect, it is very useful in the industry.

The cross-sectional schematic of one example of a typical 1P resin cap. The cross-sectional photograph of one example of a typical 1P resin cap. Plot diagram showing the relationship between the flexural modulus (X) and PolyMw (Y) of the propylene block copolymer

Explanation of symbols

1: Shell 2: Screw part 3: Outer ring 4: Inner ring 5: Top surface

Claims (7)

A propylene-based block copolymer obtained by polymerizing a crystalline propylene polymer component and then continuously polymerizing a propylene / α-olefin random copolymer component and satisfying the following characteristics (1) to (4): A propylene-based resin composition for a one-piece resin cap, comprising:
(1) The content of α-olefin is 1 to 24% by weight
(2) The flexural modulus measured based on JIS K6921 is 900 to 1600 MPa.
(3) Melt flow rate measured based on JIS K7210 (230 ° C., 2.16 kg load) is 0.5 to 100 g / 10 min. (4) Weight average molecular weight of propylene / α-olefin random copolymer component ( The relationship between Y) and the flexural modulus (X) measured based on JIS K6921 is a range represented by the following mathematical formula (A).
[Equation 1]
Y ≦ −1670X + 2804000 (A)
(However, Y ≧ 100000) 2. The one-piece resin cap according to claim 1, wherein 0.01 to 0.4 wt% of a nucleating agent composed of at least one of the following formulas (1) to (3) is blended. Propylene-based resin composition.

(In the formula, R ¹ is a direct bond, sulfur, a C 1-9 alkylene group or an alkylidene group, R ² and R ³ are a hydrogen atom or a C 1-8 alkyl group, and M is an alkali metal. Or an alkaline earth metal, where n is the valence of M.)

(Wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ² and R ³ represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and M represents group III of the periodic table or Represents a group IV metal atom, X represents HO— when M represents a group III metal atom of the periodic table, and M represents a group IV metal atom of the periodic table, O = or (HO) ₂ − is indicated.)

[Wherein, M ₁ and M ₂ are the same or different and are at least one metal cation selected from calcium, strontium, lithium and monobasic aluminum, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are the same or different and each represents hydrogen, an alkyl group having 1 to 9 carbon atoms (wherein any two vicinal or geminal alkyl groups are Together, a hydrocarbon ring having up to 6 carbon atoms may be formed), a hydroxy group, an alkoxy group having 1 to 9 carbon atoms, a hydroxyalkyl group having 1 to 9 carbon atoms, an amino group, carbon The at least 1 sort (s) of substituent selected from the alkylamino group of number 1-9, a halogen, and a phenyl group is shown. ]   The propylene-based resin composition for a one-piece resin cap according to claim 1 or 2, further comprising a lubricant in a range of 1 wt% or less.   The propylene-based resin composition for a one-piece resin cap according to any one of claims 1 to 3, further comprising less than 5 parts by weight of polyethylene based on 100 parts by weight of the propylene-based block copolymer. object.   The one-piece resin cap according to any one of claims 1 to 4, wherein the one-piece resin cap is obtained by molding a propylene-based resin composition for a one-piece resin cap.   The one-piece resin cap according to claim 5, wherein the molding is compression molding.   The one-piece resin cap according to claim 5, wherein the molding is injection molding.

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