JP2014019733A - High-density polyethylene resin composition and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high-density polyethylene resin composition yielding a molding excellent in terms of rigidity, transparency, and content visual recognizability and a simple low-cost method for manufacturing the same.SOLUTION: A high-density polyethylene resin composition including a high-density polyethylene resin and a laminar silicate wherein the maximal size of spherulites of the high-density polyethylene resin is 0.1 μm or above and 5 μm or below and a molding obtained by press-molding or injection-molding the composition are provided. The inclusion of 0.1-20 wt.% of the laminar silicate and/or the inclusion of kaolin within the laminar silicate are preferred.

Description

  The present invention relates to a high-density polyethylene resin composition and a method for producing the same.

  Conventionally, resin has been widely used as a material for containers regardless of whether the contents are liquid or solid. Among them, polyethylene resin is widely used as a container material because it can be easily molded in various ways, has a good balance of physical properties, has excellent chemical resistance, and is economical. In addition, polyethylene resin can be injection-molded like other resins, and it has a good balance of physical properties, excellent chemical resistance, and is economical. Yes.

  However, the transparency of the polyethylene resin is lowered when it is formed into a molded product having a certain thickness. In particular, since high-density polyethylene resin has almost no transparency, it is not suitable for applications that require rigidity and transparency is required, and there is a problem that the contents are not visible when it is made into a container. It has been cited as an issue since before.

  Even in the case of a low density polyethylene resin or a high density polyethylene resin, transparency has been actively improved in the film field. For example, a method for improving transparency by blending low-density polyethylene or polypropylene with high-density polyethylene resin has been reported (for example, see Patent Document 1).

  On the other hand, there is an example of improving the transparency of a high-density polyethylene resin by blending a linear low-density polyethylene resin with a high-density polyethylene resin cross-linked with γ rays (see, for example, Patent Document 2).

  Moreover, a method for improving the transparency of a high-density polyethylene resin by crosslinking the high-density polyethylene resin in the presence of oxygen during granulation has been reported (for example, see Patent Document 3).

  Furthermore, a method for imparting transparency to a high-density polyethylene resin by press-drawing a polyethylene sheet or film has been reported (for example, see Patent Document 4).

  Furthermore, a method for improving the transparency of the polyolefin resin by introducing a crystal nucleating agent or filler into the polyolefin resin has been reported (for example, see Patent Document 5).

  On the other hand, research for adding nanocomposites has been conducted as one of the studies for adding fillers to polyethylene resin (see, for example, Patent Document 6). In addition, there are examples of studying addition of non-layered kaolins to polyethylene resins (see, for example, Patent Documents 7 and 8).

JP 2004-231844 A JP-A-9-31256 Japanese Patent Laid-Open No. 10-130397 JP 2009-149816 A Special table 2008-540695 gazette Special table 2003-517488 gazette JP 2005-523966 A JP 2010-195956 A

  However, in Patent Document 1, most are high-density polyethylene resins for film use, and the density is low, resulting in insufficient rigidity when used as containers or molded products. Moreover, when polypropylene is blended, there is a concern about peeling from polypropylene.

  Further, in Patent Document 2, there is a problem that productivity is poor because an apparatus for irradiating γ rays to a high-density polyethylene resin is necessary, and it is necessary to knead and extrude and pelletize after being treated with γ rays. Comes with difficulties.

  Further, in Patent Document 3, improvement in transparency of the high-density polyethylene resin is recognized, and the productivity can be secured because it can be incorporated into the manufacturing process. However, in addition to the resin being burned by introducing oxygen into the extruder, Addition of such a heat stabilizer inhibits oxygen crosslinking, so that its use is limited, and there is a problem that the range of effective molding conditions is limited.

  Furthermore, in Patent Document 4, since it is necessary to roll a film or an extruded sheet in order to achieve transparency, the molded product is limited to a long product and cannot be applied to normal injection molding or compression molding. There's a problem.

  Furthermore, Patent Document 5 relates to the transparency of polypropylene, and cannot be expanded to polyethylene having a different crystal structure and crystal growth mechanism.

  In addition, in Patent Document 6, it is necessary to disperse the organic compound-treated layered compound in the high-density polyethylene resin composition by kneading, and even if it is effective in improving rigidity and suppressing gas permeability, it improves transparency. There is no mention about.

  Moreover, in patent document 7, although flash baking kaolin is added to a high density polyethylene resin composition, it achieves the same opacification as titanium oxide that has been conventionally performed, and is opposite to transparency. This is aimed at producing an effect.

  Furthermore, the high-density polyethylene resin composition described in Patent Document 8 requires a peroxide and a vinylsilane compound for crosslinking during extrusion, and is transparent even if effective for enhancing long-term mechanical properties. There is no mention about.

  As described above, there is no resin composition having improved transparency without adding other resins or modification such as crosslinking to the conventional high-density polyethylene resin. In addition, the description of improving transparency by kneading layered silicates such as kaolin compounds, which are white or colored, not nano-dispersed, and have a refractive index significantly different from that of polyethylene resin, into high-density polyethylene resin is described. On the contrary, it is completely unpredictable.

