JPWO2011090101A1 - Multilayer blow container and method for producing the same - Google Patents

Abstract

An object of the present invention is to provide a multilayer blow container having high gloss, excellent surface appearance, and excellent impact resistance. In the multilayer blow container of the present invention, the resin used for the outermost layer is an olefin polymer formed from a propylene resin (A), an ethylene / α-olefin copolymer (B), and a nucleating agent (D). Comprising the composition (E), the propylene resin (A) is a copolymer of (A-1) propylene and an α-olefin, and (A-2) the crystal melting point is in the range of 140 to 155 ° C. The ethylene / α-olefin copolymer (B) is a copolymer of (B-1) ethylene and one or more α-olefins having 4 to 20 carbon atoms, and (B-2) a crystalline melting point. The olefin polymer composition (E) has a (E-1) MFR in the range of 5 to 10 g / 10 min.

Description

  The present invention relates to a multilayer blow container and a method for producing the same.

  As raw materials for blow molded articles such as blow containers, resins such as vinyl chloride resin, polycarbonate resin, ethylene resin, and propylene resin are used depending on the application.

  Among these resins, when a hard ethylene resin such as high density polyethylene is used, the gloss is poor, and when a soft ethylene resin such as low density polyethylene is used, the rigidity is low. There's a problem.

  In addition, when vinyl chloride resin is used, there is an environmental problem although it is excellent in gloss. When polycarbonate resin is used, there are problems such as high manufacturing cost although it is very excellent in gloss. .

  On the other hand, when a propylene-based resin is used, the resulting blow-molded product is relatively inexpensive to manufacture, and is more glossy and transparent than high-density polyethylene. Therefore, containers for liquid detergents, cosmetics, foods, medicines, etc. Is widely used.

  The gloss of the blow molded product is a physical property that has been studied in order to meet the market demand for a good appearance, but it still has sufficient gloss, good moldability and impact resistance at the same time. Has not been proposed.

  As a blow molded article having excellent gloss, a propylene / α-olefin copolymer is used as a base resin, a linear low density polyethylene having a crystalline melting point of 110 to 125 ° C. is used as a compounding resin, and these resins and a nucleating agent are contained. A multilayer blow molded article having an olefin polymer composition as an outermost layer has been proposed (see, for example, Patent Document 1). However, as a result of investigations by the present inventors, it was found that even the multilayer blow molded article described in Patent Document 1 is still insufficient in gloss and impact resistance and needs further improvement.

  As a multilayer bottle excellent in cold resistance, a multilayer bottle having a gas barrier resin core layer and having an outermost layer formed of a polyolefin resin and a linear ultra-low density polyethylene resin has been proposed (for example, Patent Document 2). However, as a result of studies by the present inventors, it was found that even the multilayer bottle described in Patent Document 2 still has insufficient gloss and moldability, and further improvement is necessary.

  As a multilayer plastic container with a label manufactured by an in-mold method with excellent gloss and surface properties, as a resin used for the outermost layer, a polypropylene random copolymer resin containing polyethylene, polyethylene resin, nucleating agent, ethylene It has been proposed to use a material containing an α-olefin copolymer resin (for example, see Patent Document 3). However, when the present inventors examined, it turned out that the multilayer plastic container described in patent document 3 is not yet sufficient in impact resistance, and needs further improvement.

  As a high-gloss blow container with excellent gloss on the outer surface of the container, a composition comprising a polypropylene resin obtained using a metallocene catalyst and an ethylene / α-olefin copolymer obtained using a metallocene catalyst as the outermost layer. A high-gloss blow container formed by a multilayer blow molding method is known (for example, see Patent Document 4). However, as a result of investigations by the present inventors, the high-gloss blown container described in Patent Document 4 is superior in gloss when compared to conventional containers, but further improved in terms of heat resistance and gloss. I found that there was room.

Japanese Patent No. 3106634 JP-A-6-72424 JP-A-7-304123 JP 2003-137828 A

  An object of the present invention is to provide a multilayer blow container having high gloss, excellent surface appearance, excellent impact resistance, and excellent balance between impact resistance and stickiness resistance.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a multilayer blow container using a specific olefin polymer composition as the outermost layer has high gloss, excellent surface appearance, and is resistant to damage. The present invention has been completed by finding out that it has excellent impact resistance and also has an excellent balance between impact resistance and stickiness resistance.

  That is, in the multilayer blow container of the present invention, the resin used in the outermost layer is 80 to 98 parts by weight of the propylene resin (A) and 2 to 20 parts by weight of the ethylene / α-olefin copolymer (B) (however, The total of (A) and (B) is 100 parts by weight) and the olefin polymer composition (E) formed from 0.01 to 0.5 parts by weight of the nucleating agent (D), The propylene resin (A) satisfies the following requirements (A-1) and (A-2), and the ethylene / α-olefin copolymer (B) satisfies the following requirements (B-1) and (B-2). A multilayer blow container characterized in that the olefin polymer composition (E) satisfies the following requirement (E-1).

  (A-1) A copolymer of propylene and one or more olefins selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms.

  (A-2) The crystal melting point measured with a differential scanning calorimeter (DSC) in accordance with JIS-K7121 is in the range of 140 to 155 ° C.

  (B-1) A copolymer of ethylene and one or more α-olefins having 4 to 20 carbon atoms.

  (B-2) The crystal melting point measured by DSC according to JIS-K7121 is in the range of 85 ° C. or higher and lower than 110 ° C.

  (E-1) The melt flow rate (MFR) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238 is in the range of 5 to 10 g / 10 minutes.

The olefin polymer composition (E) is further formed using 0.1 to 20 parts by weight of a low density ethylene / α-olefin copolymer (F). The polymer (F) satisfies the following requirements (F-1) and (F-2), and the density (d _B [g / cm] measured by the density gradient method of the ethylene / α-olefin copolymer (B): ³ ]) and the density (d _F [g / cm ³ ]) measured by the density gradient method of the low density ethylene / α-olefin copolymer (F) satisfy the following requirement (X-1), the multilayer blow It is preferable from the viewpoint of the low temperature impact resistance of the container.

  (F-1) A copolymer of ethylene and one or more α-olefins having 3 to 20 carbon atoms.

  (F-2) The crystalline melting point measured by DSC based on JIS-K7121 is 89 ° C. or lower, or no peak based on the crystalline melting point is observed.

(X-1) d _B [g / cm ³ ]> d _F [g / cm ³ ], and 0.010 [g / cm ³ ] ≦ (d _B −d _F ) [g / cm ³ ] ≦ 0 0.050 [g / cm ³ ].

  It is preferable that the ethylene / α-olefin copolymer (B) further satisfies the following requirement (B-4).

(B-4) The density measured by the density gradient tube method is in the range of 0.880 to 0.910 g / cm ³ .

  The ethylene / α-olefin copolymer (B) further satisfies the following requirement (B-4a), and the low density ethylene / α-olefin copolymer (F) further satisfies the following requirement (F-3). Is preferable from the viewpoint of low-temperature impact resistance of the multilayer blow container.

(B-4a) density measured by a density gradient tube method ^{_{(d B [g / cm 3}} ]) is in the range of 0.890~0.910g / cm ^3.

(F-3) Density measured by density gradient tube method ^{_{(d F [g / cm 3}} ]) is in the range of 0.865~0.900g / cm ^3.

  It is preferable that the propylene-based resin (A) further satisfies the following requirement (A-4).

  (A-4) Mw / Mn measured by GPC is 4.0 or more.

  It is preferable that the propylene-based resin (A) further satisfies the following requirement (A-3).

  (A-3) Based on ASTM D-1238, the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is in the range of 5 to 10 g / 10 minutes.

  It is preferable that the ethylene / α-olefin copolymer (B) further satisfies the following requirement (B-5).

  (B-5) Mw / Mn measured by GPC is 1.2 to 3.0.

  It is preferable that the ethylene / α-olefin copolymer (B) further satisfies the following requirement (B-3).

  (B-3) Based on ASTM D-1238, the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is in the range of 5 to 10 g / 10 minutes.

  The nucleating agent (D) is one or more compounds selected from the group consisting of aromatic phosphate ester compounds, carboxylic acid metal salt nucleating agents, polymer nucleating agents, sorbitol nucleating agents and inorganic compound nucleating agents. It is preferable that

  The propylene-based resin (A) is 95.5 to 98 parts by weight, and the ethylene / α-olefin copolymer (B) is 2 to 4.5 parts by weight (provided that (A) and (B) The total is preferably 100 parts by weight.

  The multilayer blow container has a layer formed from a propylene-based polymer (G) or an ethylene-based polymer (H) as at least one inner layer. The multilayer blow container described.

  The multilayer blow container is preferably obtained by molding by a direct blow molding method or an injection stretch blow molding method.

  The multilayer blow container of the present invention uses a thermoplastic resin composition other than the olefin polymer composition (E) and the olefin polymer composition (E) described above, and the olefin polymer composition (E) has the outermost layer. And formed by a direct blow molding method or an injection stretch blow molding method so that the thermoplastic resin composition other than the olefin polymer composition (E) forms at least one inner layer.

  According to the present invention, it is possible to provide a multilayer blow container having high gloss, excellent surface appearance, excellent impact resistance, and excellent balance between impact resistance and stickiness resistance.

  Next, the present invention will be specifically described.

[Multi-layer blow container]
In the multilayer blow container of the present invention, the resin used for the outermost layer is an olefin polymer formed of a propylene resin (A), an ethylene / α-olefin copolymer (B), and a nucleating agent (D). It consists of a composition (E), It is characterized by the above-mentioned.

  The multilayer blow container of the present invention has high gloss, excellent surface appearance, and excellent impact resistance, but the olefin polymer composition (E) is further reduced in density ethylene / α-olefin copolymer (F). In the aspect formed using 0.1-20 weight part, it is excellent also in low temperature impact resistance.

<Propylene resin (A)>
The propylene-based resin (A) used in the present invention preferably satisfies the following requirements (A-1) and (A-2), and further satisfies at least one of the following requirements (A-3) and (A-4). It is more preferable to satisfy the following requirements (A-3) and (A-4). Propylene-type resin (A) may be used individually by 1 type, or may use 2 or more types.

  (A-1) A copolymer of propylene and one or more olefins selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms. Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadodecene and 4-methyl. -1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, diethyl-1-butene, trimethyl-1-butene , 3-methyl-1-pentene, ethyl-1-pentene, propyl-1-pentene, dimethyl-1-pentene, methylethyl-1-pentene, diethyl-1-hexene, trimethyl-1-pentene, 3-methyl- Examples include 1-hexene, dimethyl-1-hexene, 3,5,5-trimethyl-1-hexene, methylethyl-1-heptene, trimethyl-1-heptene, ethyl-1-octene, and methyl-1-nonene. .

  The propylene-based resin (A) used in the present invention is composed of propylene and one or more olefins selected from the group consisting of ethylene and α-olefins having 4 to 10 carbon atoms from the viewpoint of the balance between physical properties and economy. It is preferably a copolymer, more preferably a copolymer of propylene and one or more α-olefins selected from the group consisting of ethylene and 1-butene, and a copolymer of propylene and ethylene It is particularly preferred that

  Moreover, it is preferable that the propylene-type resin (A) used for this invention is a random copolymer.

  (A-2) The crystal melting point measured with a differential scanning calorimeter (DSC) in accordance with JIS-K7121 is in the range of 140 to 155 ° C. It is preferable that the crystal melting point is in the above-mentioned range since the multilayer blow container is excellent in gloss and impact resistance and is excellent in moldability when producing the multilayer blow container. If the crystal melting point measured by a differential scanning calorimeter (DSC) based on JIS-K7121 is higher than 155 ° C., the impact resistance of the multilayer blow container is inferior. Moreover, when the crystalline melting point measured by a differential scanning calorimeter (DSC) in accordance with JIS-K7121 is lower than 140 ° C., the moldability at the time of producing a multilayer blow container is inferior, and the surface of the multilayer blow container is sticky. .

  The crystalline melting point of the propylene-based resin (A) can be determined by performing measurement under the following measurement conditions using a differential scanning calorimeter (DSC) (for example, Diamond DSC manufactured by Perkin Elmer) according to JIS-K7121. it can. In addition, the top of the endothermic peak in the third step when the measurement was performed under the following measurement conditions was defined as the crystalline melting point (Tm). When there are a plurality of endothermic peaks, the peak of the endothermic peak where the peak height is maximum is defined as the crystalline melting point (Tm).

(Measurement condition)
Measurement environment: Nitrogen gas atmosphere Sample volume: 5mg
Sample shape: Press film (230 ° C molding, thickness 200-400μm)
First step: The temperature is raised from 30 ° C to 240 ° C at 10 ° C / min and held for 10 min.

  Second step: Decrease the temperature to 60 ° C at 10 ° C / min.

  Third step: Increase the temperature to 240 ° C at 10 ° C / min.

  The crystal melting point of the propylene resin (A) measured by a differential scanning calorimeter (DSC) in accordance with JIS-K7121 is, for example, propylene at the time of copolymerization in the production of the propylene resin (A), ethylene introduced, and It can be adjusted by changing the introduction ratio of one or more olefins selected from the group consisting of α-olefins having 4 to 20 carbon atoms. That is, by increasing the introduction amount of one or more olefins selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms with respect to the introduction amount of propylene, the differential scanning calorific value in accordance with JIS-K7121. The crystal melting point measured with a meter (DSC) can be lowered, and the introduction amount of one or more olefins selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms is reduced with respect to the introduction amount of propylene. By doing, the crystalline melting point measured with the differential scanning calorimeter (DSC) based on JIS-K7121 can be made high.

  (A-3) Based on ASTM D-1238, the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is in the range of 5 to 10 g / 10 minutes. In addition, MFR means a melt flow rate. When the MFR is within the above range, the fluidity of the olefin polymer composition (E) at the time of molding becomes a suitable range for molding of the present invention, and the thickness of the olefin polymer composition (E) having the highest multilayer in blow molding. Unevenness is prevented, and a multi-layer blow container having excellent smoothness and excellent gloss can be produced. In accordance with ASTM D-1238, when the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is larger than 10 g / 10 minutes, the moldability and the impact resistance of the multilayer blow container are inferior. In some cases, when the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is smaller than 5 g / 10 minutes in accordance with ASTM D-1238, the gloss of the multilayer blow container may be inferior.

  According to ASTM D-1238 of the propylene resin (A), MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is, for example, chain transfer used during copolymerization in the production of the propylene resin (A). It can adjust with the introduction amount of an agent (for example, hydrogen gas). That is, the introduction amount of the chain transfer agent (for example, hydrogen gas) is increased with respect to the amount of one or more olefins selected from the group consisting of propylene introduced at the time of polymerization and ethylene and an α-olefin having 4 to 20 carbon atoms. Thus, the MFR of the propylene-based resin (A) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg according to ASTM D-1238 can be increased. Moreover, the introduction amount of a chain transfer agent (for example, hydrogen gas) is reduced with respect to the amount of one or more olefins selected from the group consisting of propylene introduced during polymerization and ethylene and an α-olefin having 4 to 20 carbon atoms. Thus, the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238 of the propylene-based resin (A) can be lowered.

  In addition, the propylene-based resin obtained by polymerization is melt kneaded in the presence of a radical generator such as an organic peroxide, and the measurement temperature is 230 ° C. and the load is 2.16 kg according to ASTM D-1238. The MFR measured in (1) can be adjusted. For example, by performing the melt-kneading process in the presence of an organic peroxide, the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is increased in accordance with ASTM D-1238. Further, by increasing the amount of organic peroxide added, the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg can be further increased in accordance with ASTM D-1238.

  (A-4) Mw / Mn measured by GPC is 4.0 or more. GPC means gel permeation chromatography, Mw means weight average molecular weight, Mn means number average molecular weight, and Mw / Mn is an index of molecular weight distribution. As propylene resin (A), Mw / Mn is preferably 1.5 or more, more preferably 3.0 or more, but satisfies the above (A-4), that is, Mw / Mn is 4.0 or more. It is particularly preferable because a blow molded article having excellent gloss can be obtained regardless of the surface roughness of the blow mold. The reason for this is not clear, but the present inventors consider as follows. That is, when Mw / Mn is 4.0 or more, a portion having a higher molecular weight and a portion having a lower molecular weight are present than in the case where the value is less than the above range. It is considered that the presence of a higher molecular weight portion reduces resin flow deformation during blow molding, and the presence of a lower molecular weight portion accelerates solidification. For this reason, the multilayer blow container which can be obtained both when a mold having a large surface roughness and a mold having a small surface roughness is used when the component (A) is in the range of Mw / Mn. The inventors estimated that the gloss would be good without transferring the roughness of the mold surface. The upper limit of Mw / Mn is not particularly limited, but is usually 50.0, preferably 30.0, more preferably 20.0, still more preferably 16.0, and particularly preferably 12 from the viewpoint of productivity. 0.0, most preferably 8.0. In addition, Mw / Mn by GPC can be performed by the method as described in an Example.

  Mw / Mn measured by GPC of the propylene-based resin (A) can be adjusted by, for example, the type of catalyst used in the production of the propylene-based resin (A). For example, by using a Ziegler-Natta catalyst, preferably a solid titanium catalyst, as the catalyst, the propylene-based resin (A) satisfying the above requirement (A-4) can be obtained. As another example of adjusting Mw / Mn, there is a method of blending two or more propylene resins having different molecular weights. In particular, the solid titanium catalyst is advantageous from the viewpoint of forming the higher molecular weight portion.

In addition, as the propylene-based resin (A), it is derived from one or more olefins selected from the group consisting of propylene-derived structural units, ethylene, and α-olefins having 4 to 20 carbon atoms, calculated from ¹³ C-NMR. The weight of the structural unit derived from propylene is 100 to 99% by weight, preferably 90 to 99% by weight when the total amount of the structural unit is 100% by weight. The weight of the structural unit derived from one or more olefins selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms is usually in the range of 1 to 20% by weight, preferably 1 to It is in the range of 10% by weight. Within the above range, it is preferable because the balance between the moldability when producing a multilayer blow container and physical properties such as stickiness of the multilayer blow container is good.

The total of propylene-derived structural units calculated from ¹³ C-NMR and one or more olefin-derived structural units selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms is 100% by weight. The weight of the structural unit derived from propylene was measured and calculated under the following conditions.

( ¹³ C-NMR measurement conditions)
Measuring apparatus: LA400 type nuclear magnetic resonance apparatus manufactured by JEOL Measurement mode: BCM (Bilevel Complete Decoupling)
Observation frequency: 100.4 MHz
Observation range: 17006.8Hz
Pulse width: C nucleus 45 ° (7.8 μsec)
Pulse repetition time: 5 seconds Sample tube: 5 mmφ
Sample tube rotation speed: 12Hz
Integration count: 20000 times Measurement temperature: 125 ° C
Solvent: 1,2,4-trichlorobenzene: 0.35 ml / heavy benzene: 0.2 ml
Sample amount: about 40mg
(Calculation of weight of structural unit derived from propylene)
When one or more olefins selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms (that is, a comonomer) is ethylene, the obtained ¹³ C-NMR spectrum is used according to the following document (1). By determining the ratio of the monomer chain distribution (dyad (doubled) distribution), the mole fraction of the structural unit derived from ethylene in the propylene resin (A) (mol%) (hereinafter referred to as E (mol%)) And the molar fraction (mol%) of constituent units derived from propylene (hereinafter referred to as P (mol%)) can be calculated. The weight percent of the structural unit derived from propylene and the weight percent of the structural unit derived from ethylene in the propylene-based resin (A) are calculated by converting from the obtained E (mol%) and P (mol%) to weight percent. be able to.

Reference (1): Kakugo, M .; Naito, Y .; Mizunuma, K .; Miyatake, T., Macromolecules 1982, 15, (4), 1150-1152
When one or more olefins selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms (that is, a comonomer) is an α-olefin having 4 to 20 carbon atoms, from the obtained ¹³ C-NMR spectrum In accordance with the following document (2), by determining the ratio of the monomer chain distribution (dyad (doubled) distribution), the α-olefin having 4 to 20 carbon atoms in (A) of the propylene-based resin is obtained. The molar fraction (mol%) of the structural unit derived from (hereinafter referred to as A (mol%)) and the molar fraction (mol%) of the structural unit derived from propylene (hereinafter referred to as P (mol%)) are calculated. be able to. Converted from the calculated A (mol%) and P (mol%) to wt%, derived from propylene-based resin in the propylene-based resin (A) wt% and derived from α-olefin having 4 to 20 carbon atoms The weight% of the structural unit to be calculated can be calculated.

Reference (2): James C. Randall, Macromolecules, 1978, 11, 592-597
Adjustment of the weight of the structural unit derived from propylene can be made into arbitrary quantity by adjusting the manufacturing conditions mentioned later. More specifically, introduction of one or more olefins selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms with respect to the amount of propylene introduced during copolymerization in the production of propylene-based resin (A). By reducing the amount, the weight of the structural unit derived from propylene can be increased. Moreover, the weight of the structural unit derived from propylene is reduced by increasing the introduction amount of one or more olefins selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms with respect to the introduction amount of propylene. be able to.

  The propylene resin (A) is preferably a random copolymer of propylene and one or more olefins selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms. The propylene-based resin (A) is preferably a copolymer of propylene and one or more olefins selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms in the presence of a Ziegler-Natta catalyst or a metallocene catalyst. Can be obtained by random copolymerization. When a Ziegler-Natta catalyst, preferably a solid titanium catalyst, is used as the catalyst used when polymerizing the propylene-based resin (A), the requirement (A-4) can be satisfied. Moreover, it is also possible to adjust so that a requirement (A-4) may be satisfy | filled by blending 2 or more types of propylene-type resin (A) from which molecular weight differs. In the polymerization, a chain transfer agent represented by hydrogen gas can be introduced. Furthermore, the propylene-based resin (A) can also be obtained by subjecting the propylene-based resin obtained by polymerization to melt-kneading in the presence of a radical generator such as an organic peroxide.

  The organic peroxide is not particularly limited, but benzoyl peroxide, t-butyl perbenzoate, t-butyl peracetate, t-butyl peroxyisopropyl carbonate, 2,5-di-methyl-2,5 -Di- (benzoylperoxy) hexane, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexyne-3, t-butyl-diperadipate, t-butylperoxy-3, 5,5-trimethylhexanoate, methyl-ethylketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-di-methyl-2,5-di- (t -Butylperoxy) hexane, 2,5, -di-methyl-2,5-di- (t-butylperoxy) hexyne-3,1,3-bis- (t-butylperoxyisopropyl ) Benzene, t-butyl chylyl peroxide, 1,1-bis- (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis- (t-butylperoxy) cyclohexane, 2,2-bis- (t-butylperoxy) butane, p-menthane hydroperoxide, di-isopropylbenzene hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, p-cymene hydroperoxide, Illustrative are organic peroxides such as 1,1,3,3-tetra-methylbutyl hydroperoxide or 2,5-di-methyl-2,5-di- (hydroperoxy) hexane. Of these, 2,5-di-methyl-2,5-di- (benzoylperoxy) hexane and 1,3-bis- (t-butylperoxyisopropyl) benzene are more preferred. When using an organic peroxide, it is desirable to use it at 0.1 parts by weight or less with respect to 100 parts by weight of the propylene-based resin obtained by polymerization. In the melt-kneading process, after adding the organic peroxide to the propylene-based resin, the mixture is introduced into a mixer such as a Henschel mixer, a Banbury mixer, or a tumbler mixer, and then mixed.The resulting mixture is then converted into a single-screw extruder, The method of shape | molding with extruders, such as a twin-screw extruder, and obtaining the strand of propylene-type resin (A) is mentioned. The strand is usually formed into a pellet using a pelletizer or the like before blow molding.

<Ethylene / α-olefin copolymer (B)>
The ethylene / α-olefin copolymer (B) used in the present invention satisfies the following requirements (B-1) and (B-2), and at least one of the following requirements (B-3) and (B-4): It is preferable to satisfy, and it is more preferable to satisfy the following requirements (B-3) and (B-4). It is also preferable to satisfy the following requirement (B-5). The ethylene / α-olefin copolymer (B) may be used alone or in combination of two or more.

  (B-1) A copolymer of ethylene and one or more α-olefins having 4 to 20 carbon atoms. Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadodecene and 4-methyl. -1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, diethyl-1-butene, trimethyl-1-butene , 3-methyl-1-pentene, ethyl-1-pentene, propyl-1-pentene, dimethyl-1-pentene, methylethyl-1-pentene, diethyl-1-hexene, trimethyl-1-pentene, 3-methyl- Examples include 1-hexene, dimethyl-1-hexene, 3,5,5-trimethyl-1-hexene, methylethyl-1-heptene, trimethyl-1-heptene, ethyl-1-octene, and methyl-1-nonene. .

  The ethylene / α-olefin copolymer (B) used in the present invention is at least one selected from the group consisting of ethylene and α-olefins having 4 to 10 carbon atoms from the viewpoint of a balance between physical properties and economy. It is preferably a copolymer of olefins, more preferably a copolymer of ethylene and one or more α-olefins selected from the group consisting of 1-butene, 1-hexene and 1-octene. A copolymer of ethylene and 1-hexene is particularly preferable.

  (B-2) The crystal melting point measured by DSC according to JIS-K7121 is in the range of 85 ° C. or higher and lower than 110 ° C. It is preferable that the crystal melting point is in the above range because the multilayer blow container is excellent in impact resistance and adhesion between the outermost layer and other layers. When the crystalline melting point of the ethylene / α-olefin copolymer (B) measured by DSC in accordance with JIS-K7121 is 110 ° C. or higher, the adhesiveness and impact resistance are inferior, and measured by DSC in accordance with JIS-K7121. When the crystal melting point is lower than 85 ° C., the adhesiveness is inferior, and stickiness is generated, which is not preferable. Further, from the viewpoint of the balance between impact resistance, adhesion and stickiness, the crystal melting point is preferably 109 ° C. or lower, more preferably 108 ° C. or lower, and particularly preferably 105 ° C. or lower.

  The crystal melting point of the ethylene / α-olefin copolymer (B) used in the present invention measured by DSC in accordance with JIS-K7121 can be adjusted to any amount by adjusting the production conditions of the ethylene / α-olefin copolymer. It can be.

  More specifically, in the polymerization of the ethylene / α-olefin copolymer (B), it is adjusted by changing the ratio of the feed amount of ethylene / α-olefin when the ethylene / α-olefin copolymer is polymerized. Is possible. Specifically, the crystal melting point measured by DSC in accordance with JIS-K7121 can be lowered by increasing the α-olefin feed amount relative to the ethylene feed amount. Further, by reducing the feed amount of α-olefin relative to the feed amount of ethylene, it is possible to increase the crystalline melting point measured by DSC according to JIS-K7121.

  The crystalline melting point of the ethylene / α-olefin copolymer (B) can be measured using a differential scanning calorimeter (DSC) according to JIS-K7121. Specifically, it can be measured by the same method as the crystalline melting point of the propylene resin (A) described above.

  (B-3) Based on ASTM D-1238, the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is in the range of 5 to 10 g / 10 minutes. When the MFR is within the above range, the dispersibility of the ethylene / α-olefin copolymer (B) in the propylene resin (A) is good, the gloss of the multilayer blow container is excellent, and the impact resistance is excellent. Since it is excellent in adhesiveness with another layer, it is preferable.

  In addition, based on ASTM D-1238 of ethylene / α-olefin copolymer (B), the adjustment of MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg was adjusted to ethylene / α-olefin copolymer (B It can be set to an arbitrary value by adjusting the manufacturing conditions.

  More specifically, in the polymerization of the ethylene / α-olefin copolymer (B) described later, the amount of hydrogen gas is controlled by adjusting the feed amount of ethylene and / or α-olefin during polymerization. It is possible. In the case of feeding ethylene gas during polymerization or ethylene and α-olefin, the measurement temperature is increased in accordance with ASTM D-1238 by increasing the feed amount of hydrogen gas relative to the feed amount of ethylene and α-olefin. It is possible to increase the MFR measured at 230 ° C. and a 2.16 kg load. In the case of feeding ethylene gas or ethylene and α-olefin, the measurement temperature is 230 ° C., 2 ° C. in accordance with ASTM D-1238 by reducing the feed amount of hydrogen gas relative to the feed amount of ethylene and α-olefin. It is possible to lower the MFR measured with a 16 kg load.

(B-4) The density measured by the density gradient tube method is in the range of 0.880 to 0.910 g / cm ³ . It is preferable for the density to be in the above-mentioned range since the multilayer blow container is excellent in gloss and impact resistance and adhesion between the outermost layer and other layers.

  When the multilayer blow container of the present invention is used for applications requiring low temperature impact resistance, the low-density ethylene / α-olefin copolymer (F) described later is used and the ethylene / α-olefin copolymer is used. It is preferable that the polymer (B) satisfies the following requirement (B-4a).

(B-4a) density measured by a density gradient tube method ^{_{(d B [g / cm 3}} ]) is in the range of 0.890~0.910g / cm ^3. When the density is within the above range, the multi-layer blow container has excellent gloss, impact resistance, low temperature impact resistance, adhesion between the outermost layer and other layers, low stickiness, and further, impact resistance and low temperature resistance. It is preferable because the balance between impact resistance such as impact properties and resistance is good.

  The density measured by the density gradient tube method of the ethylene / α-olefin copolymer (B) used in the present invention should be an arbitrary amount by adjusting the production conditions of the ethylene / α-olefin copolymer (B). Can do.

  More specifically, in the polymerization of the ethylene / α-olefin copolymer (B) described later, the ratio of the feed amount of ethylene and α-olefin when the ethylene / α-olefin copolymer is polymerized is changed. Can be adjusted. Specifically, the density measured by the density gradient tube method can be lowered by increasing the feed amount of α-olefin relative to the feed amount of ethylene. Further, the density measured by the density gradient tube method can be increased by reducing the feed amount of α-olefin relative to the feed amount of ethylene.

  In addition, the density measured by the density gradient tube method of the ethylene / α-olefin copolymer (B) used in the present invention is the strand of the ethylene / α-olefin copolymer (B) obtained at the time of the MFR measurement. It is a measured value measured with a density gradient tube after heat treatment at 120 ° C. for 1 hour and linearly cooling to room temperature over 1 hour.

  (B-5) Mw / Mn measured by GPC is 1.2 to 3.0. As the ethylene / α-olefin copolymer (B), Mw / Mn is more preferably 1.5 to 3.0. It is preferable that Mw / Mn is within the above range because the multilayer blow container of the present invention is excellent in gloss.

  Mw / Mn measured by GPC of the ethylene / α-olefin copolymer (B) can be adjusted, for example, depending on the type of catalyst used in the production of the ethylene / α-olefin copolymer (B). . For example, by using a metallocene catalyst as the catalyst, an ethylene / α-olefin copolymer (B) satisfying the requirement (B-5) can be obtained.

  The ethylene / α-olefin copolymer (B) can be obtained by copolymerizing ethylene and an α-olefin, but the ethylene / α-olefin copolymer is obtained using a metallocene catalyst. A polymerized one is preferred. In the polymerization, a chain transfer agent represented by hydrogen gas can be introduced.

  When the ethylene / α-olefin copolymer (B) used in the present invention is an ethylene / α-olefin copolymer polymerized using a metallocene catalyst, the ethylene polymerized using a conventional so-called Ziegler-Natta catalyst -Since the composition distribution is more uniform than that of the α-olefin copolymer, the dispersibility with respect to the propylene-based resin (A) is improved, and the olefin polymer composition (E) having better gloss can be obtained. In addition, an ethylene / α-olefin copolymer polymerized using a metallocene catalyst has a narrower molecular weight distribution than an ethylene / α-olefin copolymer polymerized using a Ziegler-Natta catalyst, and has improved impact resistance. Low molecular weight components that cause deterioration are reduced. Furthermore, an ethylene / α-olefin copolymer polymerized using a metallocene catalyst has a more uniform composition distribution of the copolymer than an ethylene / α-olefin copolymer polymerized using a Ziegler-Natta catalyst. The amorphous component that causes stickiness is also reduced. Further, adhesion unevenness between the outermost layer and the other layers is reduced, and it is expected to suppress deterioration in appearance over time.

  From the above, by using the ethylene / α-olefin copolymer (B) polymerized by using a metallocene catalyst, the olefin polymer composition (E) has excellent gloss, impact resistance, and low stickiness. ) Can be obtained.

<Low density ethylene / α-olefin copolymer (F)>
When the multilayer blow container of the present invention is required to have low temperature impact resistance, as described above, as the olefin polymer composition (E), the propylene resin (A) and the ethylene / α-olefin copolymer ( In addition to B) and the nucleating agent (D), it is preferable to use a composition formed using a low-density ethylene / α-olefin copolymer (F).

  The low density ethylene / α-olefin copolymer (F) preferably satisfies the following requirements (F-1) and (F-2), and further satisfies the following requirement (F-3). The low density ethylene / α-olefin copolymer (F) may be used alone or in combination of two or more.

  (F-1) A copolymer of ethylene and one or more α-olefins having 3 to 20 carbon atoms. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-hexadodecene, 4 -Methyl-1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, diethyl-1-butene, trimethyl-1 -Butene, 3-methyl-1-pentene, ethyl-1-pentene, propyl-1-pentene, dimethyl-1-pentene, methylethyl-1-pentene, diethyl-1-hexene, trimethyl-1-pentene, 3- Methyl-1-hexene, dimethyl-1-hexene, 3,5,5-trimethyl-1-hexene, methylethyl-1-heptene, trimethyl-1-heptene, ethyl-1-octene, methyl-1-nonene, etc. Can be mentioned.

  The low density ethylene / α-olefin copolymer (F) includes at least one selected from the group consisting of ethylene and α-olefins having 3 to 10 carbon atoms from the viewpoint of a balance between physical properties and economy. It is preferably a copolymer with olefin, and is a copolymer of ethylene and one or more α-olefins selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene. More preferred. The low-density ethylene / α-olefin copolymer (F) is preferably a copolymer of ethylene and propylene, a copolymer of ethylene and 1-butene, or a copolymer of ethylene and 1-octene. More preferred is a copolymer of ethylene and 1-butene, and a copolymer of ethylene and 1-octene, and particularly preferred is a copolymer of ethylene and 1-butene.

  (F-2) The crystalline melting point measured by DSC based on JIS-K7121 is 89 ° C. or lower, or no peak based on the crystalline melting point is observed. When it has a crystalline melting point, it is preferably 75 ° C. or lower. A crystal melting point within the above range is preferable because a multilayer blow container is excellent in low-temperature impact resistance.

  The crystalline melting point of the low density ethylene / α-olefin copolymer (F) can be measured using a differential scanning calorimeter (DSC) according to JIS-K7121. Specifically, it can measure by the method as described in the below-mentioned Example.

(F-3) Density measured by density gradient tube method ^{_{(d F [g / cm 3}} ]) is in the range of 0.865~0.900g / cm ^3. The density is more preferably in the range of 0.870 to 0.900 g / cm ³ . It is preferable for the density to be in the above-mentioned range since the gloss of the multilayer blow container is excellent and the low-temperature impact resistance is particularly excellent.

The density (d _B [g / cm ³ ]) measured by the density gradient method of the ethylene / α-olefin copolymer (B) and the density gradient of the low density ethylene / α-olefin copolymer (F) The density (d _F [g / cm ³ ]) measured by the government method satisfies the following requirement (X-1).

(X-1) d _B [g / cm ³ ]> d _F [g / cm ³ ], and 0.010 [g / cm ³ ] ≦ (d _B −d _F ) [g / cm ³ ] ≦ 0 0.050 [g / cm ³ ]. That is, the density of the low-density ethylene / α-olefin copolymer (F) is smaller than the density of the ethylene / α-olefin copolymer (B), which is lower than that of the ethylene / α-olefin copolymer (B). The density difference (d _B -d _F ) from the density ethylene / α-olefin copolymer ( _F ) is from 0.010 to 0.050 [g / cm ³ ]. The density difference (d _B -d _F) is preferably 0.010~0.040 [g / cm ^3].

It is preferable that the density difference (d _B -d _F ) be in the above range because the multi-layer blow container is excellent in gloss and further excellent in low-temperature impact resistance.

  The low density ethylene / α-olefin copolymer (F) has a MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238 within a range of 0.1 to 50 g / 10 min. It is preferable that it is in the range of 0.5 to 30 g / 10 minutes, and it is particularly preferable to be in the range of 5 to 10 g / 10 minutes. When the MFR is within the above range, the dispersibility of the low-density ethylene / α-olefin copolymer (F) becomes good, and the gloss and low-temperature impact properties are improved.

  The low-density ethylene / α-olefin copolymer (F) can be obtained by copolymerizing ethylene and α-olefin, and the ethylene / α-olefin copolymer is a Ziegler-Natta catalyst. The polymer may be polymerized using a metallocene or may be polymerized using a metallocene catalyst.

<Nucleating agent (D)>
In the present invention, the nucleating agent (D) is used. As the nucleating agent (D), one or more compounds selected from the group consisting of aromatic phosphate ester compounds, carboxylic acid metal salt nucleating agents, polymer nucleating agents, sorbitol nucleating agents and inorganic compound nucleating agents. Is mentioned. It is preferable that the nucleating agent (D) does not deteriorate the odor of the multilayer blow container. A nucleating agent (D) may be used individually by 1 type, or may use 2 or more types together.

  The aromatic phosphate ester compound is preferably a compound represented by the following formula [III] and / or [IV].

In the above formula [III], [IV], R 1 is a divalent hydrocarbon group having 1 to 10 carbon atoms, each R ² and R ³ are independently a hydrogen atom or 1 to 10 carbon atoms It is a hydrocarbon group, M is a 1-3 valent metal atom, n is an integer of 1-3, and m is 1 or 2.

  Specific examples of the aromatic phosphate compound represented by the general formula [III] include sodium-2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2 '-Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2 '-Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-i-propyl-6-t-butylphenyl) phosphate, lithium-2 , 2'-methylene-bis (4-methyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, sodium-2 , 2'-Butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-butylidene-bis (4,6-di-t-butylphenol) ) Phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di) -t-butylphenyl) phosphate, calcium-bis- (2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate), magnesium-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate], sodium-2,2 ' -Methylene-bis (4-methyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, sodium-2,2 ' -Ethylidene-bis (4-m-butyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-methylphenyl) Phosphate, sodium-2,2'-methylene-bis (4,6-di-ethylphenyl) phosphate, potassium-2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate , Calcium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2'-ethylidene-bis (4,6-di-t-butyl) Phenyl) phosphate], barium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], aluminum-tris [2,2'-methylene-bis (4,6 -Di-t-butylfel) phosphate], aluminum-tris [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], and mixtures of two or more thereof be able to.

As the aromatic phosphate compound, a hydroxyaluminum phosphate compound represented by the general formula [IV] can also be used. In particular, the compound represented by the general formula [V] in which R ² and R ³ are both tert-butyl groups. Are preferred.

In the formula [V], R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and m is 1 or 2. A particularly preferred aromatic phosphate compound is a compound represented by the general formula [VI].

In the formula [VI], R ¹ is a methylene group or an ethylidene group. As the compound represented by the general formula [VI], specifically, hydroxyaluminum-bis [2,2-methylene-bis (4,6-di-t-butyl) phosphate] (also known as bis (2, 4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-oxide) aluminum hydroxide salt), or hydroxyaluminum Bis [2,2-ethylidene-bis (4,6-di-t-butyl) phosphate].

  As the carboxylic acid metal salt nucleating agent, for example, pt-butyl benzoic acid aluminum salt, aluminum adipate, sodium benzoate can be used.

  A branched α-olefin polymer is preferably used as the polymer nucleating agent. Examples of branched α-olefin polymers include 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene. 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, a homopolymer of 3-ethyl-1-hexene, or a copolymer thereof, and May include copolymers of these and other α-olefins.

  These polymer nucleating agents can be blended directly when the olefin polymer composition (E) is produced, and when the propylene resin (A) is produced, the propylene resin (A) is produced. The above-mentioned branched α-olefin is polymerized before or after the polymerization in a block manner, and blended by using a propylene resin (A) containing a branched α-olefin polymer as a nucleating agent (D). It is also possible to use a polymer nucleating agent-containing propylene resin (A ′). When using the polymer nucleating agent-containing propylene resin (A ′) as a raw material for the olefin polymer composition (E), the polymer nucleating agent contained in the polymer nucleating agent-containing propylene resin (A ′) Let the amount be the blending amount of the nucleating agent (D) in the olefin polymer composition (E). Moreover, let the part which reduced the quantity of the polymer nucleating agent from the polymer nucleating agent mixing | blending propylene-type resin (A ') be the propylene-type resin (A) in an olefin type polymer composition (E).

  The polymer nucleating agent can also be formed by prepolymerization when producing the polymer (A), the polymer (B), and the polymer (F) using a known method. ), When the polymer (F) is produced, it can also be formed by a block copolymerization method.

  At that time, a polymer nucleating agent-containing propylene resin (A ′) and a propylene resin (A) not containing a polymer nucleating agent may be used in combination. Moreover, you may use together a polymer nucleating agent mixing | blending propylene-type resin (A '), and another nucleating agent (D).

  When these polymer nucleating agents contain other resins described later in the olefin polymer composition (E), master batches containing other resins and a polymer nucleating agent are used as olefins. You may mix | blend by using when manufacturing a type | system | group polymer composition (E). When the master batch is used as a raw material for the olefin polymer composition (E), the amount of the polymer nucleating agent contained in the master batch is determined based on the nucleating agent (D) in the olefin polymer composition (E). The blending amount. The master batch and other nucleating agent (D) may be used in combination to produce an olefin polymer composition.

  As the polymer nucleating agent, a polymer of 3-methyl-1-butene is particularly preferable from the viewpoints of transparency, low-temperature impact resistance, good rigidity characteristics, and economical efficiency.

  As the sorbitol nucleating agent, nonitol, 1,2,3-trideoxy-4,6: 5,7-bis-O-[(4-propylphenyl) methylene] can be preferably used.

  As the inorganic compound nucleating agent, for example, talc, mica and calcium carbonate can be used.

  Among these nucleating agents (D), nonitol, 1,2,3-trideoxy-4,6: 5,7-bis-O— is preferred in terms of transparency, low-temperature impact resistance, rigidity and low odor. [(4-propylphenyl) methylene] and bis (2,4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin It is preferred to use at least one nucleating agent selected from -6-oxide) aluminum hydroxide salts. Among these, bis (2,4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-oxide) hydroxylation More preferably, an aluminum salt is used.

  A commercially available product can be used as the nucleating agent (D) used in the present invention. For example, ADK STAB NA-21 (manufactured by ADEKA) is bis (2,4,8,10-tetra-t-butyl-6- 6). Hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-oxide) It is commercially available as a nucleating agent containing aluminum hydroxide as a main component. , 3-Trideoxy-4,6: 5,7-bis-O-[(4-propylphenyl) methylene] is commercially available under the trade name Millard NX8000 (Milken).

<Olefin polymer composition (E)>
The olefin polymer composition (E) used in the present invention is a resin used in the outermost layer of the multilayer blow container of the present invention. The propylene resin (A) is 80 to 98 parts by weight and ethylene / α-olefin. Formed from 2 to 20 parts by weight of copolymer (B) (however, the sum of (A) and (B) is 100 parts by weight) and 0.01 to 0.5 parts by weight of nucleating agent (D) Composition.

  When the multilayer blow container of the present invention is required to have low temperature impact resistance, as described above, the olefin polymer composition (E) is composed of propylene resin (A) and ethylene / α-olefin copolymer. In addition to the coalescence (B) and the nucleating agent (D), it is preferable to use a composition formed using 0.1 to 20 parts by weight of a low density ethylene / α-olefin copolymer (F). .

  When the multilayer blow container does not require low temperature impact resistance, the olefin polymer composition (E) is formed without using the low density ethylene / α-olefin copolymer (F). It is also preferable.

  The amount of the propylene-based resin (A) and the ethylene / α-olefin copolymer (B) used is such that the propylene-based resin (A) is used from the viewpoint of good stickiness and economical and productivity. 95.5 to 98 parts by weight, and the ethylene / α-olefin copolymer (B) is 2 to 4.5 parts by weight (however, the total of (A) and (B) is 100 parts by weight) It is preferable that

  When the amount of the propylene-based resin (A) used to obtain the olefin polymer composition (E) is more than 98 parts by weight and the amount of the ethylene / α-olefin copolymer (B) is less than 2 parts by weight, a multilayer blow container The propylene-based resin (A) blended in the olefin polymer composition (E) is less than 80 parts by weight, and the ethylene / α-olefin copolymer is inferior in impact resistance and adhesion to other layers. When (B) is more than 20 parts by weight, stickiness occurs, which is not preferable.

  When the multilayer blow container is required to have low temperature impact resistance, the low-density ethylene / α-olefin copolymer (E) is blended into the olefin polymer composition (E) from the viewpoints of stickiness and economy. F) is preferably 3 to 15 parts by weight.

  The nucleating agent (D) is used in a multilayer blow container by using 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the total amount of the propylene-based resin (A) and the ethylene / α-olefin copolymer (B). The effect of improving the glossiness of the film can be obtained. When the addition amount of the nucleating agent (D) is less than 0.01 parts by weight, the effect of improving the glossiness is small. Even if the addition amount of the nucleating agent (D) is more than 0.5 parts by weight, the effect is not changed, and it is not preferable because it is economically disadvantageous.

  The olefin polymer composition (E) satisfies the following requirement (E-1).

  (E-1) The melt flow rate (MFR) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238 is in the range of 5 to 10 g / 10 minutes. When the MFR is within the above range, the fluidity of the olefin polymer composition (E) at the time of molding becomes a range suitable for molding, and fine melt fracture (MF) generated at the time of molding can be suppressed. Moreover, the thickness nonuniformity of the olefin polymer composition (E) in blow molding is prevented, and the multilayer blow container excellent in smoothness can be obtained.

  In accordance with ASTM D-1238, when the melt flow rate (MFR) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is higher than 10 g / 10 min, the moldability is inferior, and when it is lower than 5 g / 10 min, the gloss is lost. Inferior to

  The melt flow rate (MFR) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with the requirements (E-1) relating to the olefin polymer composition (E), that is, ASTM D-1238, is propylene used. Can be adjusted by appropriately selecting the resin (A), the ethylene / α-olefin copolymer (B), and the low density ethylene / α-olefin copolymer (F) used as necessary. is there.

  Both the propylene-based resin (A) and the ethylene / α-olefin copolymer (B) used were melt flow rate (MFR) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238. ) Is in the range of 5 to 10 g / 10 min, the propylene resin (A), the ethylene / α-olefin copolymer (B), and the low density ethylene / α-olefin copolymer used as necessary. By appropriately selecting the polymer (F), the requirement (E-1) can be satisfied.

  In other cases, for example, as a propylene resin (A), a melt flow rate (MFR) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238 is less than 5 g / 10 minutes. When a relatively low MFR is used, propylene resin (A), ethylene / α-olefin copolymer (B) and nucleating agent (D), and low-density ethylene used as necessary・ When forming the olefin polymer composition (E) from the α-olefin copolymer (F), by performing melt-kneading in the presence of an organic peroxide, the propylene-based resin (A) or ethylene / α- Modification of the olefin copolymer (B) or the low-density ethylene / α-olefin copolymer (F) used as necessary to change the MFR of the olefin polymer composition (E) , Can be adjusted within the range. In addition, as an organic peroxide, the thing similar to what was described by the term of the said <propylene-type resin (A)> is mentioned.

  As another example, when a propylene resin (A) having an MFR of more than 10 g / 10 minutes and a relatively high MFR is used, an ethylene / α-olefin copolymer (B) to be combined is necessary. The MFR of the olefin polymer composition (E) can be adjusted within the above range by using a low density ethylene / α-olefin copolymer (F) used depending on

  The olefin polymer composition (E) preferably has a crystal melting point measured by DSC in accordance with JIS-K7121 in the range of 140 to 155 ° C. When the crystal melting point is within the above range, a multi-layer blow container having good gloss and good impact resistance can be obtained.

  The crystalline melting point of the olefin polymer composition (E) can be measured using a differential scanning calorimeter (DSC) according to JIS-K7121. Specifically, it can be measured by the same method as the crystalline melting point of the propylene resin (A) described above.

The olefin polymer composition (E) preferably has a half crystallization time (t _1/2 ) in the range of 50 to 1000 seconds, and more preferably in the range of 100 to 500 seconds. Within the above range, the mold transferability becomes good at the time of blow molding, and a multi-layer blow container with good gloss can be obtained.

The half crystallization time (t _1/2 ) was crystallized with the olefin polymer composition (E) under an isothermal condition of 125 ° C., and the calorific value associated with crystallization was measured at this time to start the heat generation (crystallization It can be measured as the time from the start) until the calorific value becomes half the total calorific value.

The half crystallization time (t _1/2 ) of the olefin polymer composition (E) can be adjusted by the amount of the nucleating agent (D) contained in the olefin polymer composition (E). By increasing the amount of the nucleating agent (D) contained in the olefin polymer composition (E), it is possible to increase the half crystallization time (t _1/2 ), and conversely, the amount of the nucleating agent (D). It is possible to slow down the half crystallization time (t _1/2 ) by reducing.

  The olefin polymer composition (E) of the present invention includes the propylene resin (A), the ethylene / α-olefin copolymer (B), the low density ethylene / α-olefin copolymer (F), and Components other than the nucleating agent (D) may be contained.

  Examples of components other than (A), (B), (F) and (D) include other resins and various additives.

Examples of other resins include polyolefins other than propylene resin (A), ethylene / α-olefin copolymer (B), low density ethylene / α-olefin copolymer (F), and nucleating agent (D). Based resins.
Examples of the polyolefin resin include propylene resins (P) other than the propylene resin (A). Examples of the propylene resin (P) include propylene homopolymers (including syndiotactic propylene homopolymers) different from the propylene resin (A). Usually, Tm of the propylene resin (P) measured by a differential scanning calorimeter (DSC) according to JISK7121 is 140 to 155 ° C. Moreover, 0.01-20 g / 10min is preferable as MFR measured by the measurement temperature of 230 degreeC and the load of 2.16kg based on ASTM D-1238 of propylene-type resin (P), Especially 0.1-0.1 5 g / 10 min is preferred.

  Moreover, as other resin, a styrene-type elastomer or its hydrogenated substance (S) can also be illustrated, for example. When it is desired to reduce the gloss mold surface roughness dependency, it is preferable that no styrene elastomer or its hydrogenated product (S) is added.

  The styrene elastomer or hydrogenated product (S) thereof has a styrene content of 10 to 70% by weight, preferably 10 to 65% by weight, more preferably 10 to 40% by weight, and a conjugated diene content of 30 to 90% by weight. The styrenic elastomer or hydrogenated product (S) thereof is preferably 35 to 90% by weight, more preferably 60 to 90% by weight.

  As said styrene-type elastomer or its hydrogenated substance (S), a styrene-type polymer block component (it may be called a styrene block hereafter) and a conjugated diene-type polymer block component (it may be called a diene block hereafter). And a styrene / butadiene random copolymer, a styrene / isoprene random copolymer, a styrene / chloroprene random copolymer, and hydrogenated products thereof. Of these, styrene block copolymers are preferred.

  The styrenic polymer block component constituting the styrenic block copolymer is composed of styrene or a derivative thereof, and specific examples of the monomer include styrene, α-methylstyrene, p-methylstyrene, chlorostyrene, and vinylnaphthalene. Etc. Of these, styrene is preferred. These monomers are used alone or in combination of two or more.

  Specific examples of the monomer constituting the conjugated diene polymer block include butadiene, isoprene, chloroprene and the like. Of these, butadiene and isoprene are preferred. These monomers are used alone or in combination of two or more.

  The bonding form of the styrene block and the diene block in the styrenic block copolymer is not particularly limited, but the styrene block / diene block or styrene block / [diene block / styrene block] n (where n is 1 to 5) Form is preferred.

  The content of the styrene polymer block component in the styrene block copolymer is 10 to 70% by weight, preferably 10 to 65% by weight, more preferably 10 to 40% by weight, and the content of the conjugated diene polymer block component The amount is desirably 30 to 90% by weight, preferably 35 to 90% by weight, and more preferably 60 to 90% by weight.

  The styrenic block copolymer has a melt flow rate (MFR) measured at 230 ° C. and a load of 2160 g in accordance with ASTM D-1238 at 0.1 g / 10 min or more, preferably 0.3 to 20 g / 10 min. Preferably it is 5-10 g / 10min.

  Specific examples of styrenic block copolymers include styrene / ethylene / butene / styrene block copolymers (SEBS), styrene / ethylene / propylene / styrene block copolymers (SEPS), and styrene / butadiene / stin blocks. Examples thereof include a copolymer (SBS), a styrene / isoprene / styrene block copolymer (SIS), and a styrene / ethylene / propylene block copolymer (SEP).

  When the olefin polymer composition (E) contains other resins, the upper limit is usually 20 parts by weight or less, more preferably with respect to 100 parts by weight of the total of (A) and (B). Is 10 parts by weight or less, more preferably 5 parts by weight or less, and the lower limit is usually 0.1 parts by weight.

  When the propylene resin (P) is used as the other resin, the upper limit of the propylene resin (P) is usually 20 parts by weight with respect to a total of 100 parts by weight of the (A) and (B). Below, more preferably 10 parts by weight or less, still more preferably 5 parts by weight or less, and the lower limit is usually 0.1 parts by weight.

  When the styrene elastomer or its hydrogenated product (S) is used as the other resin, the styrene elastomer or its hydrogenated product (S) is in a total of 100 parts by weight of (A) and (B). On the other hand, the upper limit is usually 20 parts by weight or less, more preferably 10 parts by weight or less, still more preferably 5 parts by weight or less, and the lower limit is usually 0.1 parts by weight.

  In the case of using at least one of the propylene resin (P) and the styrene elastomer or the hydrogenated product (S) as the other resin, the propylene resin (P) and the styrene elastomer or the hydrogenated product thereof. The upper limit of the total of (S) is usually 20 parts by weight or less, more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less based on 100 parts by weight of the total of (A) and (B) The lower limit is usually 0.1 parts by weight.

  Further, when it is desirable that the gloss mold surface roughness dependency is small, an embodiment in which the propylene resin (P) is not added and an embodiment in which the styrene elastomer or its hydrogenated product (S) is not added are more desirable. It is an aspect and the aspect which does not add the said propylene-type resin (P) and the said styrene-type elastomer, or its hydrogenated substance (S) is a more desirable aspect.

  In the case of using the styrenic elastomer or the hydrogenated product (S) thereof, it is preferable that the low density ethylene / α-olefin copolymer (F) is in a small amount or not present in terms of stickiness. One.

  When the low density ethylene / α-olefin copolymer (F) is not used, 80 to 98 parts by weight of the propylene resin (A) and 2 to 20 weights of the ethylene / α-olefin copolymer (B) are used. Parts (however, the sum of (A) and (B) is 100 parts by weight), propylene-based resin (P) having an optional Tm of 140 to 155 ° C. and styrene-based elastomer or hydrogenated product thereof ( Olefin polymer composition (E) consisting essentially of 0 to 20 parts by weight of at least one polymer selected from S) (amount based on a total of 100 parts by weight of (A) and (B)) It is also a preferred embodiment of the present invention to use. In this, the sum of the propylene resin (P) having a Tm of 140 to 155 ° C. and the styrene elastomer or its hydrogenated product (S) is 0 with respect to the total 100 parts by weight of (A) and (B). The case of parts by weight is also included. As used herein, “substantially” means that the olefin polymer composition (E) may contain additives as other components within the range not impairing the effects of the present invention, but other components are included. Indicates no.

  Additives include antioxidants, hydrochloric acid absorbers, heat stabilizers, light stabilizers, UV absorbers, lubricants, antistatic agents, flame retardants, pigments, dyes, dispersants, copper damage inhibitors, neutralizing agents, Examples thereof include foaming agents, plasticizers, anti-bubble agents, crosslinkers, flowability improvers such as peroxides, weld strength improvers, and the like. There is no limitation in particular as these additives, For example, a commercial item can be used.

  When the olefin polymer composition (E) contains an additive, the amount of the olefin polymer composition (E) is not particularly limited as long as it is within the range where the effects of the present invention can be obtained. It is usually 0.01 to 1.00 parts by weight relative to 100 parts by weight in total with B).

  Since the olefin polymer composition (E) used in the present invention has a MFR in a specific range, it is difficult to blow mold only with the olefin polymer composition (E), but as a surface layer of a multilayer blow molded article. It can be used, and when used as a surface layer, it exhibits excellent gloss and has excellent physical properties.

  The method for preparing the olefin polymer composition (E) is not particularly limited. For example, a propylene resin (A), an ethylene / α-olefin copolymer (B) and a nucleating agent (D) can be arbitrarily used. A low density ethylene / α-olefin copolymer (F), other resins and additives into a mixer such as a Henschel mixer, Banbury mixer, tumbler mixer, etc., followed by mixing, and then the resulting mixture Is formed by an extruder such as a single screw extruder or a twin screw extruder to obtain a strand of the olefin polymer composition (E). The strand is usually formed into pellets using a pelletizer or the like before blow molding.

  Further, when a reactive additive such as a peroxide such as an organic peroxide or a crosslinking agent is used as the additive, at the time of mixing by the mixer, the propylene resin (A), The ethylene / α-olefin copolymer (B) or a low-density ethylene / α-olefin copolymer (F) used as necessary may be modified.

  The reason why the multilayer blow container formed using the olefin polymer composition (E) as a resin for forming the outermost layer exhibits good physical properties is not clear, but ethylene / α-olefin having a crystal melting point in a specific range. By using the copolymer (B), it is considered that the ethylene / α-olefin copolymer (B) is finely dispersed in the propylene-based resin (A). It is considered that the impact resistance is high and the impact resistance is high, and furthermore, the impact resistance and the low stickiness are compatible. Furthermore, when a later-described propylene polymer (G) or ethylene polymer (H) is used as the polymer forming the inner layer in contact with the outermost layer, it becomes an adhesion point between the layer and the outermost layer. Since the ethylene / α-olefin copolymer (B) is finely dispersed, the number of adhesion points increases, and it is considered that the adhesion to the inner layer is excellent. Further, when the low density ethylene / α-olefin copolymer (F) is used, the low density ethylene / α-olefin copolymer (F) is interposed in the presence of the ethylene / α-olefin copolymer (B). ) Is considered to be finely dispersed in the propylene-based resin (A). Therefore, it is considered that the gloss and surface appearance are excellent, the impact resistance and the low-temperature impact resistance are high, and the stickiness is also suppressed to be low because of fine dispersion. It is done.

<Multilayer blow container>
In the multilayer blow container of the present invention, the resin used for the outermost layer is composed of the above-mentioned olefin polymer composition (E). The multilayer blow container of the present invention has at least one inner layer as a layer other than the outermost layer.

  There is no limitation in particular as another layer (inner layer) which forms a multilayer blow container, Usually, it consists of thermoplastic resins other than an olefin polymer composition (E).

  As thermoplastic resins other than the olefin polymer composition (E), propylene polymer (G), ethylene polymer (H), styrene polymer, polyethylene terephthalate resin, polyamide resin, ABS resin, ethylene / acetic acid Examples thereof include vinyl copolymers, polyvinyl alcohol resins or polyvinyl chloride resins, polyvinyl chloride resins, and modified polyolefin resins. A mixture of two or more of the above resins can also be used. Among these, a propylene polymer (G) and an ethylene polymer (H) are preferable.

  The propylene polymer (G) is a propylene polymer having a propylene-derived constitutional unit of 51 mol% or more, and the ethylene polymer (H) is an ethylene-derived constitutional unit of 51 mol% or more. It is an ethylene polymer.

  Multi-layer blow container is formed from styrene polymer or polar resin such as polyethylene terephthalate resin, polyamide resin, ABS resin, ethylene-vinyl acetate copolymer, polyvinyl alcohol resin, polyvinyl chloride resin as other layer (inner layer) In the case of having a layer to be formed, it is necessary to have a layer formed from the modified polyolefin resin (I) between the outermost layer and the layer formed from the styrenic polymer or the polar resin. From the viewpoint of

  The outermost layer of the multilayer blow container of the present invention, that is, the layer formed from the olefin polymer composition (E) has high gloss. The multilayer blow container is also excellent in impact resistance.

  In the outermost layer of the multilayer blow container of the present invention, that is, the layer formed from the olefin polymer composition (E), the MFR which is an index of fluidity of the olefin polymer composition (E) is in a specific range. Yes. For this reason, in blow molding, it is estimated that the surface of the heated molten resin immediately before contacting the mold is easily smoothed, and the surface is likely to be smooth even after blow molding, thereby providing excellent surface gloss. It is considered that a multilayer blow container can be obtained. Moreover, since MFR which is an index of fluidity of the olefin polymer composition (E) is in a specific range, the surface appearance is also good.

  Further, in the olefin polymer composition (E), an ethylene / α-olefin copolymer (B) is used as a raw material of the composition. Since the ethylene / α-olefin copolymer (B) has a crystal melting point in a specific range, the obtained molded product exhibits excellent properties such as the above-described correlated adhesiveness and low stickiness, Even when the amount of the ethylene / α-olefin copolymer (B) used relative to the propylene resin (A) is small, the impact resistance can be improved efficiently. The reason for this is not clear, but by selecting an ethylene / α-olefin copolymer (B) having a melting point in a specific range, it has an appropriate lamella thickness and the amount of tie molecules that connect the lamella and lamella is also optimal. It is presumed to be a thing.

  Further, in the olefin polymer composition (E), a low density ethylene / α-olefin copolymer (F) is used as a raw material of the composition as necessary. The low-density ethylene / α-olefin copolymer (F) can efficiently improve the low-temperature impact resistance even when the amount used for the propylene-based resin (A) is small.

  As described above, the multilayer blow container of the present invention has high gloss and excellent impact resistance, and when the low density ethylene / α-olein copolymer (F) is used, low temperature impact resistance is achieved. The present inventors have estimated that it is also excellent.

  Since the multilayer blow container of the present invention is excellent in impact resistance, cracks and the like due to external impact are suppressed, and the outermost layer is highly glossy, so that the container has gloss with a transparent feeling. In addition, since the multilayer blow container of the present invention is excellent in low-temperature impact resistance, even when the multilayer blow container is filled with contents and transported, stored, etc. under low temperature conditions, it is due to impact from the outside. Cracks and the like are suppressed.

  The layer structure of the multilayer blow container of the present invention is not particularly limited as long as the outermost layer is a layer made of the olefin polymer composition (E). For example, the outermost layer made of the olefin polymer composition (E) A two-layer configuration with the innermost layer (layer configuration arranged in order of outermost layer / innermost layer), an outermost layer made of the olefin polymer composition (E), an intermediate layer adjacent to the outermost layer, Three-layer configuration with the innermost layer adjacent to the intermediate layer (layer configuration arranged in order of outermost layer / intermediate layer / innermost layer), outermost layer made of the olefin polymer composition (E), and adjacent to the outermost layer A four-layer structure (outermost layer / intermediate layer (1) /) of the intermediate layer (1), the intermediate layer (2) adjacent to the intermediate layer (1), and the innermost layer adjacent to the intermediate layer (2). Intermediate layer (2) / layer structure arranged in the order of the innermost layer).

  In the present invention, a layer located inside the outermost layer is defined as an inner layer. That is, in the present invention, the innermost layer and the intermediate layer correspond to inner layers, and the multilayer blow container of the present invention may have at least one inner layer and may have two or more layers.

  In the multilayer blow container of the present invention having the olefin polymer composition (E) in the outermost layer, when the layer adjacent to the outermost layer is formed from the propylene polymer (G) or the ethylene polymer (H), so-called Even without using an adhesive resin, strong adhesiveness was exhibited. From the viewpoint of adhesiveness with the outermost layer made of the olefin polymer composition (E) of the multilayer blow container of the present invention, the layer adjacent to the outermost layer made of the olefin polymer composition (E) is a propylene polymer ( G) or an ethylene polymer (H) is preferable.

  When the layer adjacent to the olefin polymer composition (E) is a layer other than the propylene polymer (G) and the ethylene polymer (H), the olefin polymer composition (E). From the viewpoint of adhesiveness with the outermost layer made of, it is preferable that the outermost layer made of the olefin polymer composition (E) and other layers are formed via the adhesive resin layer.

  In the multilayer blow container of the present invention, an arbitrary layer may be colored.

  The propylene polymer (G) is not particularly limited, and examples thereof include homopolypropylene, propylene / α-olefin random copolymer, propylene / α-olefin block copolymer, and the like. The MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238 of the propylene-based polymer (G) is preferably in the range of 0.1 to 20.0 g / 10 minutes. In particular, 0.1 to 5 g / 10 min is preferable. Moreover, it is preferable that the crystal | crystallization melting | fusing point measured with the differential scanning calorimeter (DSC) based on JIS-K7121 is the range of 100-168 degreeC.

The ethylene polymer (H) is not particularly limited, and examples thereof include so-called high density polyethylene, linear low density polyethylene, and low density polyethylene. The density of the ethylene polymer (H) measured by the density gradient tube method is preferably 0.860 to 0.980 g / cm ³ , and the measurement temperature is 230 ° C. in accordance with ASTM D-1238. The MFR measured with a 16 kg load is preferably 0.01 to 20 g / 10 min, and particularly preferably 0.1 to 5 g / 10 min.

  The modified polyolefin resin (I) is not particularly limited, and generally an acid-modified polyolefin can be used. Examples of the acid used for the acid modification include an ethylenically unsaturated carboxylic acid such as maleic anhydride, acrylic acid, methacrylic acid, and itaconic anhydride, or an anhydride thereof. The polyolefin resin used for modification is preferably an ethylene / α-olefin copolymer, a propylene homopolymer, or a propylene / α-olefin copolymer.

  Further, the inner layer other than the layer adjacent to the outermost layer in the multilayer blow container is composed of a propylene polymer (G), an ethylene polymer (H), a styrene polymer, a polyethylene terephthalate resin, a polyamide resin, an ABS resin. It is preferably a layer formed from at least one resin selected from ethylene-vinyl acetate copolymer, polyvinyl alcohol resin, or polyvinyl chloride resin.

  Moreover, other resins and various additives may be contained in layers other than the outermost layer.

  As a method for forming the multilayer blow container of the present invention, any method may be used as long as it is blow molding. Examples of the molding method include a direct blow molding method (hollow molding method), an injection stretch blow molding method (injection hollow molding method), an extrusion stretch blow molding method, and a sheet blow molding method. The multilayer blow container is preferably obtained by molding by a direct blow molding method or an injection stretch blow molding method from the viewpoint of productivity in mass production.

  When forming a multilayer blow container by the direct blow molding method, for example, using a multilayer blow die, the olefin polymer composition (E) and other resins are used, and the olefin polymer composition (E) is the outermost layer. Then, while the obtained parison is still in a molten state, it is sandwiched between blow molds, and fluid is blown into the parison to be molded into a predetermined shape. Since the layer formed from the olefin polymer composition (E) is the outermost layer, a high gloss multilayer blow container can be obtained.

  And (E), in view of the MFR, there are cases where blow molding is restricted by itself (for example, there may be some difficulties in large blow molding), but if the technique of the present invention is used, the outermost layer By appropriately selecting a layer other than (for example, by appropriately selecting (G) and (H)), it is possible to simultaneously achieve gloss and the like and enlargement.

The molding conditions depend on the properties of the resin, but the temperature of the resin when the fluid is blown, that is, the molding temperature is preferably 120 to 260 ° C., and the fluid blowing pressure is ² to 10 kg / cm ^2. Preferably, the blow ratio is 1.2 to 5.0 from the viewpoint of moldability.

  The blow ratio here refers to a value obtained by dividing the outer diameter of the bottle to be molded by the outer diameter of the cylindrical molten parison extruded from the extruder die portion.

  When molding a multilayer blow container by the injection stretch blow molding method, for example, the olefin polymer composition (E) and other resins are injection molded so that the olefin polymer composition (E) is the outermost layer. By doing so, a preform is formed. Next, in a state where the preform is in a molten state or a softened state, or after re-heating after the preform is solidified, the preform is forcibly stretched longitudinally using a stretching rod or the like, and then the transverse direction. A multilayer blow container can be obtained by press-fitting a pressurized fluid into the preform for further stretching. When molding a preform by injection molding, the injection temperature of the olefin polymer composition (E) is usually in the range of 160 to 260 ° C. The temperature of the preform immediately before the longitudinal stretching is preferably 110 to 150 ° C., the longitudinal stretching ratio is preferably 1.5 to 4.0 times, and the transverse stretching ratio is 1.5 to 3.0 times. It is preferable that

  The thickness and size of the multilayer blow container of the present invention are appropriately determined depending on the use of the multilayer blow container, etc., but usually the thickness is 0.3 to 10.0 mm, the size is 10 to 300 mm in diameter, and the height is 10 to 10 mm. 300 mm.

  As for the thickness of the outermost layer of the multilayer blow container of the present invention, the ratio of the thickness of the outer layer to the other inner layer (outer layer / inner layer) is preferably 50/50 to 5/95, more preferably 30/70 to 10 / 90 is preferred. Within the above-mentioned range, the high gloss of the outer layer is most easily expressed and the moldability is good, which is preferable.

  The multilayer blow container of the present invention is excellent in transparency when a transparent resin is used for layers other than the outermost layer. Specifically, the haze value (haze) measured using a haze meter in accordance with JIS-K7105 is preferably 30 or less, and more preferably 20 or less. Within the above range, it is possible to obtain a high value-added bottle with very good contents visibility.

  The multilayer blow container of the present invention is excellent in gloss. Specifically, the 60 degree gloss measured by a gloss meter in accordance with JIS-K7105 of the outermost layer is preferably 70 or more, and 75 or more. More preferably. Within the above range, it is possible to obtain a high value-added bottle exhibiting an excellent gloss appearance.

  The multi-layer blow container according to the present invention can be used for various applications, for example, filling containers such as sauces, dressings, juices, fruits, sweets, boiled vegetables, toiletries such as cosmetics and shampoos. It is suitable as a container for filling sanitary goods such as containers and liquid detergents.

[Method for producing multilayer blow container]
The method for producing a multilayer blow container of the present invention uses a thermoplastic resin composition other than the olefin polymer composition (E) and the olefin polymer composition (E) described above, and the olefin polymer composition (E) It is preferable that the outermost layer is formed and molded by a direct blow molding method or an injection stretch blow molding method so that the thermoplastic resin composition other than the olefin polymer composition (E) forms at least one inner layer.

  Propylene resin (A), ethylene / α-olefin copolymer (B), low density ethylene / α-olefin copolymer (F), nucleating agent (D), olefin heavy used in the production method of the present invention As the thermoplastic resin other than the coalescence composition (E) and the olefin polymer composition (E), those described in the above-mentioned section [Multilayer Blow Container] can be used. Other resins and various additives described above can also be used.

  In the production method of the present invention, a multilayer blow container in which the outermost layer is formed from the olefin polymer composition (E) is molded by a direct blow molding method or an injection stretch blow molding method. For this reason, the resulting multilayer blow container is highly glossy because the outermost layer of the multilayer blow container contains the ethylene / α-olefin copolymer (B). The multilayer blow container is also excellent in impact resistance.

  Since the multilayer blow container obtained by the production method of the present invention has excellent impact resistance, cracks due to external impact are suppressed, and the outermost layer is highly glossy, so that the container has gloss with a transparent feeling. .

  EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these.

[Production of Propylene Resin (A-1)]
(1) Preparation of solid catalyst component An anhydrous magnesium chloride 95.2 g, decane 442 ml and 2-ethylhexyl alcohol 390.6 g were heated at 130 ° C. for 2 hours to form a homogeneous solution, and then phthalic anhydride 21 was added to this solution. .3 g was added, and further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.

  The homogeneous solution thus obtained was cooled to room temperature, and then 75 ml of this homogeneous solution was dropped into 200 ml of titanium tetrachloride maintained at −20 ° C. over 1 hour. After the completion of charging, the temperature of the mixed solution was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.22 g of diisobutyl phthalate (DIBP) was added, followed by stirring at the same temperature for 2 hours. Retained.

  After completion of the reaction for 2 hours, the solid part was collected by hot filtration. The solid part was resuspended in 275 ml of titanium tetrachloride, and then heated again at 110 ° C. for 2 hours. After completion of the reaction, the solid part was again collected by hot filtration, and washed thoroughly with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution. The solid part after washing was defined as a solid titanium catalyst component (A). The solid titanium catalyst component (A) was stored as a decane slurry, but a portion thereof was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component (A) was 2.3 wt% titanium, 61 wt% chlorine, 19 wt% magnesium, and 12.5 wt% DIBP.

The free titanium compound was detected by the following method. 10 ml of the supernatant of the above solid catalyst component was collected with a syringe into a 100 ml branched Schlenk previously purged with nitrogen and charged. Next, the solvent hexane was dried in a nitrogen stream, and further vacuum-dried for 30 minutes. This was charged with 40 ml of ion-exchanged water and 10 ml of 50% by volume sulfuric acid and stirred for 30 minutes. This aqueous solution was transferred to a 100 ml volumetric flask through a filter paper, followed by conc. As a masking agent for iron (II) ions. 1 ml of H ₃ PO ₄ and ₅ ml of 3% H ₂ O ₂ aqueous solution were added as a coloring reagent for titanium, and the volume was further increased to 100 ml with ion-exchanged water. The volumetric flask was shaken and mixed, and after 20 minutes, the absorbance at 420 nm was observed using UV to detect free titanium. Free titanium was removed by washing and free titanium was detected until this absorption was not observed.

(2) Preparation of prepolymerization catalyst component A three-necked flask with a stirrer having an internal volume of 500 ml was replaced with nitrogen gas, and then 400 ml of dehydrated heptane, 19.2 mmol of triethylaluminum, 3.8 mmol of dicyclopentyldimethoxysilane, and the above 4 g of solid titanium catalyst component (A) was added. While maintaining the internal temperature at 20 ° C., propylene gas was continuously introduced at a rate of 8 g / hr while stirring. After 1 hour, stirring was stopped, and as a result, a prepolymerized catalyst component (B) in which 2 g of propylene was polymerized per 1 g of the solid titanium catalyst component (A) was obtained.

(3) Polymerization A stainless steel autoclave with a stirrer with an internal volume of 10 L was sufficiently dried, and after substitution with nitrogen, 6 L of dehydrated heptane, 12.5 mmol of triethylaluminum, and 0.6 mmol of dicyclopentyldimethoxysilane were added. After replacing nitrogen in the system with propylene, hydrogen was charged at 0.30 MPa-G, and then propylene and ethylene were introduced with stirring. The amount introduced was adjusted so that the ethylene concentration in the gas phase in the polymerization tank was 1.5 mol%.

  After the inside of the system was stabilized at an internal temperature of 80 ° C. and a total pressure of 0.8 MPa-G, 20.8 ml of heptane slurry containing 0.10 mmol of the prepolymerized catalyst component (B) in terms of Ti atoms was added, and the total pressure and ethylene were added. Polymerization was carried out at 80 ° C. for 3 hours while continuously supplying propylene and ethylene so as to maintain the concentration.

  When a predetermined time had elapsed, 50 ml of methanol was added to stop the reaction, and the temperature was lowered and the pressure was released. The entire contents were transferred to a filtration tank equipped with a filter, heated to 60 ° C., and solid-liquid separated. Further, the solid part was washed twice with 6 L of heptane at 60 ° C. The propylene / ethylene copolymer (propylene resin (A-1)) thus obtained was vacuum dried.

Melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the obtained propylene-based resin (A-1) was calculated from 7.0 g / 10 min, ¹³ C-NMR. The weight of the structural unit derived from ethylene is 3.2% by weight when the total of the structural unit derived from propylene and the structural unit derived from ethylene is 100% by weight, DSC melting point (measured by DSC based on JIS-K7121) Crystal melting point) was 145 ° C. and Mw / Mn (molecular weight distribution) was 5.3.

[Production of Propylene Resin (A-2)]
The production of the propylene polymer (A-1) is the same as the production of the propylene polymer (A-1) except that the ethylene concentration in the gas phase in the polymerization tank is adjusted to 2.2 mol%. Polymerization was carried out.

Melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the obtained propylene-based resin (A-2) was calculated from 7.0 g / 10 min, ¹³ C-NMR. The weight of the structural unit derived from ethylene is 4.8% by weight when the total of the structural unit derived from propylene and the structural unit derived from ethylene is 100% by weight, DSC melting point (measured by DSC based on JIS-K7121) Crystal melting point) was 136 ° C., and Mw / Mn (molecular weight distribution) was 5.5.

[Production of Propylene Resin (A-3)]
The production of the propylene polymer (A-1) is the same as the production of the propylene polymer (A-1) except that the ethylene concentration in the gas phase portion in the polymerization tank is adjusted to 0.8 mol%. Polymerization was carried out.

Melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the obtained propylene-based resin (A-3) was calculated from 7.0 g / 10 min, ¹³ C-NMR. The weight of the ethylene-derived structural unit when the total of the propylene-derived structural unit and the ethylene-derived structural unit is 100% by weight is 1.0% by weight, DSC melting point (based on JIS-K7121, measured by DSC) Crystal melting point) was 156 ° C. and Mw / Mn (molecular weight distribution) was 5.0.

[Production of Propylene Resin (A-4)]
In the production of the propylene polymer (A-1), it was the same as the production of the propylene polymer (A-1), except that nitrogen in the system was replaced with propylene and hydrogen was charged at 0.15 MPa-G. Polymerization was carried out.

Melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the obtained propylene-based resin (A-4) was calculated from ¹³ C-NMR at 3.0 g / 10 min. The weight of the structural unit derived from ethylene when the total of the structural unit derived from propylene and the structural unit derived from ethylene is 100% by weight is 3.2% by weight, DSC melting point (measured by DSC based on JIS-K7121 Crystal melting point) was 145 ° C. and Mw / Mn (molecular weight distribution) was 5.3.

[Production of Propylene Resin (A-5)]
In the production of the propylene polymer (A-1), it was the same as the production of the propylene polymer (A-1), except that nitrogen in the system was replaced with propylene and hydrogen was charged at 0.45 MPa-G. Polymerization was carried out.

Melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the obtained propylene-based resin (A-5) was calculated from ¹³ C-NMR at 15.0 g / 10 min. The weight of the structural unit derived from ethylene is 3.2% by weight when the total of the structural unit derived from propylene and the structural unit derived from ethylene is 100% by weight, DSC melting point (measured by DSC based on JIS-K7121) Crystal melting point) was 145 ° C. and Mw / Mn (molecular weight distribution) was 5.3.

[Production of ethylene / α-olefin copolymer (B-1)]
(1) Preparation of catalyst 10.0 kg of silica dried at 600 ° C. for 10 hours and 154 liters of toluene were charged in a 300 liter reactor sufficiently purged with nitrogen, and the suspension was cooled to 0 ° C. Thereafter, 23.4 liters of a toluene solution of methylaluminoxane (Al = 3.02 mol / liter) was dropped into the suspension over 1 hour. At this time, the temperature in the system was kept in the range of 0 to 5 ° C.

  Subsequently, the mixture was reacted at 0 ° C. for 30 minutes, then heated to 95 ° C. over 1.5 hours and reacted at that temperature for 4 hours. Thereafter, the temperature was lowered to 60 ° C., and the supernatant was removed by a decantation method. The solid component thus obtained was washed twice with toluene and then resuspended in 100 liters of toluene to make a total volume of 160 liters.

  To the suspension thus obtained, 20.0 liters of a toluene solution of bis (1,3-n-butylmethylcyclopentadienyl) zirconium dichloride (Zr = 25.6 mmol / liter) was added at 35 ° C. The solution was added dropwise over 30 minutes and further reacted at 35 ° C. for 2 hours. Thereafter, the supernatant was removed and washed twice with hexane to obtain a solid catalyst component (1) containing 3.2 mg of zirconium per 1 g of the solid catalyst component.

(2) Preparation of prepolymerization catalyst component In a 350 liter reactor sufficiently purged with nitrogen, 7.0 kg of the solid catalyst component (1) prepared above and hexane were charged to a total volume of 285 liters. After cooling the system to 10 ° C., ethylene was blown into hexane at a flow rate of 8 Nm ³ / hr for 5 minutes. During this time, the temperature in the system was maintained at 10 to 15 ° C. Thereafter, the ethylene supply was stopped, and 2.4 mol of diisobutylaluminum hydride (DIBALH) and 1.2 kg of 1-hexene were charged. After the inside of the system was closed, ethylene supply was started again at a flow rate of 8 Nm ³ / hr. After 15 minutes, the ethylene flow rate was lowered to 2 Nm ³ / hr, and the pressure in the system was adjusted to 0.08 MPaG. During this time, the temperature in the system rose to 35 ° C. Thereafter, ethylene was supplied at a flow rate of 4 Nm ³ / hr for 3.5 hours while adjusting the temperature in the system to 32 to 35 ° C. During this time, the pressure in the system was maintained at 0.07 to 0.08 MPaG. Next, after the inside of the system was replaced with nitrogen, the supernatant was removed and washed twice with hexane. Thus, a prepolymerized catalyst (2) in which 3 g of polymer was prepolymerized per 1 g of the solid catalyst component was obtained.

(3) Polymerization Using a continuous fluidized bed gas phase polymerization apparatus, ethylene and 1-hexene were copolymerized at a total pressure of 2.0 MPaG, a polymerization temperature of 70 ° C., and a gas linear velocity of 0.7 m / sec.

Polymerization was started while continuously supplying 4.1 g / hr of the prepolymerized catalyst (2) prepared above and TIBA at a rate of 5 mmol / hr. In order to maintain a constant gas composition during the polymerization, ethylene, 1-hexene, hydrogen and nitrogen were continuously supplied (gas composition (mol ratio); 1-hexene / ethylene = 0.04, hydrogen / ethylene = 4). 0.0 × 10 ⁻⁴ , ethylene concentration = 71%).

The yield of the obtained ethylene / 1-hexene copolymer was 6.0 kg / hr, the DSC melting point (crystal melting point measured by DSC according to JIS-K7121) was 98 ° C., measured by the density gradient tube method. Density was 0.903 g / cm ³ , MFR (ASTM-1238, measuring temperature 230 ° C., load 2.16 kg) was 7.0 g / 10 min, and Mw / Mn (molecular weight distribution) was 2.6. .

  The obtained ethylene / 1-hexene copolymer is also referred to as an ethylene / α-olefin copolymer (B-1).

[Production of ethylene / α-olefin copolymer (B-2)]
In the production of the ethylene / α-olefin copolymer (B-1), the polymerization temperature was changed to 80 ° C., and the gas composition (mol ratio) was 1-hexene / ethylene = 0.03, hydrogen / ethylene = 4.2. An ethylene / 1-hexene copolymer was obtained in the same manner as in the production of the ethylene / α-olefin copolymer (B-1) except that the ethylene concentration was changed to × 10 ⁻⁴ and ethylene concentration = 71%.

The yield of the obtained ethylene / 1-hexene copolymer was 6.0 kg / hr, the DSC melting point (crystal melting point measured by DSC according to JIS-K7121) was 113 ° C., and measured by the density gradient tube method. Density was 0.913 g / cm ³ , MFR (ASTM-1238, measuring temperature 230 ° C., load 2.16 kg) was 7.0 g / 10 min, and Mw / Mn (molecular weight distribution) was 2.6. .

  The obtained ethylene / 1-hexene copolymer is also referred to as an ethylene / α-olefin copolymer (B-2).

[Production of ethylene / α-olefin copolymer (B-3)]
In the production of the ethylene / α-olefin copolymer (B-1), the polymerization temperature was changed to 80 ° C., and the gas composition (mol ratio) was 1-hexene / ethylene = 0.02, hydrogen / ethylene = 4.6. An ethylene / 1-hexene copolymer was obtained in the same manner as in the production of the ethylene / α-olefin copolymer (B-1) except that the ethylene concentration was changed to × 10 ⁻⁴ and ethylene concentration = 70%.

The yield of the obtained ethylene / 1-hexene copolymer is 5.8 kg / hr, the DSC melting point (crystal melting point measured by DSC according to JIS-K7121) is 120 ° C., and measured by the density gradient tube method. Density was 0.924 g / cm ³ , MFR (ASTM-1238, measuring temperature 230 ° C., load 2.16 kg) was 7.0 g / 10 min, and Mw / Mn (molecular weight distribution) was 2.6. .

  The obtained ethylene / 1-hexene copolymer is also referred to as an ethylene / α-olefin copolymer (B-3).

[Example A1]
97 parts by weight of propylene-based resin (A-1), 3 parts by weight of ethylene / α-olefin copolymer (B-1), and ADEKA STAB NA-21 (manufactured by ADEKA: bis (2 , 4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-oxide) aluminum hydroxide as a main component 0.15 parts by weight of an aromatic phosphate ester compound nucleating agent) and a phenolic antioxidant [pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) as an additive ) Propionate]], 0.10 parts by weight of a phosphorus-based antioxidant [Tris (2,4-di-t-butylphenyl) phosphite], calcite stearate as a neutralizing agent 0.09 parts by weight of the rubber and 0.10 parts by weight of stearic acid monoglyceride as an antistatic agent were mixed with stirring using a Henschel mixer, and the mixture was mixed using a twin-screw extruder (NR-36) manufactured by Nakatani Machinery Co., Ltd. A strand was obtained by melt-kneading under the following conditions.

(Twin screw extruder conditions)
Model: NR-36
Screw rotation speed 250rpm
Resin temperature 200 ° C
The obtained strand was cooled with water and then cut with a pelletizer to obtain pellets of the olefin polymer composition (E-1).

  Melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-1) is 7.0 g / 10 minutes, DSC melting point (according to JIS-K7121), Crystal melting point measured by DSC) was 147 ° C.

  The results are shown in the table together with the semi-crystallization time and odor measurement results.

  Next, blow molding was performed using the pellets.

Using three types of three-layer multi-layer direct blow molding machine (Placo Co., Ltd., 3B50 / 40/40 blow molding machine), the molding temperature is set to 200 ° C. and the fluid blowing pressure is set to 5.0 kg / cm ² . Then, a molten parison having an outer diameter of 20.0 mm was formed by a crosshead die having a die hole size of 14.0 mm and a core size of 12.5 mm, weight 34 g, inner capacity 780 ml, mouth screw outer diameter 27.0 mm, waist circumference A cylindrical multilayer blow container having a two-layer structure having an outer diameter of 72 mm and a waistline average thickness of 0.5 mmt was manufactured.

  Specifically, a propylene-based random copolymer B251VT (Co., Ltd.) is used for a base material (inner layer) by using an intermediate layer and an outer layer extruder having a cylinder temperature set at 200 ° C. without using an inner layer extruder. Prime polymer, melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 1.2 g / 10 minutes, DSC melting point (according to JIS-K7121, crystal melting point measured by DSC) ) Is 146 ° C.) with an intermediate layer extruder and the olefin polymer composition (E-1) is dissolved with an outer layer extruder so that the outer layer thickness ratio is 15%. After forming a molten parison in the shape of a mold, it was sandwiched between blow molds adjusted to a temperature of 25 ° C. by a water circulation circuit, stretched and adhered to the mold with compressed air, and cooled and solidified to obtain a multilayer blow container. As the blow mold, two types of molds, that is, a mold subjected to sandblasting # 400 as a surface treatment and a mold subjected to sandblasting # 200, are used, and a multilayer blow container is formed using each mold. Obtained.

  Using the obtained multilayer blow container as a test bottle, haze, gloss (gross), moldability, adhesiveness, impact resistance (full water impact resistance) and stickiness were measured by the following evaluation methods. In order to investigate whether the surface treatment of the mold affects the gloss of the multilayer blow container, a multilayer blow container was prepared using two types of molds, and the gloss of each was evaluated. These results are shown in the table.

[Example A2]
The same procedure as in Example A1 was conducted, except that the propylene resin (A-1) was changed to 95.5 parts by weight and the ethylene / α-olefin copolymer (B-1) was changed to a ratio of 4.5 parts by weight. Melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-2) obtained in Example A2 is 7.0 g / 10 min, DSC melting point (Based on JIS-K7121, crystal melting point measured by DSC) was 147 ° C.

  The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.

[Example A3]
At the time of multilayer blow molding, instead of propylene random copolymer B251VT (manufactured by Prime Polymer Co., Ltd.) for the base material (inner layer), propylene random block copolymer B511QA (manufactured by Prime Polymer Co., Ltd., melt) Flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) is 1.2 g / 10 minutes, DSC melting point (according to JIS-K7121, crystal melting point measured by DSC is 158 ° C.) The same procedure as in Example A2 was carried out except that the intermediate layer was used.

  The results are shown in the table.

[Example A4]
In the case of multilayer blow molding, instead of the propylene random copolymer B251VT (manufactured by Prime Polymer Co., Ltd.) for the base material (inner layer), PE resin HDPE, HZ-6008B (manufactured by Prime Polymer Co., Ltd.) melt flow Rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 0.7 g / 10 min, density measured by density gradient tube method is 0.958 g / cm ³ ) Example A2 was carried out in the same manner as in Example A2.

  The results are shown in the table.

[Example A5]
The same procedure as in Example A1 was conducted, except that the ratio of propylene-based resin (A-1) was 80.0 parts by weight and the ratio of ethylene / α-olefin copolymer (B-1) was 20.0 parts by weight. Melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-3) obtained in Example A5 is 7.0 g / 10 min, DSC melting point (Based on JIS-K7121, crystal melting point measured by DSC) was 148 ° C.

  The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.

[Example A6]
As a nucleating agent (D), ADEKA STAB NA-21 (manufactured by ADEKA) was replaced by 0.15 parts by weight, and Gelol MD (product name of Shin Nippon Rika Co., Ltd., chemical name = 1, 3, 2, 4-di-) (P-methylbenzylidene) sorbitol, described as G-MD in the table) was changed to 0.30 parts by weight, and was carried out in the same manner as in Example A2. The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-7) obtained in Example A6 is 7.0 g / 10 min, DSC melting point (Based on JIS-K7121, crystal melting point measured by DSC) was 149 ° C.

  The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.

[Example A7]
When the propylene resin (A-1) is stirred and mixed with a Henschel mixer instead of the propylene resin (A-4), [2,5-di-methyl-2,5- The same procedure as in Example A2 except that 0.006 part by weight of di- (benzoylperoxy) hexane] was added.

  The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-20) obtained in Example A7 is 7.0 g / 10 min, DSC melting point (Based on JIS-K7121, crystal melting point measured by DSC) was 147 ° C. The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.

[Comparative Example A1]
The same procedure as in Example A1 was carried out except that the proportion of propylene resin (A-1) was changed to 100 parts by weight and that of ethylene / α-olefin copolymer (B-1) was changed to 0 part by weight. Melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-4) obtained in Comparative Example A1 is 7.0 g / 10 min, DSC melting point (Based on JIS-K7121, crystal melting point measured by DSC) was 147 ° C.

  The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.

  In Comparative Example A1, since the ethylene / α-olefin copolymer (B) is not blended, the requirements of this claim are not satisfied. Since the ethylene / α-olefin copolymer (B) is not blended, adhesion and impact resistance (full water drop impact strength) are inferior.

[Comparative Example A2]
The same procedure as in Example A1 was carried out except that the propylene-based resin (A-1) was changed to 70.0 parts by weight and the ethylene / α-olefin copolymer (B-1) was changed to a ratio of 30.0 parts by weight. The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-5) obtained in Comparative Example A2 is 7.0 g / 10 min, DSC melting point (Based on JIS-K7121, crystal melting point measured by DSC) was 147 ° C.

  The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.

  In Comparative Example A2, the blending amount of the ethylene / α-olefin copolymer (B) is larger than the range specified in the claims. For this reason, stickiness is inferior.

[Comparative Example A3]
The same procedure as in Example A2 was carried out except that ADK STAB NA-21 (manufactured by ADEKA) was not added as the nucleating agent (D). Melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-6) obtained in Comparative Example A3 is 7.0 g / 10 min, DSC melting point (Based on JIS-K7121, crystal melting point measured by DSC) was 145 ° C.

  The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.

  In Comparative Example A3, the case of Claim 1 is not satisfied because the nucleating agent (D) is not blended. For this reason, gloss is inferior.

[Comparative Example A4]
It carried out similarly to Example A2 except having replaced with propylene-type resin (A-1) and having changed to propylene-type resin (A-2). The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-8) obtained in Comparative Example A4 is 7.0 g / 10 min, DSC melting point (Based on JIS-K7121, crystal melting point measured by DSC) was 138 ° C.

  The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.

  In Comparative Example A4, the DSC melting point (crystal melting point measured by DSC based on JIS-K7121) of the propylene-based resin (A) is lower than the range specified in the claims. For this reason, formability and stickiness are inferior.

[Comparative Example A5]
It carried out similarly to Example A2 except having replaced with the propylene-type resin (A-1) and having changed into the propylene-type resin (A-3). The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-9) obtained in Comparative Example A5 is 7.0 g / 10 min, DSC melting point (Based on JIS-K7121, crystal melting point measured by DSC) was 158 ° C.

  The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.

  In Comparative Example A5, the DSC melting point (crystal melting point measured by DSC based on JIS-K7121) of the propylene-based resin (A) is higher than the range specified in the claims. For this reason, impact resistance (full water impact resistance) is inferior.

[Comparative Example A6]
It carried out similarly to Example A2 except having replaced with propylene-type resin (A-1) and having changed to propylene-type resin (A-4). Melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-10) obtained in Comparative Example A6 is 3.0 g / 10 min, DSC melting point (Based on JIS-K7121, crystal melting point measured by DSC) was 147 ° C.

  The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.

  In Comparative Example A6, the melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E) is lower than the range specified in the claims. For this reason, gloss is inferior.

[Comparative Example A7]
It carried out similarly to Example A2 except having replaced with the propylene-type resin (A-1) and having changed to the propylene-type resin (A-5). The melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-11) obtained in Comparative Example A7 is 15.0 g / 10 min, DSC melting point (Based on JIS-K7121, crystal melting point measured by DSC) was 147 ° C.

  The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.

  In Comparative Example A7, the melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E) is higher than the range specified in the claims. For this reason, moldability and impact resistance (full drop impact strength) are inferior.

[Comparative Example A8]
The same procedure as in Example A2 was conducted except that the ethylene / α-olefin copolymer (B-2) was changed to the ethylene / α-olefin copolymer (B-2). The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-12) obtained in Comparative Example A8 is 7.0 g / 10 min, DSC melting point (Based on JIS-K7121, crystal melting point measured by DSC) was 147 ° C.

  The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.

  The ethylene / α-olefin copolymer (B-2) used in Comparative Example A8 has a DSC melting point (crystalline melting point measured by DSC based on JIS-K7121) of the ethylene / α-olefin copolymer (B). It is higher than the range specified in the claims. For this reason, adhesiveness and impact resistance (full drop impact strength) are inferior. Furthermore, the balance between impact resistance and stickiness is not good.

[Comparative Example A9]
The same procedure as in Comparative Example A8 was conducted except that the propylene-based resin (A-1) was changed to 90.0 parts by weight and the ethylene / α-olefin copolymer (B-2) was changed to a ratio of 10.0 parts by weight. The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-13) obtained in Comparative Example A9 is 7.0 g / 10 min, DSC melting point (Based on JIS-K7121, crystal melting point measured by DSC) was 147 ° C.

  The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.

  The ethylene / α-olefin copolymer (B-2) used in Comparative Example A9 has a DSC melting point (crystal melting point measured by DSC based on JIS-K7121) of the ethylene / α-olefin copolymer (B). It is higher than the range specified in the claims. For this reason, adhesiveness and impact resistance (full drop impact strength) are inferior. Furthermore, the balance between impact resistance and stickiness is not good.

[Comparative Example A10]
The same procedure as in Comparative Example A8 was conducted except that the propylene resin (A-1) was changed to a ratio of 80.0 parts by weight and the ethylene / α-olefin copolymer (B-2) was changed to a ratio of 20.0 parts by weight. The melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-14) obtained in Comparative Example A10 is 7.0 g / 10 min, DSC melting point (Based on JIS-K7121, crystal melting point measured by DSC) was 147 ° C.

  The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.

  The ethylene / α-olefin copolymer (B-2) used in Comparative Example A10 has a DSC melting point (crystalline melting point measured by DSC based on JIS-K7121) of the ethylene / α-olefin copolymer (B). It is higher than the range specified in the claims. For this reason, adhesiveness and impact resistance (full drop impact strength) are inferior. Furthermore, the balance between impact resistance and stickiness is not good.

[Comparative Example A11]
The same procedure as in Example A2 was carried out except that the ethylene / α-olefin copolymer (B-1) was replaced with an ethylene / α-olefin copolymer (B-3). The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-15) obtained in Comparative Example A11 is 7.0 g / 10 min, DSC melting point (Based on JIS-K7121, crystal melting point measured by DSC) was 147 ° C.

  The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.

  The ethylene / α-olefin copolymer (B-3) used in Comparative Example A11 has a DSC melting point (crystal melting point measured by DSC based on JIS-K7121) of the ethylene / α-olefin copolymer (B). It is higher than the range specified in the claims. For this reason, gloss (gross), adhesiveness, and impact resistance (full water drop impact strength) are inferior. Furthermore, the balance between impact resistance and stickiness is not good.

[Comparative Example A12]
PE-based resin L-LDPE (linear low-density polyethylene) produced by a Ziegler-Natta catalyst that is not a metallocene catalyst instead of the ethylene / α-olefin copolymer (B-1), Ultzex 1030L ((stock) ) Prime polymer, density 0.909 g / cm ³ , melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 7.0 g / 10 min, DSC melting point (according to JIS-K7121) This was carried out in the same manner as in Example A2 except that the crystal melting point measured by DSC was 115 ° C.).

  Melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-16) obtained in Comparative Example A12 is 7.0 g / 10 min, DSC melting point (Based on JIS-K7121, crystal melting point measured by DSC) was 147 ° C.

  The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.

  In Comparative Example A12, Ulutex 1030L was used in place of the ethylene / α-olefin copolymer (B). The DSC melting point of ULTZEX 1030L (according to JIS-K7121, crystal melting point measured by DSC) is 115 ° C., which is higher than the DSC melting point range of the ethylene / α-olefin copolymer (B) defined in the claims. . Furthermore, since Ultzex 1030L is polymerized with a Ziegler-Natta catalyst that is not a metallocene catalyst, the multilayer blow container formed from the olefin polymer composition (E-16) has adhesiveness, stickiness and impact resistance (full water). Drop impact strength is inferior. Furthermore, the balance between impact resistance and stickiness is not good.

[Comparative Example A13]
In place of the ethylene / α-olefin copolymer (B-1), PE resin HDPE (high density polyethylene), HZ-2100J (manufactured by Prime Polymer Co., Ltd., density 0.956 g / cm ³ , melt flow rate ( MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 11.0 g / 10 min, DSC melting point (according to JIS-K7121, crystal melting point measured by DSC) is 131 ° C., Mw / Mn ( Molecular weight distribution) was changed to 7.0), 90.0 parts by weight of propylene resin (A-1) and 10.0 parts by weight of PE resin HDPE, HZ-2100J (manufactured by Prime Polymer Co., Ltd.) The same procedure as in Example A1 was conducted except that the ratio was changed.

  The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-17) obtained in Comparative Example A13 is 8.0 g / 10 min, DSC melting point (Based on JIS-K7121, crystal melting point measured by DSC) was 147 ° C.

  The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.

In Comparative Example A13, HZ-2100J was used in place of the ethylene / α-olefin copolymer (B). The DSC melting point of HZ-2100J (according to JIS-K7121, crystal melting point measured by DSC) is 131 ° C., which is higher than the DSC melting point range of the ethylene / α-olefin copolymer (B) defined in the claims. . Furthermore, the density measured by the density gradient tube method of HZ-2100J is 0.956 g / cm ³ . For this reason, the multilayer blow container formed from an olefin polymer composition (E-17) is inferior in adhesiveness and impact resistance (full water drop impact strength). Furthermore, the balance between impact resistance and stickiness is not good.

[Comparative Example A14]
Instead of the ethylene / α-olefin copolymer (B-1), Tuffmer P-0680 (polyethylene rubber (EPR), manufactured by Mitsui Chemicals, Inc., density 0. 0) was used as the ethylene / α-olefin copolymer (B). 870 g / cm ³ , melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 1.0 g / 10 min, DSC melting point (according to JIS-K7121, crystal melting point measured by DSC) ) Is not measured.) And 90.0 parts by weight of propylene-based resin (A-1) and ethylene / α-olefin copolymer (B) as Toughmer P-0680 (manufactured by Mitsui Chemicals, Inc.) Was carried out in the same manner as in Example A1, except that the ratio was changed to 10.0 parts by weight.

  The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-18) obtained in Comparative Example A14 is 6.0 g / 10 min, DSC melting point (Based on JIS-K7121, crystal melting point measured by DSC) was 147 ° C.

  The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.

In Comparative Example A14, Tafmer P-0680 (manufactured by Mitsui Chemicals, Inc.) is used instead of the ethylene / α-olefin copolymer (B). Tuffmer P-0680 does not correspond to an ethylene / α-olefin copolymer (B) because the DSC melting point (based on JIS-K7121, crystal melting point measured by DSC) is not measured. Further, the melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) was 1.0 g / 10 min, and the density measured by the density gradient tube method was 0.870 g / cm ³ . .

  For this reason, the multilayer blow container formed from an olefin polymer composition (E-18) is inferior in glossiness (gloss), adhesiveness, and stickiness.

[Comparative Example A15]
Instead of the ethylene / α-olefin copolymer (B-1), Tuffmer P-0180 (polyethylene rubber (EPR), manufactured by Mitsui Chemicals, Inc., density 0. 0) was used as the ethylene / α-olefin copolymer (B). 870 g / cm ³ , melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 8.0 g / 10 min, DSC melting point (according to JIS-K7121, crystal melting point measured by DSC) ) Is not measured.), And Tufmer P-0180 (manufactured by Mitsui Chemicals, Inc.) as propylene resin (A-1) as 90.0 parts by weight and ethylene / α-olefin copolymer (B) Was carried out in the same manner as in Example A1, except that the ratio was changed to 10.0 parts by weight.

  The melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-19) obtained in Comparative Example A15 is 7.0 g / 10 min, DSC melting point (Based on JIS-K7121, crystal melting point measured by DSC) was 147 ° C.

  The results are shown in the table together with the semi-crystallization time, the odor measurement results and the multilayer blow container test results.

In Comparative Example A15, Tafmer P-0180 (manufactured by Mitsui Chemicals, Inc.) is used instead of the ethylene / α-olefin copolymer (B). Tuffmer P-0180 does not correspond to an ethylene / α-olefin copolymer (B) because its DSC melting point (based on JIS-K7121, crystal melting point measured by DSC) is not measured. Furthermore, the density was 0.870 g / cm ³ . For this reason, the multilayer blow container formed from an olefin polymer composition (E-19) is inferior in adhesiveness and stickiness.

[Example B1]
97 parts by weight of propylene-based resin (A-1), 3 parts by weight of ethylene / α-olefin copolymer (B-1), and ADEKA STAB NA-21 (manufactured by ADEKA: bis (2 , 4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin-6-oxide) aluminum hydroxide as a main component 0.15 parts by weight of an aromatic phosphate ester compound nucleating agent) as a low density ethylene / α-olefin copolymer (F), manufactured by Mitsui Chemicals, Tuffmer P-0280 (ethylene-propylene copolymer) the density was measured by a density gradient tube method: 0.870 g / cm ^3, Ziegler-Natta catalyst, DSC melting point (according to JIS-K7121, the crystalline melting point was measured by DSC): not observed, MFR (AST -1238, measurement temperature 230 ° C., load 2.16 kg): 5.4 g / 10 min) 15 parts by weight, and phenolic antioxidant [pentaerythritol tetrakis [3- (3,5-di-t] as an additive -Butyl-4-hydroxyphenyl) propionate], 0.10 parts by weight, phosphorus antioxidant [Tris (2,4-di-t-butylphenyl) phosphite]], 0.10 parts by weight, neutralizing agent As a mixture, 0.09 part by weight of calcium stearate was stirred and mixed with a Henschel mixer, and the mixture was melt kneaded under the following conditions using a twin screw extruder (NR-36) manufactured by Nakatani Machinery Co., Ltd. to obtain a strand. .

(Twin screw extruder conditions)
Model: NR-36
Screw rotation speed 250rpm
Resin temperature 200 ° C
The obtained strand was cooled with water and then cut with a pelletizer to obtain pellets of the olefin polymer composition (E-21).

  The melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the propylene-based resin composition (E-21) is 7.0 g / 10 minutes, and the DSC melting point (according to JIS-K7121) Crystal melting point measured by DSC) was 147 ° C.

  The results are shown in the table together with the semi-crystallization time and odor measurement results.

  Next, blow molding was performed using the pellets.

Using three types of three-layer multi-layer direct blow molding machine (Placo Co., Ltd., 3B50 / 40/40 blow molding machine), the molding temperature is set to 200 ° C. and the fluid blowing pressure is set to 5.0 kg / cm ² . Then, a molten parison having an outer diameter of 20.0 mm was formed by a crosshead die having a die hole size of 14.0 mm and a core size of 12.5 mm, weight 34 g, inner capacity 780 ml, mouth screw outer diameter 27.0 mm, waist circumference A cylindrical multilayer blow container having a two-layer structure having an outer diameter of 72 mm and a waistline average thickness of 0.5 mmt was manufactured.

  Specifically, a propylene-based random copolymer B251VT (Co., Ltd.) is used for a base material (inner layer) by using an intermediate layer and an outer layer extruder having a cylinder temperature set at 200 ° C. without using an inner layer extruder. Prime polymer, melt flow rate (MFR) (ASTM D-1238, measuring temperature 230 ° C., load 2.16 kg) is 1.2 g / 10 minutes, DSC melting point (according to JIS-K7121, crystal melting point measured by DSC) ) Is 146 ° C.) with an intermediate layer extruder and the olefin polymer composition (E-21) is dissolved with an outer layer extruder so that the outer layer thickness ratio is 15%. After forming a molten parison in the shape of a mold, it was sandwiched between blow molds adjusted to a temperature of 25 ° C. by a water circulation circuit, stretched and adhered to the mold with compressed air, and cooled and solidified to obtain a multilayer blow container. As the blow mold, two types of molds, that is, a mold subjected to sandblasting # 400 as a surface treatment and a mold subjected to sandblasting # 200, are used, and a multilayer blow container is formed using each mold. Obtained.

  Using the resulting multilayer blow container as a test bottle, haze, gloss (gross), formability, adhesiveness, stickiness, impact resistance (full water drop impact strength) and low temperature impact resistance by the following evaluation methods (Full water drop impact strength) was measured. In order to investigate whether the surface treatment of the mold affects the gloss of the multilayer blow container, a multilayer blow container was prepared using two types of molds, and the gloss of each was evaluated. These results are shown in the table.

[Example B2]
The low density ethylene / α-olefin copolymer (F) was measured by Mitsui Chemicals, Tafmer A-4085S (ethylene-butene copolymer, density gradient tube method) from Mitsui Chemicals, Tafmer P-0280. Density: 0.885 g / cm ³ , DSC melting point (according to JIS-K7121, crystal melting point measured by DSC): 70 ° C., MFR (ASTM-1238, measurement temperature 230 ° C., load 2.16 kg): 6.7 g / 10 minutes), the blending amount was changed from 15 parts by weight to 7 parts by weight, and the same procedure as in Example B1 was conducted except that 0.1 part by weight of stearic acid monoglyceride was used as an antistatic agent. Obtained.

  A multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.

  The results are shown in the table.

[Example B3]
The propylene resin (A-1) was changed to 90 parts by weight, the ethylene / α-olefin copolymer (B-1) was changed to 10 parts by weight, and the low density ethylene / α-olefin copolymer (F) was changed to Mitsui. A strand was obtained in the same manner as in Example B1 except that the chemical company, Tuffmer P-0280 was changed to Mitsui Chemicals, Tuffmer A-4085S, and the blending amount was changed from 15 parts by weight to 5 parts by weight. It was.

  A multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.

  The results are shown in the table.

[Example B4]
The low density ethylene / α-olefin copolymer (F) was changed in the same manner as in Example B1 except that Mitsui Chemicals Co., Ltd., Tafmer P-0280 was changed to Mitsui Chemicals Co., Ltd., Tafmer A-4085S. Obtained.

  A multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.

  The results are shown in the table.

[Example B5]
A strand was obtained in the same manner as in Example B1 except that the low-density ethylene / α-olefin copolymer (F) was not used.

  A multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.

  The results are shown in the table.

[Example B6]
The propylene-based resin (A-1) was changed to 95.5 parts by weight, and the ethylene / α-olefin copolymer (B-1) was changed to 4.5 parts by weight to obtain a low density ethylene / α-olefin copolymer (F ) Was used, and a strand was obtained in the same manner as in Example B1 except that 0.1 part by weight of stearic acid monoglyceride was used as an antistatic agent.

  A multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.

  The results are shown in the table.

[Example B7]
The propylene resin (A-1) is changed to 90 parts by weight, and the ethylene / α-olefin copolymer (B-1) is changed to 10 parts by weight, and the low density ethylene / α-olefin copolymer (F) is not used. A strand was obtained in the same manner as in Example B1.

  A multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.

  The results are shown in the table.

[Reference Example B1]
The propylene-based resin (A-1) was changed to 95.5 parts by weight, and the ethylene / α-olefin copolymer (B-1) was changed to 4.5 parts by weight to obtain a low density ethylene / α-olefin copolymer (F ) Was changed from 15 parts by weight to 25 parts by weight in the same manner as in Example B1 to obtain a strand.

  A multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.

  The results are shown in the table.

[Comparative Example B1]
The ethylene / α-olefin copolymer (B-1) was changed to the ethylene / α-olefin copolymer (B-2), the propylene resin (A-1) was changed to 95.5 parts by weight, Using 4.5 parts by weight of ethylene / α-olefin copolymer (B-2), a low density ethylene / α-olefin copolymer (F) was obtained from Mitsui Chemicals, Tuffmer P-0280, and Mitsui Chemicals. Tuffmer P-0275 (ethylene-propylene copolymer, density measured by density gradient tube method: 0.860 g / cm ³ , DSC melting point (according to JIS-K7121, crystal melting point measured by DSC): not observed , MFR (ASTM-1238, measurement temperature 230 ° C., load 2.16 kg): 5.4 g / 10 min) was carried out in the same manner as in Example B1 to obtain a strand.

  A multilayer blow container was obtained in the same manner as in Example B1 except that the strand was used.

  The results are shown in the table.

〔Evaluation method〕
According to the method described below, the propylene-based polymer (A), the ethylene / α-olefin copolymer (B), the low density ethylene / α-olefin copolymer (F) or the olefin polymer composition (E) Physical properties were measured. The results are shown in the table.

[MFR (melt flow rate)]
The MFR of the propylene resin (A), the ethylene / α-olefin copolymer (B), the low density ethylene / α-olefin copolymer (F), and the olefin polymer composition (E) is ASTM D- It was measured according to 1238, measurement temperature 230 ° C., load 2.16 kg.

  Based on ASTM D-1238, the strand obtained at the time of MFR measurement is extract | collected and it uses for the measurement of the following density.

[Melting point (Tm)]
The crystal melting points of the propylene resin (A), the ethylene / α-olefin copolymer (B), the low density ethylene / α-olefin copolymer (F) and the olefin polymer composition (E) are in accordance with JIS-K7121. The measurement was performed using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer). The peak of the endothermic peak at the third step measured here was defined as the crystalline melting point (Tm). When there are a plurality of endothermic peaks, the endothermic peak vertex at which the peak height is maximum is defined as the crystalline melting point (Tm).

(Measurement condition)
Measurement environment: Nitrogen gas atmosphere Sample volume: 5mg
Sample shape: Press film (230 ° C molding, thickness 200-400μm)
First step: The temperature is raised from 30 ° C to 240 ° C at 10 ° C / min and held for 10 min.

  Second step: Decrease the temperature to 60 ° C at 10 ° C / min.

  Third step: Increase the temperature to 240 ° C at 10 ° C / min.

[Semi-crystallization time (T _1/2 )]
The half crystallization time (T _1/2 ) of the olefin polymer composition (E) was measured using a differential scanning calorimeter (DSC, manufactured by Perkin Elmer (DSC7)). The olefin polymer composition (E) is crystallized under an isothermal condition of 125 ° C., and the calorific value associated with the crystallization is measured at this time, and the calorific value from the start of the exotherm (crystallization start) is half the total calorific value. The time (seconds) until the crystallization time was measured as the half crystallization time (t _1/2 ). A smaller half crystallization time (t _1/2 ) means a faster crystallization rate.

(Measurement condition)
Measurement environment: Nitrogen gas atmosphere Sample volume: 5mg
Sample shape: Press film (230 ° C molding, thickness 200-400μm)
First step: The temperature is increased from 30 ° C to 220 ° C at 10 ° C / min and held for 3 min.

  Second step: The temperature is decreased to 125 ° C at 60 ° C / min.

〔density〕
The density of the ethylene / α-olefin copolymer (B) and the low density ethylene / α-olefin copolymer (F) is low when the MFR is measured. The strands of the density ethylene / α-olefin copolymer (F) were each heat-treated at 120 ° C. for 1 hour, gradually cooled to room temperature over 1 hour, and then measured with a density gradient tube.

[Mw / Mn (molecular weight distribution)]
Mw / Mn of the propylene-based resin (A) and the ethylene / α-olefin copolymer (B) was determined from the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by the following measurement method.

  Mw and Mn were measured as follows using GPC-150C Plus manufactured by Waters.

  TSKgel GMH6-HT and TSKgel GMH6-HTL were used as separation columns, the column size was 7.5 mm in inner diameter and 600 mm in length, the column temperature was 140 ° C., and o-dichlorobenzene (Wako Pure Chemical Industries) was used as the mobile phase. Yakuhin Kogyo Co., Ltd.) and 0.025% by weight of BHT (Wako Pure Chemical Industries, Ltd.) as an antioxidant, moved at 1.0 ml / min, sample concentration of 0.1% by weight, sample injection The amount was 500 microliters, and a differential refractometer was used as a detector.

Standard polystyrene used was manufactured by Tosoh Corporation for molecular weights of Mw <1000 and Mw> 4 × 10 ⁶ , and used by Pressure Chemical Co. for 1000 ≦ Mw ≦ 4 × 10 ⁶ .

[Haze]
For the haze of the multilayer blow container, the measurement site was cut out from the container body, and the haze (cloudiness value) was measured with a haze meter (NIPPON DENSHOKU (NDH2000)) in accordance with JIS-K7105. It can be said that the smaller the haze value, the better the transparency.

[Glossy]
The glossiness was evaluated by the following gloss measurement. For the gloss of the multilayer blow container, the measurement site was cut out from the container body, and the 60-degree glossiness of the outer layer was measured with a gloss meter (NIPPON DENSHOKU (VG2000)) in accordance with JIS-K7105. It can be said that the larger the gloss value, the better the glossiness.

[Formability]
The moldability of the multi-layer blow container was evaluated by observing the appearance of the obtained container and the presence or absence of wrinkles due to the rough surface of the melted parison during blowing on the container body.

AA: No wrinkles or not noticeable, good moldability BB: Wrinkles can be observed or noticeable, and moldability is poor [Adhesiveness]
Between the outermost layer formed from the olefin polymer composition (E) of the present invention and the adjacent layer of the multilayer blow container, a string-like shape due to delamination that occurs in the burr cut part, that is, the container upper part and the container lower pinch-off part at the time of container molding Evaluate the presence or absence of appearance defects observed in strips.

AA: Appearance is poor and adhesion is good BB: Appearance is poor and adhesion is slightly inferior when observed closely CC: Clear appearance is poor and adhesion is inferior [Odor]
The odor of the olefin polymer composition (E) was obtained by putting 10 g of the composition pellets in a 100 ml Erlenmeyer flask, sealing with a cap, taking out after heating in an oven at 100 ° C. for 1 hour, and immediately opening the cap. The generated odor was judged as superior or inferior in the sensory test as follows.

AA: No odor BB: Some odor CC: Some odor [impact resistance]
The impact resistance was evaluated based on the presence or absence of surface cracks by the full water drop impact strength measurement method described below. A multi-layer blow container (with an internal capacity of 780 ml) filled with water was cooled to 5 ° C. (evaluation of impact resistance), and each of the 10 containers cooled to each temperature had a bottom of 1 m from the concrete surface. It was dropped vertically from the height position and evaluated according to the following drop criteria. The determination of the crack was made based on whether or not a surface crack was generated.

AA: No cracks occur on the surface in all cases BB: More than half, no cracks occur on the surface, but cracks occur on the surface with at least one CC: Cracks occur on the surface with a majority The full drop impact strength measurement The better the evaluation of the method, the better the impact resistance.

(Low temperature impact resistance)
The low temperature impact resistance was evaluated by the presence or absence of surface cracks by the full water drop impact strength measurement method described below. A filled container filled with ethylene glycol / water = 5/5 (volume / volume) in a multi-layer blow container (internal volume 780 ml) is cooled to −5 ° C. (evaluation of low temperature impact resistance), and each temperature Each of the 10 containers cooled in the vertical direction was dropped vertically from the position where the bottom surface of the container was 1 m above the concrete surface, and the evaluation was performed according to the following drop criteria. The determination of the crack was made based on whether or not a surface crack was generated.

AA: No cracks occur on the surface in all cases BB: More than half, no cracks occur on the surface, but cracks occur on the surface with at least one CC: Cracks occur on the surface with a majority The full drop impact strength measurement The better the evaluation of the method, the better the low-temperature impact resistance.

[Stickiness]
Regarding the touch of the surface of the multilayer blow container, the presence / absence of a sticky tactile sensation on the surface of the bottle that was conditioned at 23 ° C. for 48 to 72 hours after molding was judged as superior or inferior as follows.

AA: No stickiness at all BB: Little stickiness CC: Some stickiness DD: Feeling sticky In the multilayer blow container claimed in the present application, a non-sticky one is preferable, and a sticky one is sticky. I was inferior.

[Weight of structural unit derived from α-olefin in propylene resin calculated from ¹³ C-NMR]
The total of propylene-derived structural units calculated from ¹³ C-NMR and one or more olefin-derived structural units selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms is 100% by weight. The weight of the structural unit derived from one or more olefins selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms is measured and calculated as follows based on the measurement of ¹³ C-NMR. I decided.

¹³ C-NMR measurement conditions Measurement device: LA400 type nuclear magnetic resonance apparatus manufactured by JEOL Measurement mode: BCM (Bilevel Complete Decoupling)
Observation frequency: 100.4 MHz
Observation range: 17006.8Hz
Pulse width: C nucleus 45 ° (7.8 μsec)
Pulse repetition time: 5 seconds Sample tube: 5 mmφ
Sample tube rotation speed: 12Hz
Integration count: 20000 times Measurement temperature: 125 ° C
Solvent: 1,2,4-trichlorobenzene: 0.35 ml / heavy benzene: 0.2 ml
Sample amount: about 40mg
In the case where the comonomer is ethylene, the ratio of the obtained ¹³ C-NMR spectrum is determined in accordance with the following document (1), and the ratio of the monomer chain distribution (dyad (doubled) distribution) is determined. Mole fraction of structural units derived from ethylene (mol%) (hereinafter referred to as E (mol%)) and mole fraction of structural units derived from propylene (mol%) (hereinafter referred to as P (mol%)) Was calculated. The weight percent of the structural unit derived from propylene and the weight percent of the structural unit derived from ethylene in the propylene-based resin (A) were calculated from the calculated E (mol%) and P (mol%) in weight percent. .

Reference (1): Kakugo, M .; Naito, Y .; Mizunuma, K .; Miyatake, T., Macromolecules 1982, 15, (4), 1150-1152
Of the evaluation of the physical properties of the multilayer blow container, the haze, moldability, adhesiveness, impact resistance, low temperature impact resistance and stickiness were prepared using a mold subjected to sandblasting # 400. Measurements were made on multilayer blow containers.

Claims (13)

The resin used in the outermost layer is 80 to 98 parts by weight of the propylene resin (A) and 2 to 20 parts by weight of the ethylene / α-olefin copolymer (B) (however, the total of (A) and (B) Is 100 parts by weight) and the olefin polymer composition (E) formed from 0.01 to 0.5 parts by weight of the nucleating agent (D),
The propylene resin (A) satisfies the following requirements (A-1) and (A-2),
The ethylene / α-olefin copolymer (B) satisfies the following requirements (B-1) and (B-2),
The said olefin polymer composition (E) satisfy | fills the following requirements (E-1), The multilayer blow container characterized by the above-mentioned.
(A-1) A copolymer of propylene and one or more olefins selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms.
(A-2) The crystal melting point measured with a differential scanning calorimeter (DSC) in accordance with JIS-K7121 is in the range of 140 to 155 ° C.
(B-1) A copolymer of ethylene and one or more α-olefins having 4 to 20 carbon atoms.
(B-2) The crystal melting point measured by DSC according to JIS-K7121 is in the range of 85 ° C. or higher and lower than 110 ° C.
(E-1) The melt flow rate (MFR) measured at a measurement temperature of 230 ° C. and a load of 2.16 kg in accordance with ASTM D-1238 is in the range of 5 to 10 g / 10 minutes. The olefin polymer composition (E) is further formed using 0.1 to 20 parts by weight of a low density ethylene / α-olefin copolymer (F),
The low density ethylene / α-olefin copolymer (F) satisfies the following requirements (F-1) and (F-2),
The density (d _B [g / cm ³ ]) measured by the density gradient method of the ethylene / α-olefin copolymer (B) and the density gradient method of the low density ethylene / α-olefin copolymer (F) The multilayer blow container according to claim 1, wherein the density (d _F [g / cm ³ ]) measured in step 1 satisfies the following requirement (X-1).
(F-1) A copolymer of ethylene and one or more α-olefins having 3 to 20 carbon atoms.
(F-2) The crystalline melting point measured by DSC based on JIS-K7121 is 89 ° C. or lower, or no peak based on the crystalline melting point is observed.
(X-1) d _B [g / cm ³ ]> d _F [g / cm ³ ], and 0.010 [g / cm ³ ] ≦ (d _B −d _F ) [g / cm ³ ] ≦ 0 0.050 [g / cm ³ ]. The multilayer blow container according to claim 1, wherein the ethylene / α-olefin copolymer (B) further satisfies the following requirement (B-4).
(B-4) The density measured by the density gradient tube method is in the range of 0.880 to 0.910 g / cm ³ . The ethylene / α-olefin copolymer (B) further satisfies the following requirement (B-4a), and the low density ethylene / α-olefin copolymer (F) further satisfies the following requirement (F-3). The multilayer blow container of Claim 2 characterized by these.
(B-4a) density measured by a density gradient tube method ^{_{(d B [g / cm 3}} ]) is in the range of 0.890~0.910g / cm ^3.
(F-3) Density measured by density gradient tube method ^{_{(d F [g / cm 3}} ]) is in the range of 0.865~0.900g / cm ^3. The multi-layer blow container according to any one of claims 1 to 4, wherein the propylene-based resin (A) further satisfies the following requirement (A-4).
(A-4) Mw / Mn measured by GPC is 4.0 or more. The multilayer blow container according to any one of claims 1 to 5, wherein the propylene-based resin (A) further satisfies the following requirement (A-3).
(A-3) Based on ASTM D-1238, the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is in the range of 5 to 10 g / 10 minutes. The multilayer blow container according to any one of claims 1 to 6, wherein the ethylene / α-olefin copolymer (B) further satisfies the following requirement (B-5).
(B-5) Mw / Mn measured by GPC is 1.2 to 3.0. The multilayer blow container according to any one of claims 1 to 7, wherein the ethylene / α-olefin copolymer (B) further satisfies the following requirement (B-3).
(B-3) Based on ASTM D-1238, the MFR measured at a measurement temperature of 230 ° C. and a load of 2.16 kg is in the range of 5 to 10 g / 10 minutes.   The nucleating agent (D) is one or more compounds selected from the group consisting of aromatic phosphate ester compounds, carboxylic acid metal salt nucleating agents, polymer nucleating agents, sorbitol nucleating agents and inorganic compound nucleating agents. The multilayer blow container according to claim 1, wherein the multilayer blow container is a multi-layer blow container.   The propylene-based resin (A) is 95.5 to 98 parts by weight, and the ethylene / α-olefin copolymer (B) is 2 to 4.5 parts by weight (provided that (A) and (B) The multilayer blow container according to claim 1, wherein the total is 100 parts by weight.   The multilayer blow container has a layer formed from a propylene-based polymer (G) or an ethylene-based polymer (H) as at least one inner layer. The multilayer blow container described.   The multilayer blow container according to any one of claims 1 to 11, wherein the multilayer blow container is obtained by molding by a direct blow molding method or an injection stretch blow molding method. A thermoplastic resin composition other than the olefin polymer composition (E) and the olefin polymer composition (E) according to any one of claims 1 to 9,
The direct blow molding method or injection stretching so that the olefin polymer composition (E) forms the outermost layer and the thermoplastic resin composition other than the olefin polymer composition (E) forms at least one inner layer. A method for producing a multilayer blow container, characterized by molding by a blow molding method.