KR101333450B1 - Multilayer blow-molded container, and process for production thereof - 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. The multilayer blow container of this invention consists of an olefin polymer composition (E) in which resin used for an outermost layer is formed from a propylene resin (A), an ethylene-alpha-olefin copolymer (B), and a nucleating agent (D), The propylene-based resin (A) is a copolymer of propylene and an α-olefin (A-1), the crystal melting point (A-2) is in the range of 140 to 155 ° C., and the ethylene / α-olefin copolymer (B) is (B-1) It is a copolymer of ethylene and 1 or more types of alpha-olefins of 4-20 carbon atoms, (B-2) Crystal melting point is 85 degreeC or more and less than 110 degreeC, olefin polymer composition (E) This (E-1) MFR is characterized by being in the range of 5 to 10 g / 10 minutes.

Description

MULTILAYER BLOW-MOLDED CONTAINER, AND PROCESS FOR PRODUCTION THEREOF}

The present invention relates to a multilayer blow container and a method of manufacturing the same.

As a raw material of blow molded objects, such as a blow container, resin, such as vinyl chloride resin, a polycarbonate resin, ethylene resin, and a propylene resin, is used according to a use, for example.

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

Moreover, when using a vinyl chloride resin, although gloss was excellent, there was an environmental problem. When using a polycarbonate resin, although gloss was very excellent, there existed a problem that manufacturing cost became high.

On the other hand, in the case of using a propylene resin, the blow molded article obtained is relatively inexpensive to manufacture and is widely used as a container for liquid detergents, cosmetics, foods, pharmaceuticals and the like because of its higher gloss and transparency than high density polyethylene.

Although the gloss of a blow molded object is a physical property which has been examined conventionally in order to meet the market demand for a favorable external appearance, the blow molded object which satisfy | fills sufficient glossiness, favorable moldability, and impact resistance simultaneously is not proposed.

As a blow molded article excellent in gloss, a propylene polymer composition containing these resins and a nucleating agent is best prepared by using a propylene-α-olefin copolymer as a base resin and a linear low density polyethylene having a crystal melting point of 110 to 125 ° C as a blending resin. The multilayer blow molding body made into an outer layer is proposed (for example, refer patent document 1). However, when the present inventors examined, it turned out that even if it is a multilayer blow molded object of patent document 1, gloss and impact resistance are not enough yet, and further improvement is needed.

As a multilayer bottle excellent in cold resistance, a multilayer bottle having a deep layer of a gas barrier resin and having an outermost layer formed of a polyolefin resin and a linear ultra low density polyethylene resin has been proposed ( See, for example, Patent Document 2). However, when the present inventors examined, even if it is a multilayer bottle of patent document 2, it turned out that glossiness and moldability are not enough yet, and further improvement is needed.

A multi-layered plastic container with a label manufactured by an in-mold method having excellent gloss and surface properties. A polypropylene random copolymer resin containing polyethylene powder as a resin used in the outermost layer, a polyethylene resin, and a nucleating agent. ) And use of ethylene-α-olefin copolymer resins are proposed (see Patent Document 3, for example). However, when the present inventors examined, it turned out that the multilayer plastic container of patent document 3 does not yet have enough impact resistance, and further improvement is needed.

As a high gloss blow container excellent in the gloss of the outer surface of a container, the composition which consists of a polypropylene resin obtained using a metallocene catalyst and an ethylene-alpha-olefin copolymer obtained using a metallocene catalyst is used for the outermost layer, The high gloss blow container shape | molded by the multilayer blow molding method is known (for example, refer patent document 4). However, when the present inventors examined, the high gloss blow container of patent document 4 was excellent in gloss compared with the conventional container, but it turned out that there exists room for further improvement in terms of heat resistance, glossiness, etc.

Japanese Patent No. 3106834 Japanese Patent Laid-Open No. 6-72424 Japanese Patent Laid-Open No. 7-304123 Japanese Patent Publication No. 2003-137928

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.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to achieve the said subject, the multilayer blow container which used the specific olefin polymer composition for the outermost layer is high gloss, excellent in surface appearance, excellent in impact resistance, and also excellent in impact resistance and resistance. The balance of stickiness was also found to be excellent, and the present invention was completed.

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, (A) And (B) are 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), wherein the propylene-based resin (A) has the following requirements (A-1) and ( A-2), the ethylene-α-olefin copolymer (B) satisfies the following requirements (B-1) and (B-2), and the olefin polymer composition (E) meets the following requirements (E- Multi-layer blow container characterized by satisfying 1).

(A-1) It is a copolymer of propylene and 1 or more types of olefins chosen from the group which consists of ethylene and the alpha olefin of 4-20 carbon atoms.

(A-2) The crystal melting point measured by the differential scanning calorimeter (DSC) based on JIS-K7121 is the range of 140-155 degreeC.

(B-1) It is a copolymer of ethylene and 1 or more types of alpha-olefins of 4-20 carbon atoms.

(B-2) The melting | fusing point of crystal | crystallization measured by DSC based on JIS-K7121 is 85 degreeC or more and less than 110 degreeC.

(E-1) Melt flow rate (MFR) measured by measurement temperature 230 degreeC and 2.16 kg load based on ASTMD-1238 is the range of 5-10 g / 10min.

The said olefin polymer composition (E) is further formed using 0.1-20 weight part of low density ethylene-alpha-olefin copolymers (F), and the said low density ethylene-alpha-olefin copolymer (F) has the following requirements (F) -1) and (F-2), and the density (d _B [g / cm ³ ]) and low density ethylene-α-olefin air measured by the density gradient pipe method of the ethylene-α-olefin copolymer (B). When the density (d _F [g / cm ³ ]) measured by the density gradient tube method of the coalescence (F) satisfies the following requirement (X-1), it is preferable from the viewpoint of low temperature impact resistance of the multilayer blow container.

(F-1) It is a copolymer of ethylene and 1 or more types of alpha-olefins of 3-20 carbon atoms.

(F-2) The crystal melting point measured by DSC based on JIS-K7121 is 89 degrees C or less, or the peak based on a crystal melting point is not observed.

(X-1) d _B [g / cm ³ ]> d _F [g / cm ³ ], 0.010 [g / cm ³ ] ≤ (d _B -d _F ) [g / cm ³ ] ≤0.050 [g / cm ³ ].

It is preferable that the said ethylene-alpha-olefin copolymer (B) satisfy | fills the following requirement (B-4) further.

(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). It is preferable from the viewpoint of low temperature impact resistance of the multilayer blow container.

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

(F-3) The density (d _F [g / cm ³ ]) measured by the density gradient tube method is in the range of 0.865 to 0.900 g / cm ³ .

It is preferable that the said propylene resin (A) further satisfy | fills following requirement (A-4).

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

It is preferable that the said propylene resin (A) further satisfy | fills following requirement (A-3).

(A-3) MFR measured at 230 degreeC of measurement temperature and 2.16 kg load based on ASTMD-1238 is the range of 5-10 g / 10min.

It is preferable that the said ethylene-alpha-olefin copolymer (B) satisfy | fills the following requirement (B-5) further.

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

It is preferable that the said ethylene-alpha-olefin copolymer (B) further satisfy | fills following requirement (B-3).

(B-3) MFR measured at 230 degreeC of measurement temperature and 2.16 kg load based on ASTMD-1238 is the range of 5-10 g / 10min.

It is preferable that the said nucleating agent (D) is 1 or more types of compounds chosen from the group which consists of an aromatic phosphate compound, a carboxylic acid metal salt nucleating agent, a polymer nucleating agent, a sorbitol type nucleating agent, and an inorganic compound nucleating agent.

The propylene 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 (the total of (A) and (B) is 100 parts by weight). It is preferable.

The multilayer blow container according to any one of claims 1 to 10, wherein the multilayer blow container has a layer formed of a propylene polymer (G) or an ethylene polymer (H) as at least one inner layer. Blow container.

It is preferable that the said multilayer blow container is obtained by shape | molding by the direct blow molding method or the injection stretch blow molding method.

In the multilayer blow container of the present invention, the olefin polymer composition (E) forms the outermost layer using a thermoplastic resin composition other than the olefin polymer composition (E) and the olefin polymer composition (E), and the olefin polymer composition ( The thermoplastic resin composition other than E) is formed by the direct blow molding method or the injection stretch blow molding method so as to form 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.

Next, the present invention will be described in detail.

[Multilayer blow container]

The multilayer blow container of the present invention is one in which the resin used for the outermost layer is made of an olefin polymer composition (E) formed of a propylene resin (A), an ethylene-α-olefin copolymer (B), and a nucleating agent (D). It features.

The multilayer blow container of the present invention has a high gloss, excellent surface appearance and excellent impact resistance, but the olefin polymer composition (E) further uses 0.1 to 20 parts by weight of the low density ethylene-α-olefin copolymer (F). In the present embodiment, the low temperature impact resistance is further excellent.

<Propylene-based resin (A)>

The propylene resin (A) used in the present invention 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 preferable that it is preferable, and it is more preferable to satisfy the following requirements (A-3) and (A-4). Propylene-based resin (A) may be used individually by 1 type, or may use 2 or more types.

(A-1) It is a copolymer of propylene and 1 or more types of olefins chosen from the group which consists of ethylene and the alpha olefin of 4-20 carbon atoms. On the other hand, as alpha -olefin of 4-20 carbon atoms, 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, tri Methyl-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. are mentioned.

The propylene resin (A) used in the present invention is preferably a copolymer of propylene and at least one olefin selected from the group consisting of ethylene and an α-olefin having 4 to 10 carbon atoms in terms of balance between physical properties and economical efficiency. And it is more preferable that it is a copolymer of propylene and 1 or more types of alpha-olefins chosen from the group which consists of ethylene and 1-butene, and it is especially preferable that it is a copolymer of propylene and ethylene.

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

(A-2) The crystal melting point measured by the differential scanning calorimeter (DSC) based on JIS-K7121 is the range of 140-155 degreeC. If the crystal melting point is within the above range, it is preferable because the gloss and impact resistance of the multilayer blow container are excellent, and the moldability at the time of producing the multilayer blow container is also excellent. When the crystal melting point measured by a differential scanning calorimeter (DSC) is higher than 155 degreeC based on JIS-K7121, the impact resistance of a multilayer blow container is inferior. Moreover, when the crystal melting point measured with the differential scanning calorimeter (DSC) based on JIS-K7121 is lower than 140 degreeC, moldability at the time of manufacturing a multilayer blow container is inferior, and stickiness arises on the surface of a multilayer blow container.

The crystalline melting point of the propylene resin (A) can be determined by measuring under the following measurement conditions using a differential scanning calorimeter (DSC) (for example, Diamond DSC manufactured by Perkin Elmer) according to JIS-K7121. On the other hand, the peak of an endothermic peak was defined as crystal melting point (Tm) in the 3rd step at the time of measuring on the following measurement conditions. When there are a plurality of endothermic peaks, the endothermic peak peak at which the height of the peak is maximum is defined as the crystal melting point (Tm).

(Measuring conditions)

Measuring environment: nitrogen gas atmosphere

Sample volume: 5 mg

Sample shape: press film (230 DEG C molding, thickness 200 to 400 mu m)

1st step: It heats up to 240 degreeC from 30 degreeC to 10 degreeC / min, and hold for 10 minutes.

Second step: Lower to 60 ° C. at 10 ° C./min.

3rd step: It heats up to 240 degreeC at 10 degreeC / min.

The crystalline melting point measured by differential scanning calorimetry (DSC) in accordance with JIS-K7121 of the propylene resin (A) is, for example, propylene at the time of copolymerization in the production of propylene resin (A), ethylene and carbon to be introduced. It can adjust by changing the introduction ratio of 1 or more types of olefins chosen from the group which consists of alpha-olefin of 4-20 atoms. That is, by increasing the amount of ethylene and the amount of at least one olefin selected from the group consisting of 4 to 20 carbon atoms with respect to the amount of propylene introduced, measured by a differential scanning calorimeter (DSC) in accordance with JIS-K7121. Differential scanning calorimeter in accordance with JIS-K7121 by lowering the melting point of the crystal and reducing the amount of the propylene introduced to at least one olefin selected from the group consisting of ethylene and an alpha -olefin having 4 to 20 carbon atoms. The crystal melting point measured by (DSC) can be made high.

(A-3) MFR measured at 230 degreeC of measurement temperature and 2.16 kg load based on ASTMD-1238 is the range of 5-10 g / 10min. In addition, MFR means melt flow rate. If the MFR is in the above range, the fluidity of the olefin polymer composition (E) at the time of molding becomes a preferred range for molding of the present invention, and the thickness nonuniformity of the most olefin polymer composition (E) in the blow molding is prevented, and smoothness is achieved. The multilayer blow container which is excellent in this and also excellent in glossiness can be manufactured. If the MFR measured at a measurement temperature of 230 ° C. and a 2.16 kg load in accordance with ASTM D-1238 is greater than 10 g / 10 min, the moldability and the impact resistance of the multilayer blow container may be inferior. According to ASTM D-1238, when the MFR measured at the measurement temperature of 230 degreeC and 2.16 kg load is less than 5 g / 10min, the glossiness of a multilayer blow container may be inferior.

MFR measured at a measurement temperature of 230 ° C. and a 2.16 kg load in accordance with ASTM D-1238 of the propylene resin (A) is, for example, a chain transfer agent used during copolymerization in the production of the propylene resin (A) (eg, Hydrogen gas) can be adjusted. That is, by increasing the amount of the chain transfer agent (for example, hydrogen gas) to the amount of propylene introduced at the time of polymerization and one or more olefins selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms, In accordance with ASTM D-1238 of a propylene resin (A), the MFR measured by the measurement temperature of 230 degreeC and 2.16 kg load can be made high. In addition, by reducing the amount of chain transfer agent (for example, hydrogen gas) introduced into the amount of propylene introduced at the time of polymerization and one or more olefins selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms, In accordance with ASTM D-1238 of the propylene resin (A), the MFR measured at a measurement temperature of 230 ° C. and a 2.16 kg load can be lowered.