  The present invention has been made in view of the above problems, and is a high-density polyethylene resin composition that is a molded body excellent in rigidity, transparency, and visibility of contents, and simple and low-cost production thereof. It aims to provide a method.

  As a result of intensive studies to solve the problems of the prior art, the present inventors have found that a high-density polyethylene resin composition containing a specific layered silicate in a high-density polyethylene resin that is inherently opaque has transparency. As a result, the present invention has been accomplished.

That is, the present invention is as follows.
(1) A high-density polyethylene resin composition comprising a high-density polyethylene resin and a layered silicate, wherein the maximum size of spherulites of the high-density polyethylene resin is 0.1 μm or more and 5 μm or less.
(2) The high-density polyethylene resin composition according to (1) above, comprising 0.1 to 20% by mass of the layered silicate.
(3) The high-density polyethylene resin composition according to (1) or (2), wherein the layered silicate contains kaolin.
(4) A press-molded product obtained by press-molding the high-density polyethylene resin composition according to any one of (1) to (3).
(5) An injection-molded product obtained by injection-molding the high-density polyethylene resin composition according to any one of (1) to (3).
(6) The high-density polyethylene resin and the layered silicate are contained, the content of the layered silicate is 0.1 to 20% by mass, and the maximum spherulite size is 0.1 to 5 μm. The molded object which consists of a high-density polyethylene resin composition of any one of 1)-(3).
(7) The method for producing a high-density polyethylene resin composition according to any one of (1) to (3), comprising a step of melt-kneading a high-density polyethylene resin and a layered silicate.

  According to the present invention, it is possible to provide a high-density polyethylene resin composition that can impart transparency to a high-density polyethylene resin that is inherently opaque, and becomes a molded article having excellent rigidity, transparency, and visibility of contents. Can do. Further, according to the present invention, a simple and low-cost method for producing a high-density polyethylene resin composition can be realized.

It is a photograph which shows the result of a distance visibility test of the compression molding board shape | molded with the high density polyethylene resin A and B, and the compression molding board shape | molded with the high density polyethylene resin composition of Examples 1-5. It is a photograph which shows the result of a distance visibility test of the compression molding board shape | molded with the high density polyethylene resin CF and the compression molding board shape | molded with the high density polyethylene resin composition of Comparative Examples 1-9.

  DESCRIPTION OF EMBODIMENTS Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to this, and various modifications can be made without departing from the gist thereof. Is possible.

[High-density polyethylene resin composition]
The high density polyethylene resin composition of the present embodiment is
Including high density polyethylene resin and layered silicate,
The high-density polyethylene resin has spherulites, and the maximum size of the spherulites is 0.1 μm or more and 5 μm or less.

[High-density polyethylene resin]
The high density polyethylene resin composition according to this embodiment includes a high density polyethylene resin. Although this high-density polyethylene resin is not particularly limited, specifically, it can be produced by a vessel type slurry polymerization method using a Ziegler type catalyst, a Phillips type catalyst, or a supported geometrically constrained type single site catalyst. Among these, it is particularly preferable to use a Ziegler type catalyst or a supported geometrically constrained single site catalyst. The high-density polyethylene resin may be an ethylene homopolymer, a copolymer of ethylene and an α-olefin, or a mixture of the homopolymer and / or the copolymer with another polyethylene resin. Among these, a copolymer obtained by polymerizing ethylene and one or more comonomers selected from α-olefins having 3 to 20 carbon atoms in a ratio so as to obtain a desired density is preferable.

(density)
The density of the high-density polyethylene resin is preferably from 940 kg / m ^{3 to} 980 kg / m ^3, more preferably from 940 kg / m ^{3 to} 970 kg / m ³ , and even more preferably from 940 kg / m ^{3 to} 960 kg / m ³ . The density of the high-density polyethylene resin composition is determined according to the composition ratio of the high-density polyethylene resin and the layered silicate, considering that the density of the layered silicate is 2.58 kg / m ^3. Can be calculated. In addition, the density of a high density polyethylene resin can be measured by the method as described in an Example.

(Melt flow rate: MFR)
The melt flow (hereinafter referred to as “MFR”) of the high-density polyethylene resin is not particularly defined, but is 0.01 g / 10 min to 100 g / 10 min according to the measurement using the condition code D of JIS K7210. Preferably, 0.1-50 g / 10min is more preferable, and 1-10 g / 10min is further more preferable. In order to obtain a desired MFR, a molecular weight regulator such as hydrogen may be used during the polymerization. By making MFR into said preferable range, the high density polyethylene resin composition used as the molded object excellent in rigidity, transparency, and the visibility of the content is realizable.

(Method for producing high-density polyethylene resin)
As the high-density polyethylene resin of this embodiment, an ethylene homopolymer may be produced by a single-stage polymerization method using one polymerization vessