JP2014240498A - Polyethylenic resin molding material for a container lid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide, by targeting a polyethylenic resin material for container lid members for carbonated beverages, etc., a polyethylenic resin molding material excellent, on the whole, in terms of various performances such as high-speed moldability, high fluidity, rigidity, impact resistance, durability, heat resistance, slipperiness, low odor, food safety, etc., favorable in terms of unsealability and sealability, and having improved mechanical characteristics such as stress crack resistance at the time of handling at a high temperature, full notch creep test (FNCT) rupture performance, etc.SOLUTION: The provided polyethylenic resin molding material for a container lid includes, as a main component, a polyethylenic polymer satisfying the following characteristics (1) through (3): characteristic (1): the melt flow rate (MFR) at a temperature of 190°C under a load of 2.16 kg is 0.8 g/10 min or above and below 5.0 g/10 min, the high-load melt flow rate (HLMFR) at a temperature of 190°C under a load of 21.6 kg is 180 g/10 min or above and 400 g/10 min or below, and HLMFR/MFR is 80-200; characteristic (2): the density is 0.955 g/cmor above and 0.970 g/cmor below; characteristic (3): the CSD (comonomer sequence distribution) calculated, via the formula (a), from theC-NMR spectral measurement value of a component having a molecular weight of at least 10is 0.0-3.0.

Description

  The present invention relates to a polyethylene-based resin molding material for container lids, and more particularly to a polyethylene-based resin molding material suitable for a lid of a container for storing a liquid such as a soft drink, particularly a carbonated beverage. Excellent in moldability, high fluidity, rigidity, impact resistance, stress crack resistance, slipperiness, low odor, food safety, openability, closure performance, etc. and long-term durability even at high temperatures Further, the present invention relates to a polyethylene resin molding material for container lids.

  Plastic containers are excellent in various physical properties, moldability, light weight, economy, etc., and are suitable for reusability in response to environmental issues. Recently, conventional containers made of metal or glass have been used. Overwhelming, it is widely used for daily necessities and industrial use. Among plastic containers, so-called PET bottles (polyethylene terephthalate containers) have been approved as containers for food and drink due to their excellent mechanical strength, transparency, high gas shielding properties, and non-polluting properties. Therefore, there is a great demand for containers for soft drinks. In particular, recently, small PET bottles have been heavily used by consumers as small containers for portable beverages. Also, the heat resistance and pressure resistance of PET bottles have been improved, so that they can be used for portable hot drinks for winter and long-term storage. It is also widely used as a container for high-temperature sterilized beverages.

In addition, in PET containers for soft drinks such as carbonated drinks, conventionally, metal containers such as aluminum have been used for the container lids, but in recent years, environmental conservation viewpoints such as recycling and economic efficiency have been used. For example, polyolefins are often used.
For containers for soft drinks, sealing and opening performance, food safety and durability are essential performance requirements, but lid members not only have these performances, but also moldability, rigidity, heat resistance, etc. From the viewpoint of various physical properties of the above, technical improvement studies have been continued on lid members made of polyolefin, particularly polyethylene resin, and a great number of improvements have been proposed.

Among these, as a typical improvement proposal, a polyethylene resin composition in which the MFR (melt flow rate) and density of the polyethylene component are specified in order to improve the pressure resistance and gas tightness of the cap for carbonated beverage containers. In order to improve flexibility and heat resistance, specific additives such as an ethylene / α-olefin copolymer and a glycerin fatty acid ester that define MFR, density and maximum melting peak temperature are disclosed in Patent Document 1 Patent Document 2 discloses an ethylene resin composition for injection molding comprising: However, the composition disclosed in Patent Document 1 is insufficient in high-speed moldability due to a small amount of low molecular weight components, and the composition disclosed in Patent Document 2 has a specific addition for improving mold releasability. The ingredients are contained and are not satisfactory in terms of food safety due to the elution of the ingredients.
In addition to various performance improvements such as sealability and rigidity, attempts have been made to perform injection molding and compression molding using high-fluidity polyolefin resin in order to shorten the container lid molding cycle and increase production efficiency. Patent Documents 3 and 4 disclose polyethylene resin materials that define MFR and FLR (flow ratio) of MFR in the resin itself or the composition. However, since the resin material disclosed in Patent Document 3 has a high MFR, the impact resistance is insufficient, and the resin material disclosed in Patent Document 4 has crack generation and tensile yield during warehouse storage at high temperatures in summer. There are inherent problems such as loose caps due to insufficient stress.

  On the other hand, from the viewpoint of the method of filling the container with the content liquid, a method has been adopted in which the container is heated and sterilized and filled with the content liquid, but recently, a pre-cleaned container is used. A method of filling a container with a content liquid (sterile filling method) in a clean room is adopted, and as a polyethylene resin used for the lid of such a container, the MFR and density of the resin material are used. Patent Documents 5 and 6 propose resin materials that are defined as having a monodispersibility of molecular weight and the like and that have no odor or off-flavor components and have long-term storage stability. However, according to Patent Documents 5 and 6, low odor and low taste are achieved, but it cannot be said that many of the required physical properties for the container lid described above are satisfied.

  In recent years, for the purpose of improving economy, the container lid has been made thinner while the molding speed has been increased to increase the molding speed. However, when the container lid is made thinner, the container lid is deformed by the internal pressure of the container. In order to prevent the contents from leaking from the lug, higher rigidity is required. Especially recently, containers containing beverages such as green tea have been heated and sold in a heater, and in this warming sale, the shape is maintained even at high temperatures, and cracking does not occur due to tightening of the container lid, There is a need for higher rigidity. Thus, Patent Document 7 describes the density of the resin material and the MFR and MFR of the resin material, which can improve the re-capping property even at high temperatures, as well as various performance improvements such as moldability and stress crack resistance. A material in which FLR is defined is disclosed, and Patent Document 8 discloses a material in which the density and MFR of the composition are defined, which can improve dimensional stability during warm storage as well as various performances such as rigidity and impact resistance. Is disclosed. However, in carbonated beverage container lids, stress is generated due to the large internal pressure, and the above materials may have insufficient stress crack resistance and cracks may occur, providing a sufficient balance between rigidity and stress crack resistance. There is a need for further improvements in the lids of carbonated beverage containers.

By the way, according to Patent Document 9 that presents a polyethylene-based resin material of Patent Document 4 and a material in which the density of the resin material, the MFR and MFR FLR, and the number of short chain branches are specified, the heat resistance, rigidity, and molding A material having various properties such as heat resistance and stress crack resistance can be realized, and a polyethylene-based resin material that can withstand the internal pressure of carbonated beverages is beginning to be used as a carbonated beverage container lid. Patent Document 10 discloses a polyethylene resin material that defines the MFR and density and molecular weight monodispersibility of the resin material, which are considered to be excellent in long-term storage of the container contents. However, in any case, in order to prevent the occurrence of cracks during warehouse storage at high temperatures in summer, further improvement in resistance to stress cracking due to carbonated beverage internal pressure is required.
Furthermore, in addition to the various properties that have been required in the past, polyethylene resin materials as container lid materials are also required to improve FNCT performance (break time by full notch creep test). In connection with the problem of cap loosening due to insufficient yield stress, there is also a need for improved tensile yield strength. The tensile yield strength has a close correlation with the looseness of the container lid, and if the tensile yield strength is low, the container lid is easily loosened, and the closure of the container lid with an appropriate hardness is insufficient. In order to improve the stress crack resistance of the container lid, it is necessary to reduce the density of the polyethylene-based material, so far it has been difficult to improve the tensile yield strength while improving the stress crack resistance. .

  In the above prior art, the lid member of the container is formed by the polyethylene resin or the composition thereof, but there is also an attempt to improve the performance of the lid member by the laminated material of the polyethylene resin. , A laminated lid material in which a sheet of a polyolefin and oxygen absorbent composition laminated on a polyolefin layer and a foamed layer is disclosed, aiming for a unique oxygen absorption as well as sealing and flavor retention. is there.