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

(A-4) Mw / Mn measured by GPC is 4.0 or more. On the other hand, 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-based resin (A), Mw / Mn becomes like this. Preferably it is 1.5 or more, More preferably, it is 3.0 or more, If it satisfy | fills said (A-4), ie, Mw / Mn is 4.0 or more, the surface roughness of a blow metal mold | die. It is especially preferable because the blow molded object which is excellent in glossiness is obtained, regardless of. Although this reason is not clear, the present inventors think as follows. That is, when Mw / Mn is 4.0 or more, compared with the case below the said range, a higher molecular weight part and a lower molecular weight part exist. It is considered that the presence of the higher molecular weight portion reduces the resin flow deformation during blow molding, and the presence of the lower molecular weight portion accelerates solidification. For this reason, when the thing of the said Mw / Mn range is used as (A) component, even if the metal mold | die with a large surface roughness is used or the metal mold | die with small surface roughness is used, the multilayer blow container obtained transfers the roughness of the metal mold | die surface. The inventors presumed that the result was good gloss. The upper limit of Mw / Mn is not particularly limited, but from the viewpoint of productivity, it is usually 50.0, preferably 30.0, more preferably 20.0, still more preferably 16.0, particularly preferably 12.0, 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 said propylene resin (A) can be adjusted according to the kind of catalyst used at the time of manufacture of a propylene resin (A), for example. For example, a propylene-based resin (A) satisfying the above requirement (A-4) can be obtained by using a Ziegler-Natta catalyst, preferably a solid titanium catalyst. Moreover, as an example of another method of adjusting Mw / Mn, there is a method of blending two or more types of propylene resins having different molecular weights. In particular, solid titanium catalysts are advantageous from the viewpoint of forming the above higher molecular weight portions.

In addition, as a propylene resin (A), the structural unit derived from propylene computed by ¹³ C-NMR, and 1 type or more derived from an olefin selected from the group which consists of an alpha olefin of 4-20 carbon atoms are mentioned. When the sum total of structural units is 100 weight%, the weight of the propylene-derived structural unit is normally the range of 80-99 weight%, Preferably it is the range of 90-99 weight%. Moreover, the weight of the structural unit derived from 1 or more types of olefins chosen from the group which consists of ethylene and the alpha olefin of 4-20 carbon atoms is normally 1-20 weight%, Preferably it is 1-10 weight Range of%. Within the above range, the balance between moldability and the stickiness of the multilayer blow container and the like when the multilayer blow container is manufactured is preferable.

The sum total of the structural unit derived from propylene and the structural unit derived from 1 or more types of olefins chosen from the group which consists of ethylene and the C4-20 alpha-olefin computed by ¹³ C-NMR shall be 100 weight%. In this case, the weight of the propylene-derived structural unit was measured and calculated under the following conditions.

( ¹³ C-NMR measurement conditions)

Measuring device: LA400 type nuclear magnetic resonance device made by Japan Electronics

Measurement mode: Bilevel Complete decoupling (BCM)

Observation frequency: 100.4 MHz

Viewing range: 17006.8 Hz

Pulse width: C core 45 ° (7.8μs)

Pulse repetition time: 5 seconds

Sample tube: 5 mmφ

Sample tube rotation speed: 12Hz

Cumulative Count: 20000

Measuring temperature: 125 ℃

Solvent: 1,2,4-trichlorobenzene: 0.35 ml / heavy benzene: 0.2 ml

Sample amount: approx. 40 mg

(Calculation of the weight of the structural unit derived from propylene)

In the case where at least one olefin (i.e., comonomer) selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms is ethylene, from the obtained ¹³ C-NMR spectrum according to the following document (1), a monomer By determining the ratio of the chain distribution (dyad (diad) distribution), the mole fraction (mol%) of the structural unit derived from ethylene in the propylene resin (A) (hereinafter referred to as E (mol%)) And the mole fraction (mol%) of the structural units derived from propylene (hereinafter, referred to as P (mol%)). The weight% of the structural units derived from propylene and the weight% of the structural units derived from ethylene in the propylene-based resin (A) can be calculated in terms of weight% from the obtained E (mol%) and P (mol%).

Document (1): Kakugo, M .; Naito, Y .; Mizunuma, K .; Miyatake, T., Macromolecules 1982, 15, (4), 1150-1152

From the ¹³ C-NMR spectrum obtained when the at least one olefin (ie, comonomer) selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms is α-olefins having 4 to 20 carbon atoms Of the structural units derived from α-olefins having 4 to 20 carbon atoms in the propylene-based resin (A) by determining the ratio of monomer chain distribution (diad (two-ring) distribution) according to the following document (2). The mole fraction (mol%) (hereinafter referred to as A (mol%)) and the mole fraction (mol%) of the structural units derived from propylene (hereinafter referred to as P (mol%)) can be calculated. The structural unit derived from the weight percent of the structural unit derived from propylene in the propylene-based resin (A) and the α-olefin having 4 to 20 carbon atoms in terms of weight% from the obtained A (mol%) and P (mol%). The weight percent of can be calculated.

Document 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 quantities by adjusting the manufacturing conditions mentioned later. More specifically, the amount of at least one olefin selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms with respect to the amount of propylene introduced during copolymerization in the production of the propylene resin (A) is reduced. By doing so, the weight of the propylene-derived structural unit can be increased. Moreover, the weight of the structural unit derived from propylene can be reduced by increasing the introduction amount of 1 or more types of olefins chosen from the group which consists of ethylene and the alpha olefin of 4-20 carbon atoms with respect to the introduction amount of propylene.

Moreover, it is preferable that the said propylene resin (A) is a random copolymer of propylene and 1 or more types of olefins chosen from the group which consists of alpha-olefin of 4-20 carbon atoms. The propylene-based resin (A) copolymerizes propylene and at least one olefin selected from the group consisting of ethylene and α-olefins having 4 to 20 carbon atoms in the presence of a Ziegler-Natta catalyst or a metallocene catalyst, preferably Can be obtained by random copolymerization. As a catalyst used when polymerizing the propylene resin (A), the above requirement (A-4) can be satisfied by using a Ziegler-Natta catalyst, preferably a solid titanium catalyst. In addition, it is also possible to adjust so as to satisfy the requirement (A-4) by blending two or more kinds of propylene resins (A) having different molecular weights. In addition, at the time of superposition | polymerization, the chain transfer agent like what is represented by hydrogen gas can also be introduced. The propylene resin (A) can also be obtained by melt kneading the propylene resin obtained by polymerization in the presence of a radical generator such as an organic peroxide.

Although it does not specifically limit as said organic peroxide, Benzoyl peroxide, t-butyl per benzoate, t-butyl peracetate, t-butyl peroxy isopropyl carbonate, 2, 5- dimethyl- 2, 5- di ( Benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexyn-3, t-butyl-diperadipate, t-butylperoxy-3,5,5-tri Methylhexanoate, methyl-ethyl ketone peroxide, cyclohexanone peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hex Sein, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 1,3-bis- (t-butylperoxyisopropyl) benzene, t-butyl cumyl peroxide, 1 , 1-bis- (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis- (t-butylperoxy) cyclohexane, 2,2-bis- (t -Butylperoxy) butane, p-methane hydroperoxide, diisopropylbenzenehigh Loperoxide, cumene hydroperoxide, t-butylhydroperoxide, p-cymene hydroperoxide, 1,1,3,3-tetra-methylbutylhydroperoxide or 2,5-dimethyl-2,5- Organic peroxides, such as di (hydroperoxy) hexane, can be illustrated. Moreover, 2, 5- dimethyl- 2, 5- di (benzoyl peroxy) hexane and 1, 3-bis- (t-butyl peroxy isopropyl) benzene are more preferable among these. When using an organic peroxide, it is preferable to use it at 0.1 weight part or less with respect to 100 weight part of propylene resin obtained by superposition | polymerization. In the melt kneading treatment, the organic peroxide is added to the propylene resin, and then mixed into a mixer such as a Henschel mixer, a Banbury mixer, a tumbler mixer, or the like, and the resulting mixture is mixed with a single screw extruder or a twin screw extruder. The method of shape | molding by an extruder and obtaining the strand of a propylene resin (A) is mentioned. On the other hand, the strand is usually pelletized using a pelletizer or the like before performing 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 further, at least among the following requirements (B-3) and (B-4). It is preferable to satisfy one side, and it is more preferable to satisfy the following requirements (B-3) and (B-4). Moreover, it is also preferable to satisfy the following requirement (B-5). An ethylene-alpha-olefin copolymer (B) may be used individually by 1 type, or may use 2 or more types.

(B-1) It is a copolymer of ethylene and 1 or more types of alpha-olefins of 4-20 carbon atoms. On the other hand, as alpha -olefin of 4-20 carbon atoms, 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, tri Methyl-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. are mentioned.

As an ethylene-alpha-olefin copolymer (B) used for this invention, it is a copolymer of ethylene and 1 or more types of olefins chosen from the group which consists of a C4-10 alpha-olefin from a viewpoint of the balance of physical property and economical efficiency. It is preferable that it is a copolymer of ethylene and 1 or more types of alpha-olefins chosen from the group which consists of 1-butene, 1-hexene, and 1-octene, and it is especially preferable that it is a copolymer of ethylene and 1-hexene. .

(B-2) The melting | fusing point of crystal | crystallization measured by DSC based on JIS-K7121 is 85 degreeC or more and less than 110 degreeC. If the crystal melting point is within the above range, it is preferable because the impact resistance of the multilayer blow container and the adhesiveness between the outermost layer and another layer are excellent. The crystal melting point measured by DSC in accordance with JIS-K7121 of the ethylene-α-olefin copolymer (B) is inferior in adhesiveness and impact resistance at 110 ° C or higher, and the crystal melting point measured by DSC in accordance with JIS-K7121. When lower than 85 degreeC, since adhesiveness is inferior and stickiness arises, it is unpreferable. In addition, in view of the balance of impact resistance, adhesiveness and stickiness, the crystal melting point is preferably 109 ° C or lower, more preferably 108 ° C or lower, particularly preferably 105 ° C or lower.

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

More specifically, in superposition | polymerization of an ethylene-alpha-olefin copolymer (B), when superposing | polymerizing an ethylene-alpha-olefin copolymer, it can adjust by changing the ratio of the supply amount of ethylene and alpha-olefin. Specifically, it is possible to lower the crystal melting point measured by DSC in accordance with JIS-K7121 by increasing the supply amount of α-olefin to the supply amount of ethylene. In addition, it is possible to increase the crystal melting point measured by DSC in accordance with JIS-K7121 by reducing the supply amount of α-olefin to the supply amount of ethylene.

The crystal 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 measure by the same method as the crystalline melting point of propylene resin (A) mentioned above.

(B-3) MFR measured at 230 degreeC of measurement temperature and 2.16 kg load based on ASTMD-1238 is the range of 5-10 g / 10min. When MFR exists in the said range, dispersibility to the propylene resin (A) of an ethylene-alpha-olefin copolymer (B) becomes favorable, it is excellent in the glossiness and impact resistance of a multilayer blow container, and a layer different from an outermost layer Since the adhesiveness of is excellent, it is preferable.

In addition, the adjustment of MFR measured by measurement temperature 230 degreeC and 2.16 kg load based on ASTMD-1238 of an ethylene-alpha-olefin copolymer (B) changes the manufacturing conditions of an ethylene-alpha-olefin copolymer (B). It can be set to arbitrary values by adjusting.

More specifically, in superposition | polymerization of the ethylene-alpha-olefin copolymer (B) mentioned later, it is possible to control by adjusting the supply amount of hydrogen gas with respect to the supply amount of ethylene and / or alpha-olefin at the time of superposition | polymerization. In the case of supplying ethylene gas at the time of polymerization or supplying ethylene and α-olefin, the supply amount of hydrogen gas is increased with respect to the supply amount of ethylene and α-olefin, and it is 2.16 kg measured temperature 230 degreeC based on ASTMD-1238. It is possible to increase the MFR measured in the load. When supplying ethylene gas or supplying ethylene and α-olefin, the amount of hydrogen gas supplied to the supply amount of ethylene and α-olefin is reduced, measured at 230 ° C and 2.16 kg load according to ASTM D-1238. It is possible to lower the MFR.

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

In addition, when the multilayer blow container of this invention is used for the use which requires low-temperature impact resistance, while using the low density ethylene-alpha-olefin copolymer (F) mentioned later, an ethylene-alpha-olefin copolymer (B ) Satisfies the following requirement (B-4a).

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

The density measured by the density gradient tube method of the ethylene-alpha-olefin copolymer (B) used for this invention can be made into arbitrary quantities by adjusting the manufacturing conditions of an ethylene-alpha-olefin copolymer (B).

More specifically, in polymerizing an ethylene-alpha-olefin copolymer (B) mentioned later, when superposing | polymerizing an ethylene-alpha-olefin copolymer, it can adjust by changing the ratio of the supply amount of ethylene and an alpha-olefin. . Specifically, it is possible to lower the density measured by the density gradient pipe method by increasing the supply amount of α-olefin to the supply amount of ethylene. In addition, it is possible to increase the density measured by the density gradient pipe method by reducing the supply amount of the α-olefin relative to the supply amount of ethylene.

On the other hand, the density measured by the density gradient tube method of the ethylene-alpha-olefin copolymer (B) used for this invention makes the strand of the ethylene-alpha-olefin copolymer (B) obtained at the time of the said MFR measurement at 120 degreeC. After heat-processing for 1 hour and cooling slowly to room temperature linearly over 1 hour, it is the measured value measured by the density gradient tube.

(B-5) Mw / Mn measured by GPC is 1.2-3.0. On the other hand, as ethylene-alpha-olefin copolymer (B), it is more preferable if Mw / Mn is 1.5-3.0. If Mw / Mn is in the said range, since the glossiness of the multilayer blow container of this invention is excellent, it is preferable.

Mw / Mn measured by GPC of the said ethylene-alpha-olefin copolymer (B) can be adjusted according to the kind of catalyst used at the time of manufacture of an ethylene-alpha-olefin copolymer (B), for example. For example, by using a metallocene catalyst as the catalyst, an ethylene-α-olefin copolymer (B) satisfying the above requirement (B-5) can be obtained.

In addition, although the said ethylene-alpha-olefin copolymer (B) can be obtained by copolymerizing ethylene and an alpha-olefin, it is preferable if the ethylene-alpha-olefin copolymer superposed | polymerized using the metallocene catalyst. In addition, at the time of superposition | polymerization, the chain transfer agent like what is represented by hydrogen gas can also be introduce | transduced.

If the ethylene-alpha-olefin copolymer (B) used for this invention is an ethylene-alpha-olefin copolymer superposed | polymerized using the metallocene catalyst, the ethylene-alpha- superposed | polymerized using the conventional so-called Ziegler-Natta catalyst. Since the composition distribution is more uniform than that of the olefin copolymer, the dispersibility to the propylene-based resin (A) is good, and the olefin polymer composition (E) having better gloss can be obtained. In addition, if the ethylene-α-olefin copolymer polymerized using a metallocene catalyst, the molecular weight distribution is also narrower than that of the ethylene-α-olefin copolymer polymerized using a Ziegler-Natta catalyst, which causes deterioration in impact resistance. Low molecular weight components are reduced. In addition, if the ethylene-α-olefin copolymer polymerized using a metallocene catalyst, the composition distribution of the copolymer becomes more uniform than that of the ethylene-α-olefin copolymer polymerized using a Ziegler-Natta catalyst, which causes stickiness. Also less amorphous components become. Moreover, the adhesion nonuniformity between outermost layer and another layer also becomes small, and it is also expected to suppress the appearance deterioration with time.

From the above, by using the ethylene-α-olefin copolymer (B) polymerized using a metallocene catalyst, an olefin polymer composition (E) having excellent gloss, excellent impact resistance, and low stickiness can be obtained. You can get it.

<Low Density Ethylene-α-olefin Copolymer (F)>

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

It is preferable that the said low density ethylene-alpha-olefin copolymer (F) satisfy | fills following requirements (F-1) and (F-2), and also satisfy | fills following requirements (F-3) further. The low density ethylene-α-olefin copolymer (F) may be used alone or in combination of two or more thereof.

(F-1) It is a copolymer of ethylene and 1 or more types of alpha-olefins of 3-20 carbon atoms. Meanwhile, as α-olefins having 3 to 20 carbon atoms, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene and 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, tri Methyl-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. are mentioned.

As said low density ethylene-alpha-olefin copolymer (F), it is preferable that it is a copolymer of ethylene and 1 or more types of olefins chosen from the group which consists of a C3-C10 alpha-olefin from a balance of physical property and economical efficiency. And it is more preferable that it is a copolymer of ethylene and 1 or more types of alpha-olefins chosen from the group which consists of propylene, 1-butene, 1-hexene, and 1-octene. As said low density ethylene-alpha-olefin copolymer (F), the copolymer of ethylene and propylene, the copolymer of ethylene and 1-butene, and the copolymer of ethylene and 1-octene are especially preferable, and the ethylene and 1-butene Copolymer, the copolymer of ethylene and 1-octene is more preferable, and the copolymer of ethylene and 1-butene is especially preferable.

(F-2) The crystal melting point measured by DSC based on JIS-K7121 is 89 degrees C or less, or the peak based on a crystal melting point is not observed. When it has a crystal melting point, it is preferable that it is 75 degrees C or less. If the crystal melting point is within the above range, the multilayer blow container is preferable because it is excellent in low temperature impact resistance.

The crystal 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 Example mentioned later.

(F-3) The density (d _F [g / cm ³ ]) measured by the density gradient tube method is in the range of 0.865 to 0.900 g / cm ³ . More preferably, the density is in the range of 0.870 to 0.900 g / cm ³ . When the density is in the above range, it is preferable because the gloss of the multilayer blow container is excellent and the low temperature impact resistance is particularly excellent.

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

(X-1) d _B [g / cm ³ ]> d _F [g / cm ³ ], 0.010 [g / cm ³ ] ≤ (d _B -d _F ) [g / cm ³ ] ≤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), and the ethylene-α-olefin copolymer (B) and the low density ethylene-α-olefin the difference in density (d _B -d _F) of the copolymer (F) is 0.010 to 0.050 [g / cm ^3]. On the other hand, the density difference d _B -d _F is preferably 0.010 to 0.040 [g / cm ³ ].

When the density difference d _B -d _F is within the above range, it is preferable because the gloss of the multilayer blow container is excellent and the low temperature impact resistance is excellent.

Moreover, as a low density ethylene-alpha-olefin copolymer (F), it is preferable that MFR measured at 230 degreeC of measurement temperature and 2.16 kg load based on ASTMD-1238 is 0.1-50 g / 10min, and is 0.5- It is more preferable that it is the range of 30 g / 10 minutes, and it is especially preferable to exist in the range of 5-10 g / 10 minutes. If MFR exists in the said range, the dispersibility of the low density ethylene-alpha-olefin copolymer (F) will become favorable, and glossiness and low-temperature impact property will improve.

In addition, although the said low density ethylene-alpha-olefin copolymer (F) can be obtained by copolymerizing ethylene and alpha-olefin, even if the ethylene-alpha-olefin copolymer was superposed | polymerized using the Ziegler-Natta catalyst, It may be polymerized using a metallocene catalyst.

<Nucleating agent (D)>

In the present invention, a nucleating agent (D) is used. Examples of the nucleating agent (D) include at least one compound selected from the group consisting of an aromatic phosphate compound, a carboxylic acid metal salt nucleating agent, a polymer nucleating agent, a sorbitol-based nucleating agent and an inorganic compound nucleating agent. It is preferable that a nucleating agent (D) does not worsen the bad smell of a multilayer blow container. A nucleating agent (D) may be used individually by 1 type, or may use 2 or more types together.

It is preferable that it is a compound represented with the following general formula III and / or IV as said aromatic phosphate ester compound.

[Formula III]

(IV)

In Formulas (III) and (IV), R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, R ² and R ³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and M is 1 To trivalent metal atoms, n is an integer of 1 to 3, m is 1 or 2.

Specific examples of the aromatic phosphate ester compound represented by the 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-dimethylphenyl) phosphate, sodium-2,2'-butylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6 -Dimethylphenyl) 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-dimethylphenyl Phosphate, sodium-2,2'-methylene-bis (4,6-diethylphenyl) 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-butylphenyl ) Phosphate], barium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], aluminum-tris [2,2'-methylene-bis (4,6-di -t-butylphenyl) phosphate], aluminum-tris [2,2 '-Ethylidene-bis (4,6-di-t-butylphenyl) phosphate] and mixtures of two or more thereof.

As the aromatic phosphate ester compound, a hydroxyaluminum phosphate compound represented by the general formula (IV) can also be used, and a compound represented by the general formula (V) in which R ² and R ³ together are a tert-butyl group is particularly preferable.

(V)

In the general formula (V), R ¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and m is 1 or 2. Especially preferable aromatic phosphate ester compound is a compound represented by general formula (VI).

(VI)

In formula (VI), R ¹ is a methylene group or an ethylidene group. Specific examples of the compound represented by the formula (VI) include hydroxyaluminum bis [2,2-methylene-bis (4,6-di-t-butyl) phosphate] (another name: bis (2,4,8,10) Tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphon-6-oxide) aluminum hydroxide salts) or hydroxyaluminum-bis [2,2 Ethylidene-bis (4,6-di-t-butyl) phosphate].

As the carboxylic acid metal salt nucleating agent, for example, p-t-butyl benzoate aluminum salt, aluminum adipic acid or sodium benzoate can be used.

As the polymer nucleating agent, a branched α-olefin polymer is suitably used. 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, Homopolymers of 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, or copolymers thereof; And copolymers of them with other α-olefins.

These polymer nucleating agents can also be blended directly when producing the olefin polymer composition (E), and the block-blocking agent before or after the polymerization of the propylene resin (A) during the production of the propylene resin (A). The branched α-olefin may be polymerized, and may be blended by using a propylene resin (A) containing a branched α-olefin polymer as the nucleating agent (D) (a polymer nucleating agent-containing propylene resin (A '). ). When the polymer nucleating agent-containing propylene resin (A ') is used as a raw material of the olefin polymer composition (E), the amount of the polymer nucleating agent contained in the polymer nucleating agent-containing propylene resin (A') is used as the olefin polymer composition. Let it be the compounding quantity of the nucleating agent (D) in (E). The portion obtained by subtracting the amount of the polymer nucleating agent from the polymer nucleating agent-containing propylene resin (A ') is referred to as propylene resin (A) in the olefin polymer composition (E).

Moreover, the said polymer nucleating agent can also be formed by the prepolymerization at the time of manufacturing a polymer (A), a polymer (B), and a polymer (F) using a well-known method, A polymer (B), a polymer (F) It may be formed by a block copolymerization method when preparing.

In addition, you may use together the polymer nucleating agent mix | blended propylene resin (A ') and the propylene resin (A) which does not contain a polymer nucleating agent. In addition, a polymer nucleating agent-containing propylene-based resin (A ') and another nucleating agent (D) may be used in combination.

When these polymer nucleating agents contain other resins which an olefin polymer composition (E) mentions later, the master batch containing other resins and a polymer nucleating agent is used for the olefin polymer composition (E). It can also mix | blend by using when manufacturing. When using the said masterbatch as a raw material of an olefinic polymer composition (E), the quantity of the polymer nucleating agent contained in a masterbatch is made into the compounding quantity of the nucleating agent (D) in an olefinic polymer composition (E). In addition, you may manufacture an olefin polymer composition using a masterbatch and another nucleating agent (D) together.

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

As sorbitol-based 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, talc, mica and calcium carbonate can be used, for example.

Among these nucleating agents (D), nonitol, 1,2,3-trideoxy-4,6: 5,7-bis-O-[(4- in terms of transparency, low temperature impact resistance, rigidity and low odor Propylphenyl) methylene] and bis (2,4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphosine-6- Preference is given to using at least one nucleating agent selected from oxides) aluminum hydroxide salts. Among them, bis (2,4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphosine-6-oxide) aluminum hydroxide It is more preferable to use a salt.

As a nucleating agent (D) used for this invention, a commercial item can be used, For example, Adeka Stab NA-21 (made by ADEKA Corporation) is bis (2,4,8,10- tetra- t-butyl-6-hydroxy- It is marketed as a nucleating agent containing 12H-dibenzo [d, g] [1,3,2] dioxaphosphosine-6-oxide) aluminum hydroxide salt as a main component, and nonitol, 1,2,3-tride Oxy-4,6: 5,7-bis-O-[(4-propylphenyl) methylene] is marketed under the trade name of Mirad NX8000 (made by Myriken).

<Olefin polymer composition (E)>

The olefin polymer composition (E) used for this invention is resin used for the outermost layer of the multilayer blow container of this invention, 80-98 weight part of propylene resin (A) mentioned above, and an ethylene-alpha-olefin copolymer (B) It is a composition formed from 2-20 weight part (however, the sum total of (A) and (B) is 100 weight part) and 0.01-0.5 weight part of nucleating agents (D).

On the other hand, when the low-temperature impact resistance is required for the multilayer blow container of the present invention, as described above, as the olefin polymer composition (E), a propylene-based resin (A), an ethylene-α-olefin copolymer (B) and a nucleating agent In addition to (D), it is preferable to use the composition formed using 0.1-20 weight part of low-density ethylene-alpha-olefin copolymers (F) further.

Moreover, when low-temperature impact resistance is not required for a multilayer blow container, it is also preferable that an olefin polymer composition (E) is a composition formed without using the low density ethylene-alpha-olefin copolymer (F).

The use amount of the propylene resin (A) and the ethylene-α-olefin copolymer (B) is 95.5 to 98 parts by weight of the propylene resin (A) from the viewpoint of good stickiness and from the viewpoint of economy and productivity. It is preferable that the said ethylene-alpha-olefin copolymer (B) is 2-4.5 weight part (however, the sum total of (A) and (B) is 100 weight part).

When the propylene resin (A) used to obtain the olefin polymer composition (E) is more than 98 parts by weight and the ethylene-α-olefin copolymer (B) is less than 2 parts by weight, the impact resistance of the multilayer blow container, It is inferior to adhesiveness with another layer, The said propylene resin (A) mix | blended with an olefin polymer composition (E) is less than 80 weight part, and the said ethylene-alpha-olefin copolymer (B) is more than 20 weight part It is not preferable because stickiness occurs.

In addition, when a low-temperature impact resistance is requested | required of a multilayer blow container, it is 3-15 weight part of said low density ethylene-alpha-olefin copolymers (F) mix | blended with an olefin polymer composition (E) from a stickiness and economical viewpoint. desirable.

The nucleating agent (D) has an effect of improving the glossiness of the multilayer blow container by using 0.01 to 0.5 parts by weight based on 100 parts by weight of the total amount of the propylene resin (A) and the ethylene-α-olefin copolymer (B). Lose. When the addition amount of the nucleating agent (D) is less than 0.01 part by weight, the effect of improving glossiness is small. Even if the added amount of the nucleating agent (D) is larger than 0.5 parts by weight, the effect is not changed and it is not preferable because it becomes economically disadvantageous.

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

(E-1) Melt flow rate (MFR) measured by measurement temperature 230 degreeC and 2.16 kg load based on ASTMD-1238 is the range of 5-10 g / 10min. When MFR exists in the said range, the fluidity | liquidity of the olefin polymer composition (E) at the time of shaping | molding will become a range suitable for shaping | molding, and can suppress the fine melt fracture (MF) which arises at the time of shaping | molding. Moreover, the thickness nonuniformity of the olefin polymer composition (E) in blow molding is prevented, and the multilayer blow container excellent in the smoothness can be obtained.

In accordance with ASTM D-1238, 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 minutes, inferior in moldability, and lower than 5 g / 10 minutes, inferior in gloss.

Requirements for the olefin polymer composition (E) (E-1), that is, the melt flow rate (MFR) measured at a measurement temperature of 230 ° C. and a 2.16 kg load in accordance with ASTM D-1238 is determined by using the propylene resin (A) used. It can adjust by selecting suitably the ethylene-alpha-olefin copolymer (B) and the low density ethylene-alpha-olefin copolymer (F) used as needed.

The propylene resin (A) and ethylene-α-olefin copolymer (B) to be used together measure the melt flow rate (MFR) at a measurement temperature of 230 ° C and a load of 2.16 kg in accordance with ASTM D-1238 of 5 to 10 g / 10. In the range of minutes, by appropriately selecting the propylene resin (A), the ethylene-α-olefin copolymer (B), and the low-density ethylene-α-olefin copolymer (F) used as necessary (E) It is possible to satisfy the requirements of -1).