Thus, the conventional improved technology has been demanded as a lid member for a polyethylene resin material in a soft drink container, such as a number of performances, that is, moldability, fluidity, rigidity, impact resistance, and the like. Some improvements can be achieved in terms of sealing performance, opening performance, food safety, durability, stress crack resistance, heat resistance, etc., but these performances are well balanced. Improvement proposals to improve are not yet found.
Recently, with the aim of improving all of these performances in a well-balanced manner, a polyethylene-based resin composition that regulates density, MFR, bending strength, tear strength, volatile content, Vicat softening point, etc. (patent Document 12), a polyethylene-based resin material (Patent Document 13) that defines the density, MFR, FLR, bending elastic modulus, constant strain ESCR, and the like of an injection molded sample is presented.
Patent Documents 14 and 15 disclose polyethylene resin compositions for container lids that can improve high rigidity and high fluidity, but these are containers for soft drinks having a low internal pressure such as tea-based beverages. It is suitable for lids and is difficult to use for carbonated drinks due to lack of stress crack resistance. Patent Document 16 discloses a resin molding material that can be made thin and highly rigid while maintaining the stress crack resistance performance. However, if the fluidity is further increased, the stress crack resistance performance is lowered. Therefore, it is not necessarily sufficient for speeding up the molding. Patent Document 17 discloses a polyethylene resin composition for an injection molded container lid, but is not necessarily suitable for continuous compression molding (CCM) for the purpose of high-speed molding.
Under these circumstances, polyethylene-based resin materials for lid members in thermoplastic resin containers for soft drinks, etc., have high-speed moldability, high fluidity, rigidity, impact resistance, durability, heat resistance, slipperiness, low In addition to odor and food safety, it also has good openability and sealability, as well as mechanical properties such as stress crack resistance, FNCT rupture performance and tensile yield strength due to carbonated beverage internal pressure when handling at high temperature. There is a need for improved technology that improves the balance in a variety of ways, such as excellent performance.

JP 58-103542 A (refer to summary) JP-A-8-302084 (see abstract) JP 2000-159250 A (see abstract) JP 2000-248125 A (see abstract) JP 2002-249150 A (see abstract) Japanese Patent Laying-Open No. 2005-307002 (see abstract) Japanese Unexamined Patent Application Publication No. 2004-123959 (see abstract) JP 2004-244557 A (see abstract) JP 2002-60559 A (see abstract) JP 2001-180704 A (see abstract) JP 2000-264360 A (see abstract) Japanese Patent Laying-Open No. 2005-60517 (see abstract) Japanese Patent Laying-Open No. 2005-320526 (see abstract) JP 2004-300377 A (see abstract) JP 2007-284667 A (see abstract) JP 2008-019404 A (refer to summary) JP 2009-018868 A (see abstract)

  The object of the present invention relates to a polyethylene-based resin molding material particularly suitable for a lid of a container that contains a carbonated beverage liquid, and relates to high-speed moldability, high fluidity, rigidity, impact resistance, stress crack resistance, slipperiness, low An object of the present invention is to provide a polyethylene-based resin molding material suitable for a container lid, which is excellent in odor, food safety, openability, and closure properties and has good long-term durability even at high temperatures.

In order to solve the problems of the prior art, the present inventors have intensively studied the problems of the prior art in the polyethylene-based resin material for the container lid described above, and MFR and HLMFR of the polyethylene-based resin and their FLR. Investigate the relationship between these values and resin density, the correlation with various performances of the lid material by setting each numerical value, and the performance as a composition when combining each resin material. High-speed, which is a basic performance as a resin material for container lid members, by using a polyethylene-based polymer having specific MFR, HLMFR, resin density, and CSD (comonomer sequence distribution) Excellent performance with well-balanced properties such as moldability, high fluidity, rigidity, impact resistance, durability, heat resistance, slipperiness, low odor, and food safety In addition, the polyethylene-based polymer satisfies the condition of a specific number of short-chain branches, so that the stress crack resistance, FNCT rupture performance and tensile yield strength due to carbonated beverage internal pressure when handling at high temperature are satisfied. The present inventors have found that mechanical characteristics such as can be improved, and have completed the present invention.
The polyethylene-based resin molding material for container lids of the present invention (hereinafter also referred to as polyethylene-based resin molding material) is preferably used as a composition by combining two specific polyethylene-based polymers as a composition. It is suitable as a container lid member and can be used as a container body material for soft drinks.

That is, according to the first invention of the present invention, there is provided a polyethylene-based resin molding material for a container lid, which contains a polyethylene-based polymer as a main component that satisfies the following characteristics (1) to (3). Is done.
Characteristic (1): The melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 Kg is 0.8 g / 10 minutes or more and less than 5.0 g / 10 minutes, and the high temperature at a temperature of 190 ° C. and a load of 21.6 Kg. Property (2): Density flow rate (HLMFR) is 180 g / 10 min or more and 400 g / 10 min or less and HLMFR / MFR is 80 to 200: density is 0.955 g / cm ³ or more and 0.970 g / of (Deployment comonomer - shea - - Kuensu-distributor) of molecular weight ¹⁰⁵ or more ^components, 13 C-NMR formula from the measured value of the spectrum (a) by the determined CSD: cm ³ or less is characteristic (3) The value is 0.0 to 3.0. CSD = 4 × [EE] [CC] / [EC] ² formula (a)
(In formula (a), [EE] represents the number of ethylene / ethylene chains, [CC] represents the number of comonomer / comomer chains, and [EC] represents the number of ethylene / comonomer chains.)

According to the second invention of the present invention, in the first invention, the polyethylene-based polymer contains 20% by weight or more and 40% by weight or less of the following component (A), and the following component (B): A polyethylene-based resin molding material for a container lid is provided, which is a composition containing 60% by weight or more and 80% by weight or less.
Component (A): HLMFR of 0.1 to 5.0 g / 10 min, density of 0.915 to 0.935 g / cm ³ , and the CSD determined by the formula (a) from the measured value of ¹³ C-NMR spectrum Ethylene polymer having a value (CSD _A ) of 0.0 to 3.0 Component (B): MFR is 150 g / 10 min or more and less than 600 g / 10 min, density is 0.960 g / cm ³ or more and 0.980 g / cm Less than ³ ethylene polymer

According to a third invention of the present invention, in the first or second invention, the polyethylene polymer further comprises a CSD value CSD _A of the component (A) and a ¹³ C-NMR of the component (A). For container lid, wherein the number of short-chain branches SCB _A (numbers / 1,000 C) of 1 to 20 carbon atoms per 1,000 carbon atoms of the main chain measured by spectrum satisfies the following formula (b) A polyethylene-based resin molding material is provided.
CSD _A <−0.1273 × SCB _A +3.3 Formula (b)
According to a fourth invention of the present invention, in any one of the first to third inventions, the polyethylene polymer further satisfies the following characteristics (4) and (5): A polyethylene-based resin molding material for a lid is provided.
Property (4): Flexural modulus is 900-1500 MPa Property (5): Viscosity at melting at 190 ° C. and shear rate 400 sec ⁻¹ is 200-500 Pa · s

According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the polyethylene polymer further satisfies the following characteristics (6) and (7): A polyethylene-based resin molding material for a lid is provided.
Characteristic (6): Fracture time (FNCT) at 80 ° C. and 1.9 MPa by full notch creep test is 40 hours or more Characteristic (7): Constant strain stress crack resistance of injection molded sample is 200 to 1000 hours is there

  According to a sixth invention of the present invention, in any one of the second to fifth inventions, at least one of the component (A) and the component (B) of the polyethylene polymer is present in the presence of a polymerization catalyst. By multi-stage polymerization combining at least two polymerization reactors, ethylene homopolymer is polymerized in at least one polymerization reactor, and ethylene and an α-olefin having 3 to 20 carbon atoms in at least another polymerization reactor. There is provided a polyethylene-based resin molding material for a container lid, characterized in that an ethylene copolymer is polymerized.

According to a seventh invention of the present invention, in any one of the first to sixth inventions, the polymerization catalyst for the polyethylene-based polymer is represented by the general formula Mg (OR ² ) _m X ² _2-m (wherein , R ² represents an alkyl, aryl, or cycloalkyl group, X ² represents a halogen atom, and m is 1 or 2, and a compound represented by the general formula Ti (OR ³ ) _n X ³ _4- Homogeneous hydrocarbon solution comprising a compound represented by _n (wherein R ³ represents an alkyl, aryl or cycloalkyl group, X ³ represents a halogen atom, and n is 1, 2 or 3) Is represented by the general formula AlR ¹ _l X ¹ _3-l (wherein R ¹ represents an alkyl, aryl or cycloalkyl group, X ¹ represents a halogen atom, and l represents a number of 1 ≦ l ≦ 2). Obtained by treatment with an organic aluminum halide compound represented by Polyethylene resin molding material for container closure which is a catalyst comprising a hydrogen insoluble solid catalyst and an organoaluminum compound.
According to an eighth invention of the present invention, in any one of the first to seventh inventions, the container lid is used for a container for storing carbonated beverages as contents, and the container lid polyethylene -Based resin molding material is provided.
According to a ninth invention of the present invention, in any one of the first to eighth inventions, there is provided a polyethylene-based resin molding material for a container lid, wherein the container lid is formed by continuous compression molding. Provided.

  According to the polyethylene-based resin molding material for container lids of the present invention, the basic properties of the resin material for container lid members are high-speed moldability, high fluidity, rigidity, impact resistance, durability, heat resistance, and slipperiness. It has excellent balance of performance such as low odor and food safety. In addition, the opening and sealing properties are good, and the mechanical properties such as stress crack resistance, FNCT rupture performance and tensile yield strength due to carbonated beverage internal pressure during handling at high temperatures are also improved. Therefore, it is suitable for a lid of a container for storing a liquid such as a carbonated drink.

The number of short chain branches having 1 to 20 carbon atoms per 1,000 carbon atoms in the main chain of the polyethylene-based polymer (number / 1,000 C), CSD (comonomer sequence distribution), and It is a graph which shows the relationship.

Hereinafter, the characteristics of the polyethylene resin molding material of the present invention will be specifically described in detail. The polyethylene-based resin molding material of the present invention includes a polyethylene-based polymer that satisfies the following characteristics (1) to (3) as a main component.
In the present invention, “comprising a polyethylene polymer as a main component” means that the polyethylene polymer is contained in an amount of 50% by weight or more based on the total weight of the resin molding material of the present invention. Is 75% by weight or more, more preferably 90% by weight or more, and particularly preferably 95% by weight to 100% by weight.

1. Polyethylene resin molding material (1) Requirement characteristics as material (1)
The polyethylene resin molding material of the present invention has a melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 Kg of 0.8 g / 10 min or more and less than 5.0 g / 10 min, preferably 1. It is 0 to 4.5 g / 10 minutes, more preferably 2.0 to 3.0 g / 10 minutes. When the MFR is less than 0.8 g / 10 minutes, the fluidity is insufficient and high-speed moldability cannot be expected, and when it is 5.0 g / 10 minutes or more, the stress crack resistance of the container lid is not always sufficient.
The polyethylene resin molding material of the present invention has a high melt melt flow rate (HLMFR) of 180 g / 10 min to 400 g / 10 min, preferably 180 to 350 g / 10 min, more preferably 200 to 300 g / 10 min. When the HLMFR is less than 180 g / 10 minutes, the fluidity is insufficient and high-speed moldability cannot be expected, and when it exceeds 400 g / 10 minutes, the stress crack resistance of the container lid is not always sufficient.
The ratio of melt flow rate (MFR) to high melt flow rate (HLMFR), that is, HLMFR / MFR is 80 to 200, preferably 80 to 180, more preferably 100 to 160. If the HLMFR / MFR is less than 80, there is no decrease in viscosity at a predetermined shear rate, so that the fluidity is insufficient and the high-speed moldability is deteriorated, and if it exceeds 200, shrinkage anisotropy tends to occur.
In the present invention, the MFR and HLMFR of the polyethylene resin molding material are values measured according to JIS-K6922-2: 1997.

Characteristics (2)
The polyethylene-based resin molding material of the present invention has a density of 0.955 g / cm ³ or more and 0.970 g / cm ³ or less, preferably 0.956 to 0.968 g / cm ³ , more preferably 0.958 to 0. 965 g / cm ³ . If the density is less than 0.955 g / cm ³ , the rigidity of the container lid is lowered, the container lid cannot be thinned, and is easily deformed at a high temperature. Become. When the density exceeds 0.970 g / cm ³ , the stress crack resistance of the container lid is not always sufficient.
In the present invention, the density of the polyethylene-based resin molding material is a value measured according to JIS-K6922-1, 2: 1997.

Characteristic (3)
Polyethylene resin molding material of the present invention, the molecular weight of 10 ⁵ or more components, ^{13 C-NMR} formula from the measured value by the spectrum (a) by the obtained CSD of (comonomer - Deployment Shea - - Kuensu-distributor) The value is 0.0 to 3.0. In the present invention, the CSD is preferably 0.0 to 2.5.
CSD = 4 × [EE] [CC] / [EC] ² formulas (a)
(In formula (a), [EE] represents the number of ethylene / ethylene chains, [CC] represents the number of comonomer / comomer chains, and [EC] represents the number of ethylene / comonomer chains.)

In the present invention, the CSD (comonomer sequence distribution) of the polyethylene resin molding material is described in J. Org. C. Randall, JMS-REV. MACROMOL. CHEM. PHYS. , C29 (2 & 3), pages 201-317 (1989), the polyethylene resin molding material is measured by ¹³ C-NMR spectrum. Specifically, using the JEOL-GSX400 nuclear magnetic resonance apparatus manufactured by JEOL Ltd. under the following conditions, from the values of ethylene / ethylene chain number, comonomer / comomer chain number, ethylene / comonomer chain number, The following equation (a) can be obtained.
Apparatus: JEOL-GSX400 manufactured by JEOL Ltd., pulse width: 8.0 μsec (flip angle = 40 °), pulse repetition time: 5 seconds, integration number: 5000 times or more, solvent and internal standard: 1,2,4-tri Chlorobenzene / benzene-d6 / hexamethyldisiloxane (mixing ratio: 30/10/1), measurement temperature: 120 ° C., sample concentration: 0.3 g / ml Thereafter, the spectrum obtained by the measurement is obtained based on the following literature: be able to.
(1) In the case of ethylene / 1-butene copolymer: Macromolecules, 15, 353-360 (1982) (Eric T. Hsieh and James C. Randall),
(2) In the case of ethylene / 1-hexene copolymer: Macromolecules, 15, 1402-1406 (1982) (Eric T. Hsieh and James C. Randall)

The CSD obtained here takes a value from 0 to ∞. When the CSD value is high, a comonomer is inserted in a more block manner, and when the CSD value is low, a comonomer is inserted alternately (or randomly). Indicates that It can be said that the smaller the CSD, the better the composition distribution. When the CSD is in the range of the present invention, that is, 0.0 to 3.0, the balance between rigidity and stress crack resistance (ESCR) is excellent.
On the other hand, when CSD is larger than 3.0, it indicates that the composition distribution is wide, and the balance between rigidity and ESCR is lowered. CSD is affected by both intermolecular composition distribution and intramolecular composition distribution. In the Ziegler-Natta catalyst, the influence of intermolecular composition distribution is dominant. There is little variation in the amount of comonomer copolymerization, suggesting a narrow composition distribution.
In the present invention, preferably the smaller the value of CSD, because, becomes uniform on entering and short-chain branching, in a molecular weight ¹⁰⁵ or more components or components (A), the desired density (short-chain This is because the number of components that do not satisfy the number of branches) is reduced, so that the effects of the invention are easily exhibited.

(2) Composition as composition The polyethylene resin molding material of the present invention may be composed of a single ethylene polymer, or may be composed of a plurality of types of ethylene polymers as a composition. May be used. In the present invention, it is a plurality of types of ethylene polymer compositions, and the following component (A) is contained in an amount of 20% by weight to 40% by weight and the component (B) is contained in an amount of 60% by weight to 80% by weight. It is preferable that it is a composition.
Component (A): CSD (HLMFR is 0.1 to 5.0 g / 10 min, density is 0.915 to 0.935 g / cm ³ , and CSD determined by the formula (a) from the measured value by ¹³ C-NMR spectrum ( Ethylene polymer having a comonomer sequence distribution value CSD _A of 0.0 to 3.0 Component (B): Melt flow rate (MFR at a temperature of 190 ° C. and a load of 2.16 Kg) ) is 150 g / 10 minutes or more 600 g / less than 10 minutes, a density of 0.960 g / cm ³ or more 0.980 g / cm ³ less than the ethylene polymer

(2-1) Ethylene polymer of component (A) The ethylene polymer of component (A) has an HLMFR of 0.1 to 5.0 g / 10 min, preferably 0.2 to 3.0 g / min. 10 minutes, more preferably 0.3 to 2.0 g / 10 minutes. If the HLMFR of the component (A) is less than 0.1 g / 10 minutes, the fluidity tends to be lowered and the moldability tends to be poor, and if it exceeds 5.0 g / 10 minutes, the stress crack resistance tends to be lowered.

The density of component (A) is 0.915 to 0.935 g / cm ³ , preferably 0.918 to 0.932 g / cm ³ , more preferably 0.920 to 0.930 g / cm ³ . If the density of the component (A) is less than 0.915 g / cm ³ , the rigidity becomes insufficient, and if it exceeds 0.935 g / cm ³ , the stress crack resistance tends to be lowered.

The ethylene polymer of the component (A) was measured by a ¹³ C-NMR spectrum, and the CSD (comonomer sequence distribution) value CSD _A determined by the formula (a) was 0.0. It is -3.0, Preferably it is 0.0-2.5, More preferably, it is 0.0-2.2. When the CSD _{A of the} component (A) is in the range of the present invention, that is, 0.0 to 3.0, the balance between rigidity and stress crack resistance (ESCR) is excellent. On the other hand, when CSD _A is larger than 3.0, it indicates that the composition distribution is wide, and the balance between rigidity and ESCR tends to decrease.
In the present invention, but preferably the smaller the value of CSD, because, becomes uniform entering and short-chain branching, in a molecular weight ¹⁰⁵ or more components or components (A), the desired density (short This is because the number of components that do not satisfy (the number of chain branches) is reduced, so that the effects of the invention are more easily manifested.

In addition, MFR, HLMFR, density, and CSD _A are each measured by the said measuring method.
The ethylene polymer of component (A) may be a polymer of ethylene alone, but is preferably a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, and more preferably ethylene and 1-butene. Or a copolymer of ethylene and 1-hexene. The copolymerization ratio of the α-olefin having 3 to 20 carbon atoms is preferably 0.001 to 5.0 mol%.

(2-2) Ethylene polymer of component (B) The ethylene polymer of component (B) has an MFR of 150 g / 10 min or more and less than 600 g / 10 min, preferably 180 to 500 g / 10 min, Preferably it is 200-350 g / 10min. When the MFR of the component (B) is less than 150 g / 10 minutes, the fluidity tends to be lowered and the moldability tends to be poor, and when it is 600 g / 10 minutes or more, the stress crack resistance tends to be lowered.
The density of component (B), 0.960 g / cm ³ or more 0.980 g / cm less than ^3, preferably 0.965~0.975g / cm ^3, more preferably at 0.965~0.970g / cm ³ is there. When the density of the component (B) is less than 0.960 g / cm ³ , the rigidity may be lowered, and those with 0.980 g / cm ³ or more are difficult to produce.
The ethylene polymer of the component (B) is preferably an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, more preferably an ethylene homopolymer, ethylene and 1-butene. A copolymer or a copolymer of ethylene and 1-hexene is preferred. In the case of a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, the copolymerization ratio of the α-olefin having 3 to 20 carbon atoms is preferably 0.001 to 5.0 mol%.

In order to achieve all of fluidity, rigidity, and stress crack resistance performance higher, the blending amount of component (A) and component (B) is important. The ratio of the component (A) to the component (B) is such that the component (A) is 20% by weight or more and 40% by weight or less, the component (B) is 60% by weight or more and 80% by weight or less, and preferably the component (A) is 20 to 35% by weight, component (B) is 65 to 80% by weight, more preferably component (A) is 20 to 30% by weight, and component (B) is 70 to 80% by weight.
If the component (A) is less than 20% by weight, the stress crack resistance tends to decrease, and if it exceeds 40% by weight, the moldability tends to decrease, and if the component (B) is less than 60% by weight, the moldability decreases. If it exceeds wt%, the stress crack resistance tends to decrease. When it deviates from this range, any one or more of fluidity, rigidity, and stress crack resistance tends to fail to achieve this requirement.
In the present invention, the ethylene polymer may be composed only of the component (A) and the component (B), or may contain other arbitrary resin components.

(3) Other requirements as a composition In the present invention, the ethylene polymer of component (A) is a CSD (comonomer sequence sequence) obtained by the formula (a) from the measured value by ¹³ C-NMR spectrum. views - Deployment) and value (CSD _a) ^of, 13 C-NMR was measured by spectrum, short chain branching number of 1 to 20 carbon atoms per carbon atom 1,000 main chain SCB _a (number / 1,000C) However, it is preferable to satisfy | fill following formula (b). More preferably, in the present invention, CSD _A and SCB _A satisfy the following formula (c). More preferably, the following formula (d) is satisfied.
CSD _A <−0.1273 × SCB _A +3.30 Formula (b)
CSD _A <−0.1273 × SCB _A +3.10 Formula (c)
CSD _A <−0.1273 × SCB _A +2.00 Formula (d)

In an ethylene polymer, the value of CSD is affected by the number of short chain branches, and the smaller the number of short chain branches, the greater the number of ethylene / ethylene chains, and the [CC] of [EE] in formula (a) Since the ratio to [EC] increases, the numerical value of CSD increases. Therefore, even with the same CSD value, the smaller the number of short chain branches, the better the composition distribution.
In the present invention, the short chain branching number SCB _A (pieces / 1,000 C) of 1 to 20 carbon atoms per 1,000 carbon atoms of the main chain of the ethylene polymer of the component (A) is a polyethylene resin molding. The ¹³ C-NMR spectrum measurement of the “component A” of the material is measured under the same conditions as the ¹³ C-NMR spectrum measurement used for the calculation of the CSD, and can be obtained based on the following literature.

(1) In the case of ethylene / 1-butene copolymer: Macromolecules, 15, 353-360 (1982) (Eric T. Hsieh and James C. Randall),
(2) In the case of ethylene / 1-hexene copolymer: Macromolecules, 15, 1402-1406 (1982) (Eric T. Hsieh and James C. Randall)

Here, when CSD _A and SCB _A satisfy the scope of the present invention, that is, the formula (b), it becomes a linear lower region in FIG. 1, but has an excellent balance between rigidity and stress crack resistance (ESCR). Yes. On the other hand, when the expression (b) is not satisfied, the linear upper region in FIG. 1 is obtained, but the composition distribution is wide, and the balance between rigidity and ESCR tends to decrease.
In the present invention, the relational expression between CSD _A and SCB _A is an approximate expression using CSD _A as a function of SCB _A for the sake of convenience in order to distinguish the conventional polyethylene resin molding material from the polyethylene resin molding material of the present invention. It is obtained and a preferable range is set as a boundary. In the present invention, even if the relational expression is satisfied, the desired performance cannot be obtained unless the other characteristics of the present invention are satisfied.

In the present invention, in order to obtain an ethylene polymer satisfying the relational expression between CSD _A and SCB _A , control of insertion of a comonomer is important, and various methods can be mentioned. For example, for the polymer of the present invention, the polymerization conditions and the polymerization catalyst system are one of the important factors. Known patent documents (Japanese Patent Laid-Open Nos. 56-61406 and 56-141304, Specific magnesium compounds, titanium compounds, organic halogenated compounds described in JP-A-56-166206, JP-A-57-141407, JP-A-60-23581, JP-A-61-246209) It can be easily controlled by using a catalyst comprising a combination of a solid catalyst obtained from an aluminum compound and an organoaluminum compound.

Characteristic (4)
The polyethylene-based resin molding material of the present invention preferably has a flexural modulus of 900 to 1500 MPa, more preferably 950 to 1450 MPa. When the flexural modulus is less than 900 MPa, the rigidity is lowered, and the container lid is easily deformed by the internal pressure of the container, and particularly easily deformed at a high temperature. Here, the flexural modulus is a value measured according to JIS-K6922-2: 1997, using a 4 × 10 × 80 mm plate-like body injection-molded at 210 ° C. as a test piece.

Characteristic (5)
The polyethylene resin molding material of the present invention preferably has a melt viscosity at 190 ° C. and a shear rate of 400 sec ⁻¹ of 200 to 500 Pa · s, more preferably 250 to 400 Pa · s. If the melt viscosity is less than 200 Pa · s, the high fluidity is excellent, but the stress crack resistance is lowered, and the fluidity and the stress crack resistance cannot be achieved at the same time. When the melt viscosity exceeds 500 Pa · s, the fluidity is lowered, so that the high-speed moldability is lowered.
The polyethylene-based resin molding material of the present invention preferably has a tensile yield strength of 25 MPa or more, preferably 26 MPa or more, and more preferably 27 MPa or more. If the tensile yield strength is less than 25 MPa, the brittleness of the bridge portion of the container lid is poor and the appropriate hardness is insufficient. The upper limit of the tensile yield strength is not particularly limited, but is usually 50 MPa or less. Here, the tensile yield strength is a value measured according to JIS-K6922-2: 1997.
The tensile yield strength correlates with the looseness of the container lid. If the tensile yield strength is low, the container lid tends to loosen, and the container lid is not sufficiently hard to close. In order to improve the stress crack resistance of the container lid, it is necessary to reduce the density of the polyethylene-based material. Therefore, it is difficult to improve the tensile yield strength while improving the stress crack resistance. However, according to the present invention, it is possible to improve both the looseness of the container lid and the stress crack resistance.
The polyethylene resin molding material preferably has a hydrocarbon volatile content of 80 ppm or less. The hydrocarbon volatile content is preferably 50 ppm or less, more preferably 30 ppm or less. The hydrocarbon referred to in the present invention refers to a compound containing at least carbon and hydrogen in the molecule, and is usually measured by gas chromatography. The effects of smell and flavor can be prevented. Here, the hydrocarbon volatile content is obtained by measuring 1 g of polyethylene resin molding material in a 25 ml glass sealed container and measuring the air in the head space when heated at 130 ° C. for 60 minutes by gas chromatography. It is done.

Characteristic (6)
The polyethylene resin molding material has a breaking time (FNCT) at 80 ° C. and 1.9 MPa by a full notch creep test of preferably 40 hours or more, more preferably 50 hours or more, and further preferably 60 hours or more. If the FNCT is less than 40 hours, there is a high possibility that breakage due to stress cracks will occur in the container lid during high temperature storage in summer. Here, FNCT is measured according to JIS-K6774: 1998 at a temperature of 80 ° C. using a 1% aqueous solution of Emal manufactured by Kao Corporation.

Characteristic (7)
The polyethylene-based resin molding material of the present invention preferably has a constant strain stress crack resistance (constant strain ESCR) of an injection molded sample for 200 to 1000 hours. When it is less than 200 hours, cracks occur when a liquid having a high internal pressure such as a carbonated beverage is stored. On the other hand, when it exceeds 1000 hours, the stress crack resistance is excellent, but the rigidity and fluidity are lowered, and the performance cannot be satisfied in all items.
The polyethylene-based resin molding material of the present invention preferably has a shrinkage ratio anisotropy (MD / TD) of 1.0 or more and less than 2.5. MD / TD is preferably 1.0 or more and less than 2.3, and more preferably 1.1 or more and less than 2.0. This value is obtained by forming a 120 × 120 × 2 mm flat plate of one side film gate (gate thickness 0.2 mm) at a molding temperature of 190 ° C. and a mold temperature of 40 ° C., and after molding at 23 ° C. It is a numerical value obtained by measuring the shrinkage rate in the flow direction (MD) and the flow right angle method (TD) after standing for 48 hours and dividing the MD value by the TD value. When the shrinkage ratio anisotropy (MD / TD) is 2.5 or more, the molded product is easily broken, and when it is less than 1.0, the product is easily deformed. Shrinkage ratio anisotropy (MD / TD) can be adjusted by molecular weight distribution.

2. Production of polyethylene resin molding material The polyethylene polymer contained in the polyethylene resin molding material of the present invention can be produced by homopolymerization of ethylene alone or copolymerization of ethylene and α-olefin. The polyethylene-based polymer contained in the polyethylene-based resin molding material can be obtained by normal one-stage polymerization, but the polymerized components can be mixed under different conditions or manufactured as a composition by sequential multi-stage polymerization. You can also.

(1) Production of Composition by Mixing or Sequential Multi-stage Polymerization In the present invention, the polyethylene resin molding material is obtained by mixing the ethylene polymer of component (A) and the ethylene polymer of component (B). be able to.
For reasons such as the uniformity of the resin, those obtained by sequentially and successively polymerizing the ethylene polymer of component (A) and the ethylene polymer of component (B) (sequential multistage polymerization method) are preferred. It can be obtained by successively polymerizing ethylene and α-olefin in a plurality of reactors connected in series.
In this case, an ethylene homopolymer is polymerized in one polymerization reactor, and a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms is polymerized in the other polymerization reactor, one polymerization reactor Can be used to polymerize a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, and to further copolymerize ethylene and an α-olefin having 3 to 20 carbon atoms in another polymerization reactor. The former is preferred.
That is, in the present invention, at least one of the component (A) and the component (B) of the polyethylene polymer is polymerized by multistage polymerization in which at least two polymerization reactors are combined in the presence of a polymerization catalyst. It is preferable that an ethylene homopolymer is polymerized in a reactor, and an ethylene copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms is polymerized in at least another polymerization reactor.

  Moreover, the composition which consists of a component (A) and a component (B) of this invention may mix after mixing a component (A) and a component (B) separately. Furthermore, each of the ethylene polymer of component (A) and component (B) can be composed of a plurality of components. The ethylene polymer may be a polymer successively polymerized in a multistage polymerization reactor using one type of catalyst, and may be produced in a single stage or multistage polymerization reactor using a plurality of types of catalysts. A polymer obtained by polymerizing using one kind or plural kinds of catalysts may be used.

(2) Polymerization method In the present invention, the ethylene-based polymer can be produced by a production process such as a gas phase polymerization method, a solution polymerization method, a slurry polymerization method, etc., and a slurry polymerization method is preferred. Among the polymerization conditions for the ethylene-based polymer, the polymerization temperature can be selected from the range of 0 to 300 ° C. In slurry polymerization, the polymerization is performed at a temperature lower than the melting point of the produced polymer. The polymerization pressure can be selected from the range of atmospheric pressure to about 100 kg / cm ² . It is selected from aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, etc. in a state where oxygen and moisture are substantially cut off. It can preferably be produced by slurry polymerization of ethylene and α-olefin in the presence of an inert hydrocarbon solvent.

The hydrogen supplied to the polymerization vessel in the slurry polymerization is consumed as a chain transfer agent, determines the average molecular weight of the ethylene-based polymer to be produced, and partly dissolves in a solvent and is discharged from the polymerization vessel. The solubility of hydrogen in the solvent is small, and the hydrogen concentration near the polymerization active point of the catalyst is low unless a large amount of gas phase is present in the polymerization vessel. Therefore, if the hydrogen supply amount is changed, the hydrogen concentration at the polymerization active point of the catalyst changes rapidly, and the molecular weight of the produced ethylene polymer changes following the hydrogen supply amount in a short time. Therefore, if the amount of hydrogen supply is changed in a short cycle, a more homogeneous product can be produced. Therefore, it is preferable to employ a slurry polymerization method as the polymerization method. Moreover, although the aspect of change of the hydrogen supply amount may be changed continuously, the effect of widening the molecular weight distribution can be obtained by changing it discontinuously.
In the present invention, it is important to change the hydrogen supply amount during the polymerization of the ethylene-based polymer, but other polymerization conditions such as polymerization temperature, catalyst supply amount, ethylene and other olefin supply amount, 1-butene It is also important to change the supply amount of the comonomer, the supply amount of the solvent, etc. at the same time as the hydrogen change or separately.

(3) Sequential multi-stage polymerization A so-called sequential multi-stage polymerization method, in which polymerization is performed sequentially in a plurality of reactors connected in series, produces a high molecular weight component in the first polymerization zone (first-stage reactor), The obtained polymer may be transferred to the next reaction zone (second stage reactor) to produce a low molecular weight component in the second stage reactor, or the first polymerization zone (first stage reactor). The low molecular weight component is produced in the first reactor), the obtained polymer is transferred to the next reaction zone (second stage reactor), and the high molecular weight component is produced in the second stage reactor. Either method is acceptable.
A specific preferable polymerization method is the following method. That is, using a Ziegler catalyst containing a titanium-based transition metal compound and an organoaluminum compound and at least two reactors, ethylene and α-olefin are introduced into the first stage reactor, and a low-density high molecular weight is obtained. The component polymer is manufactured, the polymer extracted from the first stage reactor is transferred to the second stage reactor, and ethylene and hydrogen are introduced into the second stage reactor to increase the density. This is a method for producing a polymer having a low molecular weight component.
In the case of multistage polymerization, the amount of ethylene polymer produced in the second and subsequent polymerization zones and its properties are determined by determining the amount of polymer produced in each stage (which can be determined by unreacted gas analysis). The physical properties of the polymer extracted after each step can be measured, and the physical properties of the polymer produced at each step can be determined based on the additivity.

(4) Polymerization catalyst As the polymerization catalyst for the ethylene polymer, various catalysts such as a Ziegler catalyst, a Phillips catalyst, and a metallocene catalyst are used. Any polymerization catalyst can be used as long as hydrogen exhibits a chain transfer action of olefin polymerization. Specifically, any catalyst can be used as long as it is composed of a solid catalyst component and an organometallic compound and is suitable for slurry-type olefin polymerization in which hydrogen exhibits a chain transfer action of olefin polymerization. Preferred is a heterogeneous catalyst in which polymerization active sites are localized. The solid catalyst component is not particularly limited as long as it is used as a solid catalyst for olefin polymerization containing a transition metal compound.

As the transition metal compound, a metal compound of Group IV to Group VIII, preferably Group IV to Group VI of the periodic table can be used. Specific examples include Ti, Zr, Hf, V, Examples of the compound include Cr and Mo. An example of a preferred catalyst is a solid Ziegler catalyst comprising a Ti and / or V compound and an organometallic compound of a Group I to Group III metal of the periodic table. Furthermore, a combination of a complex called a metallocene catalyst, which is a ligand having a cyclopentadiene skeleton coordinated to a transition metal, and a promoter is exemplified. As a specific metallocene catalyst, a complex catalyst in which a ligand having a cyclopentadiene skeleton such as methylcyclopentadiene, dimethylcyclopentadiene or indene is coordinated to a transition metal containing Ti, Zr, Hf, lanthanide series, etc. In combination with an organometallic compound of a Group I to Group III metal such as aluminoxane as a co-catalyst, and a supported type in which these complex catalysts are supported on a carrier such as silica. It is done. Particularly preferred solid catalyst components for olefin polymerization include those containing at least titanium and / or vanadium and magnesium.
As the organometallic compound that can be used together with the solid catalyst component containing at least titanium and / or vanadium and magnesium, an organoaluminum compound, particularly, a trialkylaluminum is preferable. Although the amount of the organoaluminum compound used in the polymerization reaction is not particularly limited, it is usually preferably in the range of 0.05 to 1,000 moles per mole of the titanium compound.
More specifically, a Ziegler catalyst composed of a solid catalyst component and an organoaluminum compound is preferred, and in particular, it can be suitably carried out by using a catalyst and a production method described in the following known literature. That is, JP-A 56-61406, JP-A 56-141304, JP-A 56-166206, JP-A 57-141407, JP-A 60-235813, JP It is preferable to polymerize olefins using the catalyst system described in JP-A-61-246209.
In the present invention, the polymerization catalyst for the ethylene-based polymer has a general formula Mg (OR ² ) _m X ² _2-m (wherein R ² represents an alkyl, aryl, or cycloalkyl group, and X ² represents a halogen atom. And m is 1 or 2) and the general formula Ti (OR ³ ) _n X ³ _4-n (wherein R ³ represents an alkyl, aryl, or cycloalkyl group, X ³ represents a halogen atom, and n is 1, 2 or 3. A homogeneous hydrocarbon solution containing a compound represented by the general formula AlR ¹ _l X ¹ _3-l (wherein R ¹ is alkyl, A hydrocarbon-insoluble solid catalyst obtained by treatment with an organic aluminum halide compound represented by the following formula: aryl or cycloalkyl group, X ¹ represents a halogen atom, and l represents a number of 1 ≦ l ≦ 2. Catalyst system containing bismuth and organoaluminum compound Preferred.

(5) Polymerized monomer
In the present invention, the ethylene polymer is a homopolymer of ethylene, or ethylene and an α-olefin having 3 to 12 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1- It is obtained by copolymerization with pentene, 1-octene or the like, and in the case of copolymerization, 1-butene and 1-hexene are mentioned as preferred monomers.
Also, copolymerization with a diene for the purpose of modification is possible. Examples of the diene compound used at this time include butadiene, 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene, and the like.
The comonomer content during the polymerization can be arbitrarily selected. For example, in the case of copolymerization of ethylene and an α-olefin having 3 to 12 carbon atoms, an ethylene / α-olefin copolymer is used. The α-olefin content therein is 0 to 40 mol%, preferably 0 to 30 mol%.
As raw material ethylene, it can also superpose | polymerize using plant-derived ethylene and can also be used as an ethylene-type polymer using this ethylene.

3. Control method of characteristic value in polyethylene resin molding material (1) MFR and HLMFR
In the production of the polyethylene resin molding material of the present invention, MFR and HLMFR can be adjusted to a desired range by the temperature in the polymerization of the ethylene monomer and the use of a chain transfer agent. That is, the molecular weight can be decreased by increasing the polymerization temperature of ethylene and α-olefin, resulting in an increase in MFR and HLMFR, and the molecular weight can be increased by decreasing the polymerization temperature, resulting in a decrease in MFR and HLMFR. can do. Moreover, in the copolymerization reaction of ethylene and α-olefin, the molecular weight can be lowered by increasing the amount of coexisting hydrogen (amount of chain transfer agent), and as a result, MFR and HLMFR can be increased. By decreasing (chain transfer agent amount), the molecular weight can be increased, and as a result, MFR and HLMFR can be reduced.

(2) HLMFR / MFR
In the production of the polyethylene resin molding material of the present invention, the HLMFR / MFR (flow ratio FLR) can be increased or decreased by adjusting the molecular weight distribution. This HLMFR / MFR correlates with monodispersity of molecular weight (weight average molecular weight Mw / number average molecular weight Mn) by gel permeation chromatography, and HLMFR / MFR of 100 is about 18 of monodisperse Mw / Mn. It corresponds to. HLMFR / MFR or Mw / Mn can be adjusted by the type of catalyst, the type of promoter, the polymerization temperature, the residence time in the polymerization reactor, the number of polymerization reactors, etc. The speed can be adjusted, and preferably can be increased or decreased by adjusting the mixing ratio of the high molecular weight component and the low molecular weight component.
The ethylene polymer HLMFR / MFR or Mw / Mn is easily affected by the type of catalyst. Generally, the molecular weight distribution is wide according to the Phillips catalyst, and the molecular weight distribution is narrow according to the metallocene catalyst. Therefore, the polymer has an intermediate molecular weight distribution.

(3) Density In the production of the polyethylene-based resin molding material of the present invention, the density can be adjusted to a desired range by changing the kind and amount of the copolymer to be copolymerized with ethylene.

(4) CSD
In the polyethylene-based resin molding material of the present invention, when the CSD has a high value, the comonomer is inserted in a block manner, and when the CSD value is low, the comonomer is inserted alternately (or randomly). The control of the insertion of the comonomer is subject to various technological innovations in the polyolefin polymerization field, and there are various methods. For the polymer of the present invention, the polymerization catalyst system is one of the important factors. The above-mentioned known patent documents (Japanese Patent Laid-Open Nos. 56-61406, 56-141304, 56-166206, 57-141407, Japanese Patent 60) Easy to use a catalyst comprising a combination of a solid catalyst obtained from a specific magnesium compound, a titanium compound and an organic aluminum halide compound described in JP-A No. 235813 and JP-A No. 61-246209) and an organic aluminum compound. Can be controlled.

(5) Number of short-chain branches having 1 to 20 carbon atoms per 1,000 carbon atoms in the main chain In the production of the polyethylene-based resin molding material of the present invention, the number of short-chain branches is the type of copolymer to be copolymerized with ethylene. The amount can be adjusted to a desired range by changing the amount. Short chain branching number is correlated with density, for example, density 0.916 g / cm ³ at approximately 14 / 1,000C, is approximately four / 1,000C about a density 0.930 g / cm ^3.

(6) Control of other characteristic values
In the production of the polyethylene-based resin molding material of the present invention, the flexural modulus can be adjusted by increasing or decreasing the molecular weight and density of polyethylene, and the flexural modulus can be increased by increasing the molecular weight or density.
The melt viscosity at 190 ° C. and a shear rate of 400 sec ⁻¹ can be adjusted by increasing or decreasing the molecular weight and density of polyethylene, and the melt viscosity can be increased by increasing the molecular weight.
The tensile yield strength can be adjusted by increasing or decreasing the density, and can be increased by increasing the density.
In order to reduce the hydrocarbon volatile content to a predetermined value or less, the polymerized polyethylene polymer is subjected to volatile content removal operations such as steam stripping treatment, hot air deodorization treatment, vacuum treatment, nitrogen purge treatment, etc. This control operation can be exhibited remarkably by performing a steam deodorizing process. The conditions for the steam treatment are not particularly limited, but it is preferable that the ethylene polymer is brought into contact with a steam at 100 ° C. for about 8 hours.
Furthermore, in order to increase the breaking time (FNCT) at 80 ° C. and 1.9 MPa according to the full notch creep test, it can be achieved by adding a low density and high molecular weight component.
The constant strain ESCR can be achieved by adjusting the density, molecular weight and molecular weight distribution, and appropriately using the low density and high molecular weight component of the component (A) in the present invention.

4). Molding material An ethylene-based resin molding material containing an ethylene-based polymer produced by the above method is pelletized by mechanical melting and mixing with a pelletizer or homogenizer according to a conventional method, and then by various molding machines. The container lid can be formed by molding.
In order to enhance various physical properties or add other physical properties to ethylene-based resin molding materials, other than olefin polymers and rubbers, antioxidants (phenolic, phosphorus, etc.) are used in accordance with conventional methods. System, sulfur system), UV absorber, light stabilizer, lubricant, antistatic agent, antifogging agent, antiblocking agent, processing aid, color pigment, crosslinking agent, foaming agent, inorganic or organic filler, flame retardant, etc. 1 type, or 2 or more types can be mix | blended suitably.

As filler, calcium carbonate, talc, metal powder (aluminum, copper, iron, lead, etc.), silica, diatomaceous earth, alumina, gypsum, mica, clay, asbestos, graphite, carbon black, titanium oxide, etc. are used. Among them, it is preferable to use calcium carbonate, talc, mica, and the like.
In the present invention, it is also an effective technique to use a nucleating agent in order to accelerate the crystallization rate. The nucleating agent is not particularly limited, and a general organic or inorganic nucleating agent can be used. In any case, various additives may be blended with the polyethylene as necessary, and kneaded with a kneading extruder, a Banbury mixer, or the like to obtain a molding material.

5. Use as a container lid member A container lid member is manufactured by using the polyethylene-based resin molding material of the present invention as a raw material and molding it by an injection molding method or a compression molding method. The container lid member is preferably manufactured by a continuous compression molding method.
Since the polyethylene-based resin molding material of the present invention satisfies various characteristics, it is excellent in moldability, high fluidity, odor, impact resistance, food safety, rigidity, etc., and excellent in heat resistance. Therefore, it is suitable for uses such as containers and container lids that require such characteristics, and particularly suitable for soft drinks such as carbonated drinks having a high internal pressure.
In addition, it can also be used for containers and container lids for foods and beverages such as edible oil and wasabi, seasonings and alcoholic beverages, and containers and container lids for cosmetics and hair creams. Molded with.
In particular, the polyethylene-based resin molding material of the present invention exhibits an excellent effect when used for a container lid of a carbonated beverage liquid from the viewpoint of pressure resistance. The container lid for carbonated beverages using the material of the present invention can be molded at a high speed and formed into a one-piece shape, and is optimally used for containers such as PET bottles.

  Hereinafter, in order to show the present invention more specifically and clearly, examples and comparative examples will be described. However, the present invention is not limited to these examples. The measurement methods and evaluation methods used in the examples are as follows.

(1) Melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 kg: Measured according to JIS-K6922-2: 1997.
(2) High melt flow rate (HLMFR) at a temperature of 190 ° C. and a load of 21.6 kg: Measured according to JIS-K6922-2: 1997.
(3) Density: Measured according to JIS-K6922-1, 1997.

(4) Comonomer sequence distribution (CSD): C. Randall, JMS-REV. MACROMOL. CHEM. PHYS. , C29 (2 & 3), pages 201-317 (1989), the polyethylene-based resin molding material was measured by ¹³ C-NMR spectrum. Specifically, the JEOL-GSX400 nuclear magnetic resonance apparatus manufactured by JEOL Ltd. was used to measure the number of ethylene / ethylene chains, the number of comonomer / comomer chains, and the number of ethylene / comonomer chains. It calculated | required by Formula (a).
CSD = 4 × [EE] [CC] / [EC] ² formulas (a)
Specifically, the measurement was performed under the following conditions.
Apparatus: JEOL-GSX400 manufactured by JEOL Ltd., pulse width: 8.0 μsec (flip angle = 40 °), pulse repetition time: 5 seconds, integration number: 5000 times or more, solvent and internal standard: 1,2,4-tri Chlorobenzene / benzene-d6 / hexamethyldisiloxane (mixing ratio: 30/10/1), measurement temperature: 120 ° C., sample concentration: 0.3 g / ml.
Moreover, the spectrum obtained by measurement was calculated | required based on the following literature.
(I) In the case of ethylene / 1-butene copolymer: Macromolecules, 15, 353-360 (1982) (Eric T. Hsieh and James C. Randall),
(Ii) In the case of ethylene / 1-hexene copolymer: Macromolecules, 15, 1402-1406 (1982) (Eric T. Hsieh and James C. Randall)

(5) The number of short chain branches having 1 to 20 carbon atoms per 1,000 carbon atoms in the main chain SCB _A : ¹³ C-NMR spectrum measurement of “component A” of polyethylene resin molding material is used for the calculation of CSD Measurement was performed under the same conditions as the ¹³ C-NMR spectrum measurement used, and the measurement was performed based on the following literature.
(I) In the case of ethylene / 1-butene copolymer: Macromolecules, 15, 353-360 (1982) (Eric T. Hsieh and James C. Randall),
(Ii) In the case of ethylene / 1-hexene copolymer: Macromolecules, 15, 1402-1406 (1982) (Eric T. Hsieh and James C. Randall)

(6) Fracture time at 1.9 MPa (FNCT) by full-notch creep test: JIS-K6774: In accordance with 1998, at a temperature of 80 ° C., a 1% aqueous solution of detergent emulsion manufactured by Kao Corporation is used. Measured.
(7) Flexural modulus: Measured according to JIS-K6922-2: 1997, using a 4 × 10 × 80 mm plate-like body injection-molded at 210 ° C. as a test piece.
(8) Tensile yield strength: measured in accordance with JIS-K6922-2: 1997.
(9) Viscosity at melting: Using a capillary rheometer manufactured by Intesco, the melt viscosity at a shear rate of 400 sec ^-1 was measured using a capillary having a diameter of 1 mm and L / D: 35 at 190 ° C.

(10) High-speed moldability: Molding is performed at a molding temperature of 190 ° C. and a mold temperature of 40 ° C. using a cylindrical container lid mold having a diameter of 30 mm and a height of 20 mm and a Toshiba Machine IS-80 injection molding machine. evaluated. A product having a cooling time of 6 seconds or less was marked with ◯, and a product that was soft within 6 seconds or poorly slidable with the mold and therefore could bite into the mold and could not be released was marked with ×.
(11) Sustained pressure test: 500 ml of carbonated water having a carbon dioxide concentration of 2,250 ml with respect to 500 ml in a 500 ml PET bottle is filled at 5 ° C., and the container obtained by molding (10) above The container was sealed with a lid, kept in a heated state at 50 ° C. and 60 ° C. for one month, and the state of the container lid was observed. The case where the top surface of the container lid was not deformed was rated as ◯, and the case where liquid leakage or gas leakage occurred due to the deformation was rated as x.
(12) Top surface crack test: In the above-mentioned sustained pressure test, the case where no crack was generated on the top surface was indicated as ◯, and the case where a crack occurred was indicated as ×.
(13) Constant strain ESCR: A predetermined test piece was cut out from a 120 × 120 × 2 mm injection-molded plate as a test piece and measured according to ASTM D1693-01: 2001.
(14) Shrinkage anisotropy (MD / TD): using a FANUC ROBOSHOT 200i-100B injection molding machine at a molding temperature of 190 ° C. and a mold temperature of 40 ° C. 120 × 120 × 2 mm flat plate having a thickness of 0.2 mm), and after forming, the shrinkage rate in the flow direction (MD) and the flow right angle method (TD) after standing at 23 ° C. for 48 hours was measured. MD / TD was calculated from the measured value.

[Example 1]
(Manufacture of catalyst)
115 g of magnesium ethoxide, 151 g of tri-n-butoxymonochloro titanium and 37 g of n-butanol were mixed at 150 ° C. for 6 hours to homogenize. Next, the temperature was lowered to 60 ° C., and n-hexane was added to obtain a uniform solution. Next, 457 g of ethylaluminum sesquichloride was dropped at a predetermined temperature and stirred for 1 hour. 210g of catalyst components were obtained by wash | cleaning the produced | generated precipitation with n-hexane. The obtained solid was dried to obtain a powder. The powder contained 11.0% by weight of Mg and 10.5% by weight of Ti.
(Manufacture of polymer)
Supply the solid catalyst component 1.5g / hr obtained in the above (Manufacture of catalyst) from the catalyst supply line and the organometallic compound triethylaluminum from the catalyst supply line to the first stage polymerizer with an internal volume of 200 liters as the first stage reactor. A polymerization solvent (n-hexane) 70 (l / hr), hydrogen 78 (mg / hr), ethylene 13.8 at 70 ° C. while supplying 40 mmol / hr from the line and discharging the polymerization contents at a required rate. (Kg / hr), 1-butene was fed at a rate of 0.35 (kg / hr), and the first-stage copolymerization was carried out continuously under conditions of a total pressure of 1.3 MPa and an average residence time of 2.4 hr. .
A part of the polymerization product in the first-stage reactor was collected, the polymer was recovered, and the physical properties were measured. The result was designated as “high molecular weight component (A)”.
The slurry-like polymerization product produced in the first stage reactor was introduced into the second stage reactor having an internal volume of 400 liters as it was through a continuous tube having an inner diameter of 50 mm, and the contents of the polymerizer were discharged at the required speed. The polymerization solvent (n-hexane) 100 (l / hr), hydrogen 31.9 (g / hr), ethylene 43.8 (kg / hr) were fed at 82 ° C. at a total pressure of 1.1 MPa, The second stage polymerization was carried out continuously under the condition of an average residence time of 1.8 hours.
The polymerization product discharged from the second stage reactor was introduced into a flushing tank, the polymerization product was continuously withdrawn, and unreacted gas was removed from the degassing line. The resulting polymer was subjected to steam stripping treatment, granulated with a pelletizer, and then evaluated for physical properties. The results are shown in Table 2. In Table 2, the physical properties of the “low molecular weight component (B)” produced in the second stage reactor are the physical properties of the polyethylene composition as the final product and the component (A) obtained in the first stage reactor. It was calculated from the physical properties by calculation based on the additivity rule.
The material obtained by the above method had high tensile yield strength, excellent mechanical properties such as flexural modulus, and excellent suitability for container lids that required durability.

[Examples 2 to 7]
An ethylene polymer was obtained in the same manner as in Example 1 except for the conditions shown in Table 1. The “component (A)” and “component (B)” polymerized by the above method were blended in the proportions shown in Table 2 to produce the polyethylene-based resin molding material of the present invention. The evaluation results of the obtained materials are shown in Table 2. The obtained material had high tensile yield strength, excellent mechanical properties such as flexural modulus, and excellent container lid suitability requiring durability.

[Comparative Examples 1-3]
An ethylene polymer was obtained in the same manner as in Example 1 except for the conditions shown in Table 1. The “component (A)” and “component (B)” polymerized by the above method were blended in the proportions shown in Table 2 to produce a comparative polyethylene resin molding material. The evaluation results of the obtained materials are shown in Table 2. As shown in Table 2, since Comparative Example 1 has a low density, the rigidity is insufficient, and since the CSD of the component (A) is large, the stress crack resistance performance such as FNCT is lowered, and the container lid performance is not sufficient. Further, Comparative Example 2 had a low HLMFR and could not withstand high speed molding. In Comparative Example 3, due to the high MFR of the component (A), the stress crack resistance performance such as FNCT was low, and the suitability of the container lid was not sufficient.

[Contrast of results of Example and Comparative Example]
As described above, when the polyethylene-based resin molding materials of Examples 1 to 7 are used as a lid material for containers such as carbonated drinks in order to satisfy various characteristic requirements of the present invention, high-speed moldability, pressure resistance and durability are achieved. Excellent in properties. On the other hand, the polyethylene-based resin materials of Comparative Examples 1 to 3 have a low HLMFR, a high MFR of the component (A), a large CSD, and do not satisfy the various characteristic requirements of the present invention. Cannot be used for container lid material.
Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

  The polyethylene-based resin molding material for container lids of the present invention is the basic performance of the resin material for container lid members, which is high-speed moldability, high fluidity, rigidity, impact resistance, durability, heat resistance, slipperiness, low Various performances such as odor and food safety are well balanced and have excellent opening and sealing properties. Furthermore, stress crack resistance due to internal pressure of carbonated beverages during handling at high temperatures, FNCT fracture performance and tensile yield Since mechanical properties such as strength are also improved, it can be preferably used for forming a lid of a container that contains a liquid such as carbonated beverages.

Claims (9)

A polyethylene-based resin molding material for container lids, comprising as a main component a polyethylene-based polymer that satisfies the following characteristics (1) to (3).
Characteristic (1): The melt flow rate (MFR) at a temperature of 190 ° C. and a load of 2.16 Kg is 0.8 g / 10 minutes or more and less than 5.0 g / 10 minutes, and the high temperature at a temperature of 190 ° C. and a load of 21.6 Kg. Property (2): Density flow rate (HLMFR) is 180 g / 10 min or more and 400 g / 10 min or less and HLMFR / MFR is 80 to 200: density is 0.955 g / cm ³ or more and 0.970 g / of (Deployment comonomer - shea - - Kuensu-distributor) of molecular weight ¹⁰⁵ or more ^components, 13 C-NMR formula from the measured value of the spectrum (a) by the determined CSD: cm ³ or less is characteristic (3) The value is 0.0 to 3.0. CSD = 4 × [EE] [CC] / [EC] ² formula (a)
(In formula (a), [EE] represents the number of ethylene / ethylene chains, [CC] represents the number of comonomer / comomer chains, and [EC] represents the number of ethylene / comonomer chains.) The polyethylene polymer is a composition containing 20% by weight to 40% by weight of the following component (A) and 60% by weight or more and 80% by weight or less of the component (B). The polyethylene-based resin molding material for container lids according to 1.
Component (A): HLMFR was 0.1 to 5.0 g / 10 min, the density was 0.915 to 0.935 g / cm ³ , and the value was determined by the formula (a) from the measured value of ¹³ C-NMR spectrum. Ethylene polymer having a CSD value (CSD _A ) of 0.0 to 3.0 Component (B): MFR 150 g / 10 min or more and less than 600 g / 10 min, density 0.960 g / cm ³ or more and 0.980 g / Cm ³ ethylene polymer The polyethylene-based polymer further has a short C 1-20 carbon number per 1,000 carbon atoms of the main chain measured by the CSD value CSD _A of the component (A) and the ¹³ C-NMR spectrum of the component (A). The polyethylene-based resin molding material for container lid according to claim 1 or 2, wherein the number of chain branches SCB _A (pieces / 1,000 C) satisfies the following formula (b).
CSD _A <−0.1273 × SCB _A +3.3 Formula (b) The said polyethylene-type polymer further satisfy | fills the following characteristics (4) and (5), The polyethylene-type resin molding material for container lids in any one of Claims 1-3 characterized by the above-mentioned.
Property (4): Flexural modulus is 900-1500 MPa Property (5): Viscosity at melting at 190 ° C. and shear rate 400 sec ⁻¹ is 200-500 Pa · s The polyethylene-based resin molding material for container lids according to any one of claims 1 to 4, wherein the polyethylene-based polymer further satisfies the following characteristics (6) and (7).
Characteristic (6): Fracture time (FNCT) at 80 ° C. and 1.9 MPa by full notch creep test is 40 hours or more Characteristic (7): Constant strain stress crack resistance of injection molded sample is 200 to 1000 hours is there   At least one of the component (A) and the component (B) of the polyethylene polymer is subjected to ethylene single polymerization in at least one polymerization reactor by multistage polymerization combining at least two polymerization reactors in the presence of a polymerization catalyst. The polymer is polymerized, and an ethylene copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms is polymerized at least in another polymerization reactor. Polyethylene resin molding material for container lids. The polymerization catalyst of the polyethylene polymer has a general formula Mg (OR ² ) _m X ² _2-m (wherein R ² represents an alkyl, aryl or cycloalkyl group, X ² represents a halogen atom, m is 1 or 2, and a general formula Ti (OR ³ ) _n X ³ _4-n (wherein R ³ represents an alkyl, aryl or cycloalkyl group, and X ³ represents a halogen atom) A homogenous hydrocarbon solution containing a compound represented by the formula: n is 1, 2 or 3 is substituted with a general formula AlR ¹ _l X ¹ _3-l (wherein R ¹ is alkyl, aryl) Or a hydrocarbon insoluble solid catalyst obtained by treatment with an organic aluminum halide compound represented by the following formula: X ¹ represents a halogen atom, and l represents a number of 1 ≦ l ≦ 2. A catalyst containing a compound Polyethylene resin molding material for container closure according to any one of claims 1 to 6, wherein.   The said container lid is used for the container which accommodates carbonated drinks as a content, The polyethylene-type resin molding material for container lids in any one of Claims 1-7 characterized by the above-mentioned.   The polyethylene-based resin molding material for a container lid according to any one of claims 1 to 8, wherein the container lid is molded by continuous compression molding.

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