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

As another example, when using a propylene-based resin (A) having a relatively high MFR in which MFR exceeds 10 g / 10 minutes, the ethylene-α-olefin copolymer (B) to be combined and the low density ethylene used as necessary By using a thing with a low MFR as alpha-olefin copolymer (F), MFR of an olefin polymer composition (E) can be adjusted within the said range.

It is preferable that the said olefin polymer composition (E) is the range of 140-155 degreeC of crystal melting point measured by DSC based on JIS-K7121. If the crystal melting point is within the above range, a multilayer blow container having good gloss and good impact resistance can be obtained.

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

Further, it is the olefin polymer composition (E) is more preferably, a half (半) crystallization time (t _1/2) is 50 to 1000 seconds, the range of preferable and the range from 100 to 500 seconds. Within this range, the mold transfer property becomes good at the time of blow molding, and a multilayer blow container with favorable gloss can be obtained.

On the other hand, the half-crystallization time (t _1/2) is, 125 ℃ crystallization in isothermal conditions with the olefin polymer composition (E) and, at this time by measuring the calorific value according to the crystallization, the half of the total amount of heat generated heat output from the heat generation start (crystallization start) It can measure as time until it becomes.

The half-crystallization time (t _1/2) of the olefin polymer composition (E) is, it is possible to adjust the amount of the nucleating agent (D) contained in the olefin polymer composition (E). It can be an olefin polymer composition (E) for the half-crystallization time (t _1/2) to increase the amount of the nucleating agent (D) rapidly contained in and, conversely, to reduce the amount of the nucleating agent (D) The half-crystallization it is possible to slow down the time (t _1/2).

In the olefin polymer composition (E) of the present invention, components other than the above-described propylene resin (A), ethylene-α-olefin copolymer (B), low density ethylene-α-olefin copolymer (F) and nucleating agent (D) It may contain.

As components other than said (A), (B), (F), and (D), other resin, various additives, etc. are mentioned.

As other resins, polyolefin resins other than a propylene resin (A), an ethylene-alpha-olefin copolymer (B), a low density ethylene-alpha-olefin copolymer (F), and a nucleating agent (D) are mentioned, for example. have. As polyolefin resin, propylene resin (P) other than propylene resin (A) can be illustrated. Examples of the propylene resin (P) include homopolymers of propylene resin (A) and other propylene (including syndiotactic propylene homopolymer and the like). Usually, Tm measured with the differential scanning calorimeter (DSC) based on JISK7121 of propylene resin (P) is 140-155 degreeC. Moreover, as MFR measured by measurement temperature 230 degreeC and 2.16 kg load based on ASTMD-1238 of propylene resin (P), 0.01-20 g / 10min is preferable, and it is especially preferable that it is 0.1-5 g / 10min.

Moreover, as other resin, styrene-type elastomer or its hydrogenated substance (S) can also be illustrated, for example. On the other hand, when it is desired to make the gloss mold surface roughness dependency small, it is a preferable aspect not to add a styrene-type elastomer or its hydrogenated substance (S).

As the styrene-based elastomer or its hydrogenated substance (S), 10 to 70% by weight of styrene content, preferably 10 to 65% by weight, more preferably 10 to 40% by weight and conjugated diene content of 30 to 90% by weight, Preferably 35-90 weight%, More preferably, 60-90 weight% of styrene-type elastomer or its hydrogenated substance (S) is mentioned.

As said styrene-type elastomer or its hydrogenated substance (S), it consists of a styrene-type polymer block component (henceforth a styrene block), and a conjugated diene-type polymer block component (henceforth a diene block). A styrene block copolymer, a styrene butadiene random copolymer, a styrene isoprene random copolymer, a styrene chloroprene random copolymer, these hydrogenated substances, etc. are mentioned. Among these, styrene block copolymers are preferable.

The styrene-based polymer block component constituting the styrene-based block copolymer is composed of styrene or a derivative thereof, and specific examples of the monomer include styrene, α-methyl styrene, p-methyl styrene, chloro styrene and vinyl naphthalene. Etc. can be mentioned. Among these, styrene is preferable. These monomers are used individually by 1 type or in combination of 2 or more types.

Butadiene, isoprene, chloroprene, etc. are mentioned as a specific thing of the monomer which comprises the said conjugated diene type polymer block. Among these, butadiene and isoprene are preferable. These monomers are used individually by 1 type or in combination of 2 or more types.

Although the coupling | bonding form of the styrene block and diene block in a styrene-type block copolymer is not specifically limited, Styrene block, diene block, or styrene block [diene block styrene block] n (where n is The form of 1-5 is preferable.

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 is 30. It is preferred that it is from 90 to 90% by weight, preferably 35 to 90% by weight, more preferably 60 to 90% by weight.

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

Specific examples of the styrene block copolymer include styrene ethylene butene styrene block copolymer (SEBS), styrene ethylene propylene styrene block copolymer (SEPS), and styrene butadiene styrene A styrene block copolymer (SBS), a styrene isoprene styrene block copolymer (SIS), a styrene ethylene propylene block copolymer (SEP), etc. are mentioned.

When the olefin polymer composition (E) contains other resins, the upper limit is usually 20 parts by weight or less, more preferably 10 parts by weight or less based on 100 parts by weight in total of the above-mentioned (A) and (B). More preferably, it is 5 weight part or less, and a minimum is 0.1 weight part normally.

When using the said propylene resin (P) as other resin, the said propylene resin (P) has an upper limit normally 20 weight part or less with respect to a total of 100 weight part of said (A) and (B), More preferably, it is 10 weight part or less, More preferably, it is 5 weight part or less, and a minimum is 0.1 weight part normally.

As another resin, when using the said styrene-type elastomer or its hydrogenated substance (S), the said styrene-type elastomer or its hydrogenated substance (S) is an upper limit with respect to a total of 100 weight part of said (A) and (B). Usually this is 20 weight part or less, More preferably, it is 10 weight part or less, More preferably, it is 5 weight part or less, and a minimum is 0.1 weight part normally.

As other resin, when using at least any one of the said propylene resin (P), the said styrene elastomer, or its hydrogenated substance (S), the said propylene resin (P), the said styrene elastomer, or its hydrogenated substance (S) ), The total 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, with respect to 100 parts by weight of the total of (A) and (B). Usually this is 0.1 weight part.

Moreover, when it is preferable that glossiness mold surface roughness dependence is small, the aspect which does not add the said propylene resin (P), the aspect which does not add the said styrene-type elastomer or its hydrogenated substance (S) is a more preferable aspect, The aspect which does not add the said propylene resin (P) and the said styrene-type elastomer or its hydrogenated substance (S) is a further preferable aspect.

Moreover, when using the said styrene-type elastomer or its hydrogenated substance (S), it is one of the preferable aspects that the said low density ethylene-alpha-olefin copolymer (F) is small or does not exist from a sticky point.

When the said low density ethylene-alpha-olefin copolymer (F) is not used, 80-98 weight part of propylene resins (A) mentioned above and 2-20 weight part of ethylene-alpha-olefin copolymers (B) (wherein , (A) and (B) is 100 parts by weight), at least 1 selected from propylene-based resin (P) and styrene-based elastomer or its hydrogenated substance (S) having an optional component, Tm of 140 to 155 ° C. It is also one suitable aspect of the present invention to use an olefinic polymer composition (E) consisting essentially of 0 to 20 parts by weight of the polymer of the species (amount relative to a total of 100 parts by weight of (A) and (B)). Among these, the sum total of the propylene-based resin (P) and styrene-type elastomer or its hydrogenated substance (S) whose Tm is 140-155 degreeC is 0 weight part with respect to a total of 100 weight part of (A) and (B). . In addition, although substantially made, the olefin type polymer composition (E) may contain an additive in the range which does not impair the effect of this invention as another component, but shows that other components are not contained.

As additives, antioxidants, hydrochloric acid absorbers, heat stabilizers, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents, flame retardants, pigments, dyes, dispersants, anti-inflammatory agents, neutralizing agents, foaming agents, plasticizers, antifoaming agents, crosslinking agents, peroxides Fluidity improvers, weld strength improvers, etc. are mentioned. 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 may be any amount within the range in which the effect of the present invention can be obtained. There is no particular limitation, but the total amount of the above (A) and (B) is 100 parts by weight. It is usually from 0.01 to 1.00 parts by weight.

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

There is no restriction | limiting in particular as a preparation method of an olefin polymer composition (E), For example, a propylene resin (A), an ethylene-alpha-olefin copolymer (B), and a nucleating agent (D), the low density ethylene-alpha-olefin air which can be used arbitrarily The coalescence (F) and other resins and additives are added to a mixer such as a Henschel mixer, a Banbury mixer, a tumbler mixer, and the like is mixed, and then the obtained mixture is fed to an extruder such as a single screw extruder or a twin screw extruder. Shaping | molding and the method of obtaining the strand of an olefin polymer composition (E) are mentioned. On the other hand, the strand is usually molded into pellets using a pelletizer or the like before blow molding.

In addition, in the case of using a reactive additive such as a peroxide such as an organic peroxide or a crosslinking agent, the propylene-based resin (A) or the ethylene-α-olefin copolymer (B) As needed, you may carry with modification of the low density ethylene-alpha-olefin copolymer (F) used.

Moreover, although the reason why the multilayer blow container formed using the olefin polymer composition (E) as resin which forms an outermost layer shows favorable physical property is not clear, the ethylene-alpha-olefin copolymer (B) which has a crystalline melting point of a specific range is not clear. It is considered that the ethylene-α-olefin copolymer (B) is finely dispersed in the propylene-based resin (A) by using the polymer. Therefore, the gloss and surface appearance of the multilayer blow container obtained are excellent, and impact resistance It is thought that it is high and both impact resistance and low stickiness are compatible. In addition, when using the propylene polymer (G) or ethylene polymer (H) mentioned later as a polymer which forms an inner layer which contact | connects an outermost layer, the ethylene-alpha-olefin copolymer used as an adhesive point of the said layer and outermost layer ( Since B) is undispersed, the number of adhesive points increases, and it is thought that adhesiveness with an inner layer is also excellent. When the low density ethylene-α-olefin copolymer (F) is used, the low density ethylene-α-olefin copolymer (F) is a propylene-based resin (A) under the intervening of the ethylene-α-olefin copolymer (B). It is considered to be undispersed, and therefore, it is considered to be excellent in gloss and surface appearance, to have high impact resistance and low temperature impact resistance, and to be undispersed, so that stickiness is also low.

<Multilayer blow container>

In the multilayer blow container of this invention, resin used for an outermost layer consists 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 restriction | limiting 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 an olefin polymer composition (E), a propylene polymer (G), an ethylene polymer (H), a styrene polymer, a polyethylene terephthalate resin, a polyamide resin, an ABS resin, an ethylene vinyl acetate copolymer, poly Vinyl alcohol resins or polyvinyl chloride resins, polyvinyl chloride resins, modified polyolefin resins, etc .; Among these, a propylene polymer (G) and an ethylene polymer (H) are preferable.

On the other hand, a propylene polymer (G) is a propylene polymer which has 51 mol% or more of structural units derived from propylene, and an ethylene polymer (H) is an ethylene polymer which has 51 mol% or more of structural units derived from ethylene.

The multilayer blow container is formed of a polar resin such as a styrene polymer or a polyethylene terephthalate resin, a polyamide resin, an ABS resin, an ethylene-vinyl acetate copolymer, a polyvinyl alcohol resin, a polyvinyl chloride resin as another layer (inner layer). In the case of having a layer to be formed, it is preferable to have a layer formed of the modified polyolefin resin (I) between the outermost layer and a layer formed from a styrene polymer or a polar resin in view of the adhesive strength between the layers.

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

As for the outermost layer of the multilayer blow container of this invention, ie, the layer formed from the olefin polymer composition (E), MFR which is an index of fluidity of an olefin polymer composition (E) becomes a specific range. For this reason, in blow molding, the surface of the hot-melt resin just before contacting with a metal mold | die is easy to be smooth, and it is estimated that a surface tends to be smooth even after blow molding, and thereby the multilayer which was excellent in surface glossiness It is thought that a blow container can be obtained. Moreover, since MFR which is an index of fluidity | liquidity of an olefin polymer composition (E) is in a specific range, surface appearance also becomes favorable.

In addition, an ethylene-alpha-olefin copolymer (B) is used as an olefin polymer composition (E) as a raw material of the said composition. Since the ethylene-α-olefin copolymer (B) has a specific range of crystal melting point, the obtained molded article exhibits excellent properties such as excellent interlayer adhesion and low stickiness, as described above, and ethylene. Even when the amount of the α-olefin copolymer (B) to the propylene resin (A) is small, it is possible to efficiently improve the impact resistance. Although this reason is not clear, it is guessed that by selecting the ethylene-alpha-olefin copolymer (B) which has a melting | fusing point of a specific range, it has an appropriate lamellar thickness, and the quantity of the binding molecule which connects lamellar and lamellar is also optimal.

In addition, a low density ethylene-alpha-olefin copolymer (F) is used as a raw material of the said composition as an olefin polymer composition (E) as needed. The low density ethylene-α-olefin copolymer (F) can efficiently improve low-temperature impact resistance even when the amount of the low-density ethylene-α-olefin copolymer (F) is small.

From the above, the present inventors estimated that the multilayer blow container of the present invention is not only high gloss but also excellent in impact resistance, and excellent in low temperature impact resistance when the low density ethylene-α-olefin copolymer (F) is used.

Since the multilayer blow container of this invention is excellent in impact resistance, the crack by the impact from the outside is suppressed, and since the outermost layer is high gloss, the container has glossiness with transparency. Moreover, since the multilayer blow container of this invention is excellent in low-temperature impact resistance, even if it is a case where the content is filled in a multilayer blow container and it is transported, stored, etc. in low temperature conditions, the crack etc. by an external shock will be prevented. Suppressed.

As a layer structure of the multilayer blow container of this invention, what is necessary is just a layer which consists of an olefin polymer composition (E), and although there is no limitation in particular, the outermost layer consists of a two-layer structure of the outermost layer which consists of an olefin polymer composition (E) and an innermost layer, for example. (Layer structure arranged in order of outermost layer / inner layer), outermost layer which consists of olefin polymer composition (E), the intermediate | middle layer adjacent to the said outermost layer, and the innermost layer adjacent to the said intermediate | middle layer 3-layer constitution (outer layer / Middle layer / innermost layer), the outermost layer consisting of the olefin polymer composition (E), the intermediate layer (1) adjacent to the outermost layer, and the intermediate layer (2) adjacent to the intermediate layer (1) And a four-layer constitution (layer constitution arranged in the order of outermost layer / intermediate layer 1 / intermediate layer 2 / inner layer) of the innermost layer adjacent to the intermediate layer 2, and the like.

In addition, in this invention, the layer located inside innermost layer is defined as an inner layer. That is, in this invention, the said innermost layer and an intermediate | middle layer correspond to an inner layer, and the multilayer blow container of this 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 of propylene polymer (G) or ethylene polymer (H), so-called adhesive resins are not used. Even strong adhesiveness was expressed. 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. It is preferable that it is (H).

On the other hand, when the layer adjacent to an olefin polymer composition (E) is a layer other than the said propylene polymer (G) and ethylene polymer (H), it is from a viewpoint of adhesiveness with the outermost layer which consists of an olefin polymer composition (E). It is preferable that the outermost layer which consists of an olefin polymer composition (E), and another layer are formed through an adhesive resin layer.

Arbitrary layers may be colored in the multilayer blow container of this invention.

There is no restriction | limiting in particular as said propylene polymer (G), A homo polypropylene, a propylene alpha-olefin random copolymer, a propylene alpha-olefin block copolymer, etc. are mentioned. The MFR measured at a measurement temperature of 230 ° C. and a 2.16 kg load in accordance with ASTM D-1238 of the propylene polymer (G) is preferably in the range of 0.1 to 20.0 g / 10 minutes, particularly preferably 0.1 to 5 g / 10 minutes. desirable. Moreover, it is preferable that the crystal melting point measured with the differential scanning calorimeter (DSC) based on JIS-K7121 is 100-168 degreeC.

There is no limitation in particular as said ethylene polymer (H), What is called high density polyethylene, linear low density polyethylene, and low density polyethylene is mentioned. The density measured by the density gradient tube method of the ethylene-based polymer (H) is preferably 0.860 to 0.980 g / cm ³ , and as the MFR measured at a measurement temperature of 230 ° C. and a 2.16 kg load according to ASTM D-1238. 20g / 10min is preferable, and it is especially preferable that it is 0.1-5g / 10min.

There is no restriction | limiting in particular as said modified polyolefin resin (I), Generally an acid modified polyolefin can be used. Examples of the acid used for acid modification include ethylenic unsaturated carboxylic acids such as maleic anhydride, acrylic acid, methacrylic acid and itaconic anhydride or anhydrides thereof. Moreover, as a polyolefin resin used for modification, an ethylene-alpha-olefin copolymer, a propylene homopolymer, and a propylene-alpha-olefin copolymer are preferable.

In addition, the inner layer of the multilayer blow container other than the layer adjacent to the outermost layer is a propylene polymer (G), an ethylene polymer (H), a styrene polymer, or a polyethylene terephthalate resin, a polyamide resin, an ABS resin, or an ethylene. -It is preferable that it is a layer formed from 1 or more types of resin chosen from vinyl acetate copolymer, polyvinyl alcohol resin, or polyvinyl chloride resin.

In addition, other resins and various additives may be contained in layers other than outermost layer.

As a shaping | molding method of the multilayer blow container of this invention, as long as blow molding, what kind of method may be sufficient. Examples of the molding method include a direct blow molding method (hollow molding method), an injection stretch blow molding method (injection blow molding method), an extrusion stretch blow molding method, a sheet blow molding method, and the like. As a multilayer blow container, what was obtained by shape | molding by the direct blow molding method or the injection stretch blow molding method from the viewpoint of the productivity at the time of carrying out mass production is preferable.

In the case of forming the multilayer blow container by the direct blow molding method, the olefin polymer composition (E) and other resins are formed in a pipe shape such that the olefin polymer composition (E) is the outermost layer, for example, using a die for multilayer blow. Extruded, while the obtained parison is still in a molten state, it is inserted into a blow mold, and the fluid is blown into the parison to be molded into a predetermined shape. Since the layer formed from an olefin polymer composition (E) becomes an outermost layer, a high gloss multilayer blow container can be obtained.

And in consideration of the MFR, (E) may be restricted to blow molding alone (for example, there may be some difficulties in large blow molding), but using the technique of the present invention, the outermost layer By appropriately selecting other layers (for example, by appropriately selecting (G) or (H)), glossiness, enlargement, and the like can also be simultaneously achieved.

The molding conditions depend on the properties of the resin, but the resin temperature at the time of blowing the fluid, that is, the molding temperature is preferably 120 to 260 ° C, and the blowing pressure of the fluid is preferably 2 to 10 kg / cm ² , It is preferable from a viewpoint of moldability that blow ratio is 1.2-5.0.

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 tubular molten flyson extruded from the extruder die portion.

When the multilayer blow container is molded by the injection stretch blow molding method, for example, the olefin polymer composition (E) and other resins are preformed by injection molding such that the olefin polymer composition (E) is the outermost layer. Mold. Subsequently, when the preform is in a molten state or a softened state, or once the preform is solidified and reheated, the preform is forcibly longitudinally stretched using a stretching rod or the like, and then further stretched in the horizontal direction. In order to pressurize a pressurized fluid in a preform, a multilayer blow container can be obtained. 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. It is preferable that the temperature of the preform immediately before the said longitudinal stretch is 110-150 degreeC, It is preferable that the longitudinal stretch magnification is 1.5-4.0 times, and it is preferable that the lateral stretch magnification is 1.5-3.0 times.

Although the thickness and size of the multilayer blow container of this invention are suitably determined by the use of a multilayer blow container, etc., Usually, thickness is 0.3-10.0 mm, size is 10-300 mm in diameter, and 10-300 mm in height.

As for the thickness of the outermost layer of the multilayer blow container of this invention, the ratio (outer layer / inner layer) of the thickness of an outer layer and another inner layer becomes like this. Preferably it is 50/50-5/95, More preferably, it is 30/70-10 / It is preferable that it is 90. Within the above range, high gloss of the outer layer is most likely to be expressed, and moldability is also good, which is preferable.

The multilayer blow container of this invention is excellent in transparency, when transparent resin is used also for layers other than outermost layer. Specifically, it is preferable that haze value measured using the haze meter based on JIS-K7105 is 30 or less, and it is more preferable that it is 20 or less. Within this range, a bottle with a high added value with excellent visibility of the contents can be obtained.

Although the multilayer blow container of this invention is excellent in glossiness, it is preferable that the 60 degree glossiness measured with the glossmeter specifically based on JIS-K7105 of an outermost layer is 70 or more, and it is more preferable that it is 75 or more. Within the said range, the bottle with high added value which shows the outstanding gloss appearance can be obtained.

Although the multilayer blow container which concerns on this invention can be used for various uses, For example, the container which fills foodstuffs, such as a sauce, dressing, juice, fruit, sweetener, boiled vegetables, the container which fills cosmetics, such as cosmetics and shampoo, liquid It is suitable as a container for filling sanitary articles such as detergents.

[Manufacturing method of a multilayer blow container]

In the manufacturing method of the multilayer blow container of this invention, the said olefin polymer composition (E) forms outermost layer using thermoplastic resin compositions other than the olefin polymer composition (E) and olefin polymer composition (E) mentioned above, It is preferable to mold by the direct blow molding method or the injection stretch blow molding method so that thermoplastic resin compositions other than the olefin polymer composition (E) form at least one inner layer.

Propylene-based resin (A), ethylene-α-olefin copolymer (B), low density ethylene-α-olefin copolymer (F), nucleating agent (D), and olefin polymer composition (E) used in the production method of the present invention. And as thermoplastic resins other than an olefin polymer composition (E), the thing demonstrated by the term of the [multilayer blow container] mentioned above can be used, The other resins and various additives demonstrated by the term of [Multilayer blow container] can also be used.

In the manufacturing method of this invention, the multilayer blow container by which the outermost layer is formed of an olefin polymer composition (E) is shape | molded by the direct blow molding method or the injection stretch blow molding method. For this reason, the multilayer blow container obtained is high gloss because the ethylene-alpha-olefin copolymer (B) is contained in the outermost layer of the said multilayer blow container. In addition, the multilayer blow container is also excellent in impact resistance.

Since the multilayer blow container obtained by the manufacturing method of this invention is excellent in impact resistance, the crack by the impact from the outside is suppressed, and since an outermost layer is high glossiness, a container has glossiness with transparency.

Example

Next, although an Example is given and this invention is demonstrated in more detail, this invention is not limited by these.

[Production of Propylene Resin (A-1)]

(1) Preparation of solid catalyst component

95.2 g of anhydrous magnesium chloride, 442 ml of decane, and 390.6 g of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to form a homogeneous solution, and then 21.3 g of phthalic anhydride was added to this solution, followed by 1 at 130 ° C. The mixture was stirred for a while to dissolve phthalic anhydride.

After cooling the homogeneous solution thus obtained to room temperature, 75 ml of this homogeneous solution was dripped in 1 hour over 200 ml of titanium tetrachloride maintained at -20 degreeC. After the charging was completed, 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 thereto, and the mixture was stirred at the same temperature for 2 hours.

After completion | finish of reaction of 2 hours, the solid part was extract | collected by heat filtration, and this solid part was resuspended in 275 ml of titanium tetrachloride, and it heated at 110 degreeC again for 2 hours. After completion | finish of reaction, the solid part was extract | collected by heat filtration again, and it fully wash | cleaned until the titanium compound liberated in the solution by decane and hexane of 110 degreeC was not detected. The solid part after washing | cleaning was set as the solid titanium catalyst component (A). Although the solid titanium catalyst component (A) was preserve | saved as a decane slurry, some of these were dried for the purpose of investigating a 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.

In addition, detection of the said free titanium compound was performed with the following method. 10 ml of the supernatant of the solid catalyst component was collected by a syringe into 100 ml of branched Schlenk, which had been nitrogen-substituted in advance. Next, the solvent hexane was dried in a nitrogen stream and further vacuum dried for 30 minutes. 40 ml of ion-exchange water and 10 ml of 50 volume% sulfuric acid were charged to this, and it stirred for 30 minutes. The aqueous solution was transferred to a 100 ml volumetric flask through a filter paper, and then conc. As a masking agent for iron (II) ions. 1 ml of H ₃ PO ₄ and ₅ ml of a 3% H ₂ O ₂ aqueous solution were added as a coloring reagent of titanium, and further diluted to 100 ml with ion-exchanged water. After shaking the mixture, the volumetric flask was observed for 20 minutes after observing absorbance at 420 nm using UV to detect free titanium. Until this absorption was not observed, washing | cleaning removal of free titanium and detection of free titanium were performed.

(2) Preparation of Prepolymerization Catalyst Component

After replacing a 500 ml three-necked flask with a stirrer with nitrogen gas, 400 ml of dehydrated heptane, 19.2 mmol of triethylaluminum, 3.8 mmol of dicyclopentyldimethoxysilane, and 4 g of the solid titanium catalyst component (A) Added. The internal temperature was maintained at 20 ° C. and propylene gas was continuously introduced at a rate of 8 g / hr while stirring. After 1 hour, stirring was stopped to give a prepolymerization catalyst component (B) in which 2 g of propylene was polymerized per 1 g of the solid titanium catalyst component (A).

(3) Polymerization

A stainless steel autoclave with a volume of 10 L was thoroughly dried, and after nitrogen replacement, 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 with 0.30 MPa-G, and propylene and ethylene were introduced while stirring was continued. In addition, the introduction amount was adjusted so that the ethylene concentration of the gas phase part in a polymerization tank might be 1.5 mol%.

After the system was stabilized at an internal temperature of 80 ° C. and a total pressure of 0.8 MPa-G, 20.8 ml of a heptane slurry containing 0.10 mmol of the prepolymerization catalyst component (B) in terms of Ti atoms was added thereto to maintain the total pressure and ethylene concentration. And superposition | polymerization was performed at 80 degreeC for 3 hours, supplying ethylene continuously.

When a predetermined time elapsed, 50 ml of methanol was added to stop the reaction, and the temperature was decreased and depressurized. The contents were transferred to the filter tank with a whole quantity filter, and it heated up at 60 degreeC, and solid-liquid separation was carried out. In addition, 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 degreeC, load 2.16 kg) of the obtained propylene resin (A-1) was derived from propylene calculated by 7.0 g / 10min by ¹³ C-NMR. 145 degreeC is 3.2 weight%, and DSC melting point (crystal melting point measured by DSC based on JIS-K7121) of the weight of the structural unit derived from ethylene when the sum total of the structural unit and structural unit derived from ethylene is 100 weight% And Mw / Mn (molecular weight distribution) were 5.3.

[Production of Propylene Resin (A-2)]

In the production of the propylene polymer (A-1), polymerization was carried out in the same manner as in the production of the propylene polymer (A-1) except that the ethylene concentration in the gaseous phase portion in the polymerization tank was adjusted to 2.2 mol%.

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

[Production of Propylene Resin (A-3)]

In the production of the propylene polymer (A-1), polymerization was carried out in the same manner as in the production of the propylene polymer (A-1) except that the ethylene concentration in the gas phase portion in the polymerization tank was adjusted to 0.8 mol%.

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

[Production of Propylene Resin (A-4)]

In the production of the propylene polymer (A-1), polymerization is carried out in the same manner as in the production of the propylene polymer (A-1) except that 0.15 MPa-G is charged after replacing nitrogen in the system with propylene. Done.

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

[Production of Propylene Resin (A-5)]

In the production of the propylene polymer (A-1), the polymerization was carried out in the same manner as in the preparation of the propylene polymer (A-1) except that 0.45 MPa-G was charged after replacing nitrogen in the system with propylene. Done.

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

[Production of Ethylene-α-olefin Copolymer (B-1)]

(1) Preparation of catalyst

10.0 kg of silica and 154 liters of toluene dried at 600 degreeC for 10 hours were charged to the 300-liter reactor fully nitrogen-substituted, and it cooled to 0 degreeC as suspension phase. Then, 23.4 liters of toluene solution of methylaluminoxane (Al = 3.02 mol / liter) was dripped at this suspension over 1 hour. At this time, the temperature in the system was kept in the range of 0 to 5 ° C.

Then, it was made to react at 0 degreeC for 30 minutes, Then, it heated up to 95 degreeC over 1.5 hours, and made it react at that temperature for 4 hours. Then, it cooled to 60 degreeC and the supernatant liquid was removed by the decantation method. The solid component thus obtained was washed twice with toluene, and then resuspended in 100 liters of toluene to make the whole amount 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 dropwise at 35 ° C. over 30 minutes, and further The reaction was carried out 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 gram of solid catalyst component.

(2) Preparation of Prepolymerization Catalyst Component

Into the 350 liter reactor sufficiently nitrogen-substituted, 7.0 kg and hexane of the solid catalyst component (1) prepared above were charged, and the total volume was 285 liters. After cooling the system to 10 degreeC, ethylene was blown in hexane for 5 minutes by the flow volume of 8 Nm <^3> / hr. In the meantime, the temperature in the system was kept at 10 to 15 ° C. Then, supply of ethylene was stopped and 2.4 mol of diisobutyl aluminum hydride (DIBALH) and 1.2 kg of 1-hexene were charged. After making the inside of a system a closed system, supply of ethylene was started again by the flow volume of 8 Nm <^3> / hr. After 15 minutes, the flow rate of ethylene was lowered to 2 Nm ³ / hr, and the pressure in the system was set to 0.08 MPaG. In the meantime, the temperature in a system rose to 35 degreeC. 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. In the meantime, the pressure in the system was maintained at 0.07 to 0.08 MPaG. Subsequently, after substituting with nitrogen for the inside of the system, the supernatant was removed and washed twice with hexane. This gave a prepolymerization catalyst 2 in which 3 g of polymer per 1 g of solid catalyst component was prepolymerized.

(3) Polymerization

Copolymerization of ethylene and 1-hexene was performed at a voltage of 2.0 MPaG, polymerization temperature of 70 deg.

The polymerization was started while continuously supplying 4.1 g / hr and TIBA at a ratio of 5 mmol / hr of the prepolymerization catalyst 2 prepared above. 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 × 10 ^-4 , ethylene Concentration = 71%).

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

In addition, the obtained ethylene 1-hexene copolymer is also described as an ethylene-alpha-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 is changed to 80 ° C., and the gas composition (mol ratio) is 1-hexene / ethylene = 0.03, hydrogen / ethylene = 4.2 × 10 ⁻⁴ , Except having changed into ethylene concentration = 71%, the ethylene 1-hexene copolymer was obtained like manufacture of the ethylene-alpha-olefin copolymer (B-1).

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

In addition, the obtained ethylene 1-hexene copolymer is also described as an ethylene-alpha-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 is changed to 80 ° C., and the gas composition (mol ratio) is 1-hexene / ethylene = 0.02, hydrogen / ethylene = 4.6 × 10 ⁻⁴ , Except having changed into ethylene concentration = 70%, the ethylene 1-hexene copolymer was obtained like manufacture of the ethylene-alpha-olefin copolymer (B-1).

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

In addition, the obtained ethylene 1-hexene copolymer is also described as an ethylene-alpha-olefin copolymer (B-3).

EXAMPLE A1

97 parts by weight of propylene-based resin (A-1) and 3 parts by weight of ethylene-α-olefin copolymer (B-1), and as a nucleating agent (D), Adeka Stab NA-21 (manufactured by ADEKA Corporation: Bis ( 2,4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphosine-6-oxide) aluminum hydroxide salt as a main component Phenol-based antioxidant [pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] as 0.15 parts by weight and an additive; ] 0.10 part by weight, phosphorus antioxidant [tris (2,4-di-t-butylphenyl) phosphite] 0.10 part by weight, 0.09 part by weight of calcium stearate as a neutralizing agent, and monoglycerides stearate as an antistatic agent 0.10 parts by weight of stirring and mixing with a Henschel mixer, the mixture was melt-kneaded under the following conditions using a twin screw extruder (NR-36) manufactured by Nakatani Machinery, Inc. De was obtained.

(Twin screw extruder condition)

Type: NR-36

Screw speed 250rpm

Resin temperature 200 ℃

The obtained strands were cut with a pelletizer after water cooling 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) was 7.0 g / 10 min, DSC melting point (determined by DSC, according to JIS-K7121) Melting point) was 147 ° C.

The results are shown in the table together with the semicrystallization time and the measurement results of the odor.

Next, blow molding was performed using the pellets.

Using three kinds of three-layer multi-layer direct blow molding machines (Placo Co., Ltd., 3B50, 40, 40 blow molding machine), the cylinder temperature is set to 200 ℃ as the molding conditions, the blowing pressure of the fluid to 5.0 kg / cm ² , A crosshead die with a hole size of 14.0 mm and a core size of 12.5 mm is used to form a tubular molten flyson with an outer diameter of 20.0 mm, weight 34 g, content 780 ml, inlet screw outer diameter 27.0 mm, trunk outer diameter 72 mm, and trunk average thickness 0.5 mmt. The cylindrical multilayer blow container of the 2-layer structure of was manufactured.

Specifically, a propylene random copolymer B251VT (manufactured by Prime Polymer Co., Ltd.) is melted for a base material (inner layer) by using an extruder of an intermediate layer and an outer layer in which a cylinder temperature is set to 200 ° C. without using an extruder of an inner layer. Flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) was 1.2 g / 10 min, DSC melting point (crystal melting point measured by DSC in accordance with JIS-K7121) was 146 ° C.) In the extruder of the outer layer, the olefin polymer composition (E-1) was dissolved so as to have an outer layer thickness ratio of 15%, and a cylindrical molten parason was molded by a crosshead die, followed by a water circulation circuit at 25 ° C. The temperature was adjusted to a blow mold, stretched and tightly adhered to the mold with compressed air, and cooled and solidified to obtain a multilayer blow container. On the other hand, as a blow metal | die, two types of metal mold | die which performed the sand blast processing # 400 and the metal mold which performed the sand blast processing # 200 were used as surface treatment, and the multilayer blow container was obtained using each metal mold.

Using the obtained multilayer blow container as a test bottle, haze, gloss, moldability, adhesiveness, impact resistance (full drop impact strength) and stickiness were measured by the evaluation method of the following description. On the other hand, in order to investigate whether the surface treatment of a metal mold affects the glossiness of the multilayer blow container obtained, the multilayer blow container was created using two types of metal molds, and each gloss was evaluated. The results are shown in the table.

Example A2

It carried out similarly to Example A1 except having changed 95.5 weight part of propylene resin (A-1) and 4.5 weight part of ethylene-alpha-olefin copolymers (B-1). Melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-2) obtained in Example A2 was 7.0 g / 10 min, based on DSC melting point (JIS-K7121). And melting point measured by DSC) were 147 ° C.

The results are shown in the table with semicrystallization time, odor measurement results and multilayer blow container test results.

EXAMPLE A3

Propylene random block copolymer B511QA (manufactured by Prime Polymer, Inc., Melt Flow Rate (MFR) (ASTM D) in place of propylene random copolymer B251VT (manufactured by Prime Polymer Co., Ltd.) -1238, measurement temperature 230 ° C., load 2.16 kg) was 1.2 g / 10 min, DSC melting point (crystal melting point measured by DSC based on JIS-K7121) was 158 ° C.) The same was done.

The results are shown in the table.

Example A4

In the case of multilayer blow molding, instead of propylene random copolymer B251VT (prime polymer Co., Ltd.) for the base material (inner layer), PE resin HDPE, HZ-6008B (prime polymer Co., Ltd. melt flow rate (MFR) (ASTM D) -1238, measurement temperature 230 ° C., load 2.16 kg) was carried out in the same manner as in Example A2 except that 0.758 / 10 min and the density measured by the density gradient tube method were 0.958 g / cm ³ ) in the intermediate layer.

The results are shown in the table.

Example A5

It carried out similarly to Example A1 except having changed 80.0 weight part of propylene resin (A-1) and the ethylene-alpha-olefin copolymer (B-1) in the ratio of 20.0 weight part. Melt flow rate (MFR) (ASTM D-1238, measured temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-3) obtained in Example A5 was 7.0 g / 10 min, based on DSC melting point (JIS-K7121). And melting point measured by DSC) were 148 ° C.

The results are shown in the table with semicrystallization time, odor measurement results and multilayer blow container test results.

Example A6

Instead of 0.15 parts by weight of Adeka Stav NA-21 (manufactured by ADEKA) as the nucleating agent (D), gel ol MD (Shin Nippon Chemical Co., Ltd. product name, chemical name = 1,3,2,4-di (p-methylbenzyl) It carried out similarly to Example A2 except having changed to the order of 0.30 weight part of the laden) sorbitol and G-MD). Melt flow rate (MFR) (ASTM D-1238, measured temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-7) obtained in Example A6 was 7.0 g / 10 min, based on DSC melting point (JIS-K7121). And melting point measured by DSC) were 149 ° C.

The results are shown in the table with semicrystallization time, odor measurement results and multilayer blow container test results.

Example A7

When propylene-based resin (A-1) was replaced with propylene-based resin (A-4) and stirred and mixed with a Henschel mixer, it was [2,5-dimethyl-2,5-di (benzoyl peroxy) as an organic peroxide. It carried out similarly to Example A2 except having added 0.006 weight part of hexane].

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

(Comparative Example A1)

It carried out similarly to Example A1 except having changed 100 weight part and ethylene-alpha-olefin copolymer (B-1) of propylene resin (A-1) in the ratio of 0 weight part. Melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-4) obtained in Comparative Example A1 was 7.0 g / 10 min, based on DSC melting point (JIS-K7121). And melting point measured by DSC) were 147 ° C.

The results are shown in the table with semicrystallization time, odor measurement results and multilayer blow container test results.

In the comparative example A1, since the ethylene-alpha-olefin copolymer (B) is not mix | blended, the requirement of this claim is not satisfied. Since the ethylene-α-olefin copolymer (B) is not blended, the adhesiveness and the impact resistance (full drop impact strength) are inferior.

Comparative Example A2

It carried out similarly to Example A1 except having changed 70.0 weight part of propylene resin (A-1) and 30.0 weight part of ethylene-alpha-olefin copolymers (B-1). Melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-5) obtained in Comparative Example A2 was 7.0 g / 10 min, based on DSC melting point (JIS-K7121). And melting point measured by DSC) were 147 ° C.

The results are shown in the table with semicrystallization time, odor measurement results and multilayer blow container test results.

In the comparative example A2, the compounding quantity of an ethylene-alpha-olefin copolymer (B) is more than the range prescribed | regulated in a claim. For this reason, stickiness is inferior.

Comparative Example A3

It carried out similarly to Example A2 except having not added Adeka Stab NA-21 (made by ADEKA Corporation) as a nucleating agent (D). Melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-6) obtained in Comparative Example A3 was 7.0 g / 10 min, based on DSC melting point (JIS-K7121). And crystal melting point measured by DSC) were 145 ° C.

The results are shown in the table with semicrystallization time, odor measurement results and multilayer blow container test results.

In the comparative example A3, since the nucleating agent (D) is not mix | blended, the item of this claim 1 is not satisfied. For this reason, gloss is inferior.

(Comparative Example A4)

It carried out similarly to Example A2 except having changed to propylene resin (A-2) instead of propylene resin (A-1). Melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-8) obtained in Comparative Example A4 was 7.0 g / 10 min, based on DSC melting point (JIS-K7121). And crystal melting point measured by DSC) were 138 ° C.

The results are shown in the table with semicrystallization time, odor measurement results and multilayer blow container test results.

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

(Comparative Example A5)

It carried out similarly to Example A2 except having changed to propylene resin (A-3) instead of propylene resin (A-1). Melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-9) obtained in Comparative Example A5 was 7.0 g / 10 min, based on DSC melting point (JIS-K7121). And melting point measured by DSC) were 158 ° C.

The results are shown in the table with semicrystallization time, odor measurement results and multilayer blow container test results.

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

(Comparative Example A6)

It carried out similarly to Example A2 except having changed to propylene resin (A-4) instead of propylene resin (A-1). Melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-10) obtained in Comparative Example A6 was 3.0 g / 10 min, based on DSC melting point (JIS-K7121). And melting point measured by DSC) were 147 ° C.

The results are shown in the table with semicrystallization time, odor measurement results and 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 changed to propylene resin (A-5) instead of propylene resin (A-1). 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 was 15.0 g / 10 min, based on DSC melting point (JIS-K7121). And melting point measured by DSC) were 147 ° C.

The results are shown in the table with semicrystallization time, odor measurement results and 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)

It carried out similarly to Example A2 except having changed into the ethylene-alpha-olefin copolymer (B-2) instead of the ethylene-alpha-olefin copolymer (B-1). Melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-12) obtained in Comparative Example A8 was 7.0 g / 10 min, based on DSC melting point (JIS-K7121). And melting point measured by DSC) were 147 ° C.

The results are shown in the table with semicrystallization time, odor measurement results and multilayer blow container test results.

As for the ethylene-alpha-olefin copolymer (B-2) used by the comparative example A8, DSC melting | fusing point (crystal melting point measured by DSC based on JIS-K7121) of an ethylene-alpha-olefin copolymer (B) is prescribed | regulated to a claim. Higher than the specified range. For this reason, adhesiveness and impact resistance (full drop impact strength) are inferior. In addition, the balance between impact resistance and stickiness characteristics is not good.

(Comparative Example A9)

It carried out similarly to the comparative example A8 except having changed 90.0 weight part of propylene resin (A-1) and the ethylene-alpha-olefin copolymer (B-2) in the ratio of 10.0 weight part. Melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-13) obtained in Comparative Example A9 was 7.0 g / 10 min, based on DSC melting point (JIS-K7121). And melting point measured by DSC) were 147 ° C.

The results are shown in the table with semicrystallization time, odor measurement results and multilayer blow container test results.

As for the ethylene-alpha-olefin copolymer (B-2) used by the comparative example A9, DSC melting point (crystal melting point measured by DSC based on JIS-K7121) of an ethylene-alpha-olefin copolymer (B) is prescribed | regulated to a claim. Higher than the specified range. For this reason, adhesiveness and impact resistance (full drop impact strength) are inferior. In addition, the balance between impact resistance and stickiness characteristics is not good.

(Comparative Example A10)

It carried out similarly to the comparative example A8 except having changed 80.0 weight part of propylene resin (A-1) and the ethylene-alpha-olefin copolymer (B-2) in the ratio of 20.0 weight part. 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 was 7.0 g / 10 min, based on DSC melting point (JIS-K7121). And melting point measured by DSC) were 147 ° C.

The results are shown in the table with semicrystallization time, odor measurement results and multilayer blow container test results.

As for the ethylene-alpha-olefin copolymer (B-2) used by the comparative example A10, DSC melting | fusing point (crystal melting point measured by DSC based on JIS-K7121) of an ethylene-alpha-olefin copolymer (B) is prescribed | regulated to a claim. Higher than the specified range. For this reason, adhesiveness and impact resistance (full drop impact strength) are inferior. In addition, the balance between impact resistance and stickiness characteristics is not good.

(Comparative Example A11)

It carried out similarly to Example A2 except having changed into the ethylene-alpha-olefin copolymer (B-3) instead of the ethylene-alpha-olefin copolymer (B-1). Melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of the olefin polymer composition (E-15) obtained in Comparative Example A11 was 7.0 g / 10 min, based on DSC melting point (JIS-K7121). And melting point measured by DSC) were 147 ° C.

The results are shown in the table with semicrystallization time, odor measurement results and multilayer blow container test results.

As for the ethylene-alpha-olefin copolymer (B-3) used by the comparative example A11, DSC melting | fusing point (crystal melting point measured by DSC based on JIS-K7121) of an ethylene-alpha-olefin copolymer (B) is prescribed | regulated to a claim. Higher than the specified range. For this reason, gloss, adhesiveness, and impact resistance (full drop impact strength) are inferior. In addition, the balance between impact resistance and stickiness characteristics is not good.

(Comparative Example A12)

PE-based resin L-LDPE (linear low density polyethylene) produced by Ziegler-Natta catalyst instead of metallocene catalyst instead of ethylene-α-olefin copolymer (B-1), ULT ZEX 1030L (manufactured by Prime Polymer Co., Ltd.) , 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 (crystal melting point measured by DSC in accordance with JIS-K7121) It carried out similarly to Example A2 except having changed to this 115 degreeC.

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

The results are shown in the table with semicrystallization time, odor measurement results and multilayer blow container test results.

In Comparative Example A12, ULT ZEX 1030L was used instead of the ethylene-α-olefin copolymer (B). DSC melting point (crystal melting point measured by DSC based on JIS-K7121) of ULT ZEX 1030L is 115 degreeC, and is higher than the DSC melting point of the ethylene-alpha-olefin copolymer (B) of Claim. In addition, since ULT ZEX 1030L is polymerized not by a metallocene catalyst but by a Ziegler-Natta catalyst, the multilayer blow container formed of the olefin polymer composition (E-16) has adhesiveness, stickiness, and impact resistance (full drop impact strength). ) Is behind. In addition, the balance between impact resistance and stickiness characteristics is not good.

(Comparative Example A13)

PE-based resin HDPE (high density polyethylene), HZ-2100J (manufactured by Prime Polymer Co., Ltd., density 0.956 g / cm ³ , melt flow rate (MFR) instead of ethylene-α-olefin copolymer (B-1) (ASTM D- 1238, measurement temperature 230 ° C, load 2.16kg) changed to 11.0g / 10min, DSC melting point (crystal melting point measured by DSC in accordance with JIS-K7121) to 131 ° C and Mw / Mn (molecular weight distribution) of 7.0 And it carried out similarly to Example A1 except having changed 90.0 weight part of propylene resin (A-1) and PE resin HDPE and HZ-2100J (made by Prime Polymer Co., Ltd.) at the ratio of 10.0 weight part.

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

The results are shown in the table with semicrystallization time, odor measurement results and multilayer blow container test results.

In Comparative Example A13, HZ-2100J was used instead of the ethylene-α-olefin copolymer (B). DSC melting point (crystal melting point measured by DSC based on JIS-K7121) of HZ-2100J is 131 degreeC, and is higher than the DSC melting point of the ethylene-alpha-olefin copolymer (B) of Claim. In addition, 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 the olefin polymer composition (E-17) is inferior in adhesiveness and impact resistance (full drop impact strength). In addition, the balance between impact resistance and stickiness characteristics is not good.

[Comparative Example A14]

· Ethylene α- olefin copolymer (B-1) an ethylene · α- olefin copolymer (B) instead of the tarp Murray P-0680 (polyethylene rubber (EPR), manufactured by Mitsui Chemical Co., Ltd. Co., Ltd., density 0.870g / cm ³ Melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) is 1.0 g / 10 min, DSC melting point (crystal melting point measured by DSC in accordance with JIS-K7121) is not measured.) Changed to 90.0 parts by weight of propylene-based resin (A-1) and ethylene-α-olefin copolymer (B) in which the ratio of tarpmer P-0680 (manufactured by Mitsui Chemicals Co., Ltd.) was 10.0 parts by weight. The same procedure was followed as in Example A1.

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

The results are shown in the table with semicrystallization time, odor measurement results and multilayer blow container test results.

In the comparative example A14, the tamper P-0680 (made by Mitsui Chemicals Co., Ltd.) is used instead of the ethylene-alpha-olefin copolymer (B). Tafmer P-0680 does not measure DSC melting point (crystal melting point measured by DSC in accordance with JIS-K7121) and does not correspond to ethylene-α-olefin copolymer (B). The melt flow rate (MFR) (ASTM D-1238, measurement 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 the olefin polymer composition (E-18) is inferior to glossiness, adhesiveness, and stickiness.

(Comparative Example A15)

Ethylene · α- olefin copolymer (B-1) an ethylene · α- olefin copolymer (B) instead of the tarp Murray P-0180 (polyethylene rubber (EPR), manufactured by Mitsui Chemical Co., Ltd. Co., Ltd., density 0.870g / cm ³ Melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) is 8.0 g / 10 min, DSC melting point (crystal melting point measured by DSC in accordance with JIS-K7121) is not measured.) Changed to 90.0 parts by weight of propylene-based resin (A-1) and ethylene-α-olefin copolymer (B) in which the ratio of tamper P-0180 (manufactured by Mitsui Chemicals Co., Ltd.) was 10.0 parts by weight. The same procedure was followed as in Example A1.

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

The results are shown in the table with semicrystallization time, odor measurement results and multilayer blow container test results.

In Comparative Example A15, a tamper P-0180 (manufactured by Mitsui Chemicals Co., Ltd.) was used instead of the ethylene-α-olefin copolymer (B). Tafmer P-0180 does not measure DSC melting point (crystal melting point measured by DSC based on JIS-K7121) and does not correspond to an ethylene-alpha-olefin copolymer (B). Moreover, 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 to adhesiveness and stickiness.

EXAMPLE B1

97 parts by weight of propylene-based resin (A-1) and 3 parts by weight of ethylene-α-olefin copolymer (B-1), and as a nucleating agent (D), Adeka Stab NA-21 (manufactured by ADEKA Corporation: Bis ( 2,4,8,10-tetra-t-butyl-6-hydroxy-12H-dibenzo [d, g] [1,3,2] dioxaphosphosine-6-oxide) aluminum hydroxide salt as a main component 0.15 parts by weight of the containing aromatic phosphate compound-based nucleating agent), a low density ethylene-α-olefin copolymer (F), manufactured by Mitsui Chemicals, Tafmer P-0280 (ethylene-propylene copolymer, density measured by density gradient tube method) : 0.870 g / cm ³ , Ziegler-Natta catalyst, DSC melting point (crystal melting point measured by DSC in accordance with JIS-K7121): Not observed, MFR (ASTM-1238, measuring temperature 230 ° C., load 2.16 kg): 5.4 g / 10 min), and 0.10 weight part of phenolic antioxidant [pentaerythritol tetrakis [3- (3,5-di-t- butyl- 4-hydroxyphenyl) propionate] as 15 weight part Wealth, phosphorus oxidation prevention 0.10 parts by weight of [tris (2,4-di-t-butylphenyl) phosphite] and 0.09 parts by weight of calcium stearate as a neutralizing agent were stirred and mixed with a Henschel mixer, and the mixture was a twin screw extruder manufactured by Nakatani Machine. The strands were obtained by melt kneading under the following conditions using (NR-36).

(Twin screw extruder condition)

Type: NR-36

Screw speed 250rpm

Resin temperature 200 ℃

The obtained strands were cut with a pelletizer after water cooling to obtain pellets of the olefin polymer composition (E-21).

Melt flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) of propylene resin composition (E-21) was 7.0 g / 10 min, DSC melting point (based on JIS-K7121, measured by DSC) Crystal melting point) was 147 ° C.

The results are shown in the table together with the semicrystallization time and the measurement results of the odor.

Next, blow molding was performed using the pellets.

Using three kinds of three-layer multi-layer direct blow molding machines (Placo Co., Ltd., 3B50, 40, 40 blow molding machine), the cylinder temperature is set to 200 ℃ as the molding conditions, the blowing pressure of the fluid to 5.0 kg / cm ² , A crosshead die with a hole size of 14.0 mm and a core size of 12.5 mm is used to form a tubular molten flyson with an outer diameter of 20.0 mm, weight 34 g, content 780 ml, inlet screw outer diameter 27.0 mm, trunk outer diameter 72 mm, and trunk average thickness 0.5 mmt. The cylindrical multilayer blow container of the 2-layer structure was manufactured.

Specifically, a propylene random copolymer B251VT (manufactured by Prime Polymer Co., Ltd.) is melted for a base material (inner layer) by using an extruder of an intermediate layer and an outer layer in which a cylinder temperature is set to 200 ° C. without using an extruder of an inner layer. Flow rate (MFR) (ASTM D-1238, measurement temperature 230 ° C., load 2.16 kg) was 1.2 g / 10 min, DSC melting point (crystal melting point measured by DSC in accordance with JIS-K7121) was 146 ° C.) In the extruder of the outer layer, the olefin polymer composition (E-21) was dissolved so as to have an outer layer thickness ratio of 15%, and a cylindrical molten parason was molded by a crosshead die, followed by a water circulation circuit at 25 ° C. The temperature was adjusted to a blow mold, stretched and tightly adhered to the mold with compressed air, and cooled and solidified to obtain a multilayer blow container. On the other hand, as a blow metal | die, two types of metal mold | die which performed the sand blast processing # 400 and the metal mold which performed the sand blast processing # 200 were used as surface treatment, and the multilayer blow container was obtained using each metal mold.

The obtained multilayer blow container was used as a test bottle, and the haze, gloss, moldability, adhesiveness, stickiness, impact resistance (full drop impact strength) and low temperature impact resistance (full drop resistance) were evaluated by the evaluation method described below. Strength). On the other hand, in order to investigate whether the surface treatment of a mold affects the glossiness of the multilayer blow container obtained, the multilayer blow container was created using two types of molds, and each gloss was evaluated. The results are shown in the table.

EXAMPLE B2

The low density ethylene-alpha-olefin copolymer (F) measured by Mitsui Chemicals Co., Ltd., Tafmer P-0280, Mitsui Chemicals Co., Ltd., Tafmer A-4085S (ethylene-butene copolymer, density gradient pipe method: 0.885 g / cm ³ , DSC melting point (crystal melting point measured by DSC in accordance with JIS-K7121): 70 ° C., MFR (ASTM-1238, measurement temperature 230 ° C., load 2.16 kg): 6.7 g / 10 min), The compounding quantity was changed from 15 weight part to 7 weight part, and it carried out similarly to Example B1 except having used 0.1 weight part of stearic acid monoglycerides as an antistatic agent, and obtained the strand.

Except having used the said strand, it carried out similarly to Example B1, and obtained the multilayer blow container.

The results are shown in the table.

EXAMPLE B3

90 parts by weight of propylene resin (A-1) and 10 parts by weight of ethylene-α-olefin copolymer (B-1) were changed, and the low-density ethylene-α-olefin copolymer (F) was manufactured by Mitsui Chemicals, Inc. A strand was obtained in the same manner as in Example B1 except that the product was changed from Merc P-0280 to Tafmer A-4085S manufactured by Mitsui Chemicals, and the amount thereof was changed from 15 parts by weight to 5 parts by weight.

Except having used the said strand, it carried out similarly to Example B1, and obtained the multilayer blow container.

The results are shown in the table.

EXAMPLE B4

A strand was obtained in the same manner as in Example B1 except that the low density ethylene-α-olefin copolymer (F) was changed from Mitsui Chemicals, Tafmer P-0280 to Mitsui Chemicals, Tafmer A-4085S. did.

Except having used the said strand, it carried out similarly to Example B1, and obtained the multilayer blow container.

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.

Except having used the said strand, it carried out similarly to Example B1, and obtained the multilayer blow container.

The results are shown in the table.

Example B6

Antistatic agent without changing 95.5 weight part of propylene resin (A-1) and 4.5 weight part of ethylene-alpha-olefin copolymers (B-1), and using a low density ethylene-alpha-olefin copolymer (F) 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.

Except having used the said strand, it carried out similarly to Example B1, and obtained the multilayer blow container.

The results are shown in the table.

Example B7

Except having changed 90 weight part of propylene resin (A-1) and 10 weight part of ethylene-alpha-olefin copolymers (B-1), and did not use the low density ethylene-alpha-olefin copolymer (F). In the same manner as in Example B1, a strand was obtained.

Except having used the said strand, it carried out similarly to Example B1, and obtained the multilayer blow container.

The results are shown in the table.

[Reference Example B1]

95.5 parts by weight of propylene resin (A-1) and ethylene-α-olefin copolymer (B-1) were changed to 4.5 parts by weight, and the low-density ethylene-α-olefin copolymer (F) was 25 parts by weight from 15 parts by weight. The strand was obtained like Example B1 except having changed to negative.

Except having used the said strand, it carried out similarly to Example B1, and obtained the multilayer blow container.

The results are shown in the table.

(Comparative Example B1)

The ethylene-α-olefin copolymer (B-1) was changed to ethylene-α-olefin copolymer (B-2), the propylene-based resin (A-1) was changed to 95.5 parts by weight, and the ethylene-α-olefin air 4.5 weight part of copolymers (B-2) are used, and the low density ethylene-alpha-olefin copolymer (F) is manufactured by Mitsui Chemicals, Tafmer P-0280, Mitsui Chemicals, Tafmer P-0275 (ethylene-propylene Copolymer, Density measured by density gradient method: 0.860 g / cm ³ , DSC melting point (crystal melting point measured by DSC in accordance with JIS-K7121): Not observed, MFR (ASTM-1238, measuring temperature 230 ° C., load) 2.16 kg): Strand was obtained similarly to Example B1 except having changed to 5.4 g / 10min).

Except having used the said strand, it carried out similarly to Example B1, and obtained the multilayer blow container.

The results are shown in the table.

〔Assessment Methods〕

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

(MFR (melt flow rate))

MFR of the said propylene resin (A), an ethylene-alpha-olefin copolymer (B), a low density ethylene-alpha-olefin copolymer (F), and an olefin polymer composition (E) is ASTM D-1238, the measurement temperature 230 degreeC, It measured according to the load of 2.16 kg.

Based on ASTMD-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 point 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 a differential scanning calorimeter according to JIS-K7121. The measurement was carried out using (DSC, Perkin Elmer (Diamond DSC)). The peak of the endothermic peak in the 3rd step measured here was defined as crystal melting point (Tm). When there are a plurality of endothermic peaks, the endothermic peak peak at which the peak height is maximum is defined as the crystal melting point (Tm).

(Measuring conditions)

Measuring environment: nitrogen gas atmosphere

Sample volume: 5 mg

Sample shape: press film (230 DEG C molding, thickness 200 to 400 mu m)

1st step: It heats up to 240 degreeC from 30 degreeC to 10 degreeC / min, and hold for 10 minutes.

Second step: Lower to 60 ° C. at 10 ° C./min.

3rd step: It heats up to 240 degreeC at 10 degreeC / min.

[Half-crystallization time (T _1/2)]

The half-crystallization time of the olefin polymer composition _{(E) (T 1/2} ) is a differential scanning calorimeter (DSC, manufactured by Perkin Elmer (DSC7)) was measured using a. The olefin polymer composition (E) was crystallized under 125 ° C isothermal conditions, and the calorific value accompanying crystallization was measured, and the time (seconds) from the exothermic onset (crystallization onset) to the calorific value at half the total calorific value was determined by the semicrystallization time. It was measured as a (t _1/2). The smaller the value of the half-crystallization time (t _1/2) means that a fast rate of crystallization.

(Measuring conditions)

Measuring environment: nitrogen gas atmosphere

Sample volume: 5 mg

Sample shape: press film (230 DEG C molding, thickness 200 to 400 mu m)

First step: The temperature was raised from 30 ° C. to 10 ° C./min to 220 ° C. and maintained for 3 minutes.

Second step: Lower to 125 ° C. at 60 ° C./min.

〔density〕

The density of the ethylene-alpha-olefin copolymer (B) and the low density ethylene-alpha-olefin copolymer (F) is the ethylene-alpha-olefin copolymer (B) and the low density ethylene-alpha-olefin obtained at the time of the said MFR measurement. The strands of the copolymer (F) were each heat-treated at 120 ° C. for 1 hour and slowly cooled to room temperature over 1 hour, and then measured by a density gradient tube.

(Mw / Mn (molecular weight distribution))

Mw / Mn of the said propylene resin (A) and ethylene-alpha-olefin copolymer (B) was calculated | required from the weight average molecular weight (Mw) and number average molecular weight (Mn) measured by the following measuring method.

Mw and Mn were measured in the same manner as below using GPC-150C Plus manufactured by Waters.

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

Standard polystyrene is a molecular weight of Mw <1000 and Mw> 4 × 10 ⁶ As for the Tosoh Co., Ltd. by using the first, and when it comes to 1000≤Mw≤4 × 10 ⁶ Pressure Chemical Co. were used.

[Haze]

The haze of a multilayer blow container cut out the measurement site | part from the container trunk | drum, and measured the haze (haze value) with the haze meter (NIPPON DENSHOKU (NDH2000)) based on JIS-K7105. The smaller the value of the haze, the more excellent the transparency.

〔Polish〕

Evaluation of glossiness was evaluated by the measurement of the following glossiness. The glossiness of the multilayer blow container cut out the measurement site | part from the container trunk | drum, and measured 60 degree glossiness of the outer layer with the gloss meter (NIPPON DENSHOKU (VG2000)) based on JIS-K7105. It can be said that the greater the value of glossiness, the more excellent glossiness.

[Forming]

The moldability of the multilayer blow container was observed by observing the obtained container appearance, and evaluated by the presence or absence of wrinkles due to surface skin roughness of the molten flyson during blow to the container body.

AA: No wrinkles or inconspicuous, good moldability.

BB: Wrinkles are observed or outstanding, and moldability is inferior.

[Adhesiveness]

Between the outermost layer and the adjacent layer formed of the olefin polymer composition (E) of the multi-layer blow container, burr cuts, i.e., pinch-off portions at the top of the container and at the bottom of the container, are formed at the time of forming the container. The presence or absence of the appearance defect observed in the strip | belt shape and strip | belt shape by the layer peeling which generate | occur | produces is evaluated.

AA: No appearance defects and good adhesion.

BB: When observed, poor appearance was observed, and the adhesion was slightly inferior.

CC: There is obvious appearance defect, and adhesiveness is inferior.

〔stink〕

The odor of the olefin polymer composition (E) is placed in a 100 ml Erlenmeyer flask, and sealed with a lid stopper, and then taken out after heating for 1 hour in an oven at 100 ° C., the lid is opened immediately, and the odor generated is a sensory test. As judged superiority as follows.

AA ... No smell.

BB ... There is some odor.

CC ··· There is a bad smell.

[Impact resistance]

Evaluation of impact resistance was evaluated by the presence or absence of the occurrence of surface cracks by the following full-water drop impact strength measurement method. The filling container filled with water in the multilayer blow container (capacity 780 ml) was cooled to 5 ° C. (evaluation of impact resistance), and each of the ten containers cooled to each temperature was placed at a position where the bottom of the container was 1 m high from the concrete surface. It was made to fall vertically and the evaluation was performed according to the following fall criteria. The determination of cracks was determined by the presence or absence of surface cracks.

AA: No cracking on the entire surface.

BB: More than half the surface does not crack, but at least one crack occurs on the surface.

CC: cracks on the surface in a majority.

It can be said that impact resistance is so favorable that evaluation of the full-water fall impact strength measurement method is so good.

[Low temperature impact resistance]

Evaluation of low temperature impact resistance was evaluated by the presence or absence of the occurrence of surface cracks by the following full-water drop impact strength measurement method. In a multi-layer blow container (inner capacity 780 ml), a filling container filled with a liquid consisting of ethylene glycol / water = 5/5 (volume / volume) was cooled to -5 ° C (evaluation of low temperature impact resistance) and cooled to each temperature. Each of the 10 containers thus made was vertically dropped at a position where the bottom of the container became a height of 1 m from the concrete surface, and evaluation was performed according to the following falling criteria. The determination of cracks was determined by the presence or absence of surface cracks.

AA: No cracking on the entire surface.

BB: More than half the surface does not crack, but at least one crack occurs on the surface.

CC: cracks on the surface in a majority.

It can be said that the low temperature impact resistance is so favorable that evaluation of a full-water fall impact strength measurement method is favorable.

[Stickyness]

Regarding the texture of the surface of the multilayer blow container, it was judged as follows with respect to the surface of the bottle adjusted to the condition at 48 ° C. for 48 to 72 hours after molding by the sensory test with or without sticky touch.

AA: I don't feel sticky at all.

BB: I almost never feel sticky.

CC: I feel a bit sticky.

DD: Feeling sticky.

In the multilayer blow container of the present application, it is preferable that there is no stickiness, and that stickiness is inferior to stickiness.

[Weight of the structural unit derived from the alpha olefin in propylene resin computed by ¹³ C-NMR]

The sum total of the structural unit derived from propylene and the structural unit derived from 1 or more types of olefins chosen from the group which consists of ethylene and the C4-20 alpha-olefin computed by ¹³ C-NMR shall be 100 weight%. At this time, 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 was measured and calculated as follows based on the measurement of ¹³ C-NMR. .

¹³ C-NMR Measurement Conditions

Measuring device: LA400 type nuclear magnetic resonance device made by Nippon Electronics

Measurement mode: Bilevel Complete decoupling (BCM)

Observation frequency: 100.4 MHz

Viewing range: 17006.8 Hz

Pulse width: C core 45 ° (7.8μs)

Pulse repetition time: 5 seconds

Sample tube: 5 mmφ

Sample tube rotation speed: 12Hz

Cumulative Count: 20000

Measuring temperature: 125 ℃

Solvent: 1,2,4-trichlorobenzene: 0.35 ml / heavy benzene: 0.2 ml

Sample amount: approx. 40 mg

In the case where the comonomer is ethylene, the obtained ¹³ C-NMR spectrum is determined based on the following document (1) to determine the ratio of monomer chain distribution (diad (double-ring) distribution), and ethylene in (A) of the propylene resin. Calculate the mole fraction (mol%) of the structural unit derived from (hereinafter referred to as E (mol%)) and the mole fraction (mol%) of the structural unit derived from propylene (hereinafter referred to as P (mol%)). did. From the obtained E (mol%) and P (mol%), the weight percent of the structural units derived from propylene in the propylene resin (A) and the weight percent of structural units derived from ethylene were calculated.

Document (1): Kakugo, M .; Naito, Y .; Mizunuma, K .; Miyatake, T., Macromolecules 1982, 15, (4), 1150-1152

On the other hand, during the evaluation of the physical properties of the multilayer blow container, the haze, moldability, adhesiveness, impact resistance, low temperature impact resistance, and stickiness were measured with respect to the multilayer blow container created using a mold subjected to sand blast treatment # 400. did.

Claims (13)

The resin used for outermost layer is 80-98 weight part of propylene resin (A), and 2-20 weight part of ethylene-alpha-olefin copolymers (B) (However, the sum total of (A) and (B) is 100 weight part. ) 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).
(A-1) It is a copolymer of propylene and 1 or more types of olefins chosen from the group which consists of ethylene and the alpha olefin of 4-20 carbon atoms.
(A-2) The crystal melting point measured by the differential scanning calorimeter (DSC) based on JIS-K7121 is the range of 140-155 degreeC.
(B-1) It is a copolymer of ethylene and 1 or more types of alpha-olefins of 4-20 carbon atoms.
(B-2) The melting | fusing point of crystal | crystallization measured by DSC based on JIS-K7121 is 85 degreeC or more and less than 110 degreeC.
(E-1) Melt flow rate (MFR) measured by measurement temperature 230 degreeC and 2.16 kg load based on ASTMD-1238 is the range of 5-10 g / 10min. The method of claim 1,
The said olefin polymer composition (E) is further formed using 0.1-20 weight part of low-density ethylene-alpha-olefin copolymers (F),
The low density ethylene-α-olefin copolymer (F) satisfies the following requirements (F-1) and (F-2),
The ethylene-density density gradient tube method of measuring the α- olefin copolymer _{(B) (d B [g} / cm 3]) and low density ethylene-a density measured by the density gradient tube method of α- olefin copolymer (F) ( d _F [g / cm ³ ]), wherein the multilayer blow container meets the following requirements (X-1).
(F-1) It is a copolymer of ethylene and 1 or more types of alpha-olefins of 3-20 carbon atoms.
(F-2) The crystal melting point measured by DSC based on JIS-K7121 is 89 degrees C or less, or the peak based on a crystal melting point is not observed.
(X-1) d _B [g / cm ³ ]> d _F [g / cm ³ ], 0.010 [g / cm ³ ] ≤ (d _B -d _F ) [g / cm ³ ] ≤0.050 [g / cm ³ ]. The method of claim 1,
The said ethylene-alpha-olefin copolymer (B) further satisfy | fills following requirement (B-4), The multilayer blow container characterized by the above-mentioned.
(B-4) The density measured by the density gradient tube method is in the range of 0.880 to 0.910 g / cm ³ . 3. The method of claim 2,
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). Multi-layer blow container, characterized in that.
(B-4a) is a density ^{_{(d B [g / cm 3}} ]) in the range of 0.890 to 0.910g / cm ³ measured by the density gradient tube method.
(F-3) The density (d _F [g / cm ³ ]) measured by the density gradient tube method is in the range of 0.865 to 0.900 g / cm ³ . The method of claim 1,
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 method of claim 1,
The said propylene resin (A) further satisfy | fills following requirement (A-3), The multilayer blow container characterized by the above-mentioned.
(A-3) MFR measured at 230 degreeC of measurement temperature and 2.16 kg load based on ASTMD-1238 is the range of 5-10 g / 10min. The method of claim 1,
The said ethylene-alpha-olefin copolymer (B) further satisfy | fills following requirement (B-5), The multilayer blow container characterized by the above-mentioned.
(B-5) Mw / Mn measured by GPC is 1.2-3.0. The method of claim 1,
The said ethylene-alpha-olefin copolymer (B) further satisfy | fills following requirement (B-3), The multilayer blow container characterized by the above-mentioned.
(B-3) MFR measured at 230 degreeC of measurement temperature and 2.16 kg load based on ASTMD-1238 is the range of 5-10 g / 10min. The method of claim 1,
And said nucleating agent (D) is at least one compound selected from the group consisting of an aromatic phosphate compound, a carboxylic acid metal salt nucleating agent, a polymer nucleating agent, a sorbitol nucleating agent and an inorganic compound nucleating agent. The method of claim 1,
The propylene 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 the total of (A) and (B) is 100 parts by weight. Multi-layer blow container, characterized in that. The method of claim 1,
And said multilayer blow container has a layer formed of propylene polymer (G) or ethylene polymer (H) as at least one inner layer. The method of claim 1,
And said multilayer blow container is obtained by molding by a direct blow molding method or an injection stretch blow molding method. Using thermoplastic resin compositions other than the olefin polymer composition (E) and olefin polymer composition (E) of Claim 1,
The said olefin polymer composition (E) forms outermost layer, and it forms by the direct blow molding method or injection stretch blow molding method so that thermoplastic resin compositions other than the said olefin polymer composition (E) may form at least one inner layer. The manufacturing method of the multilayer blow container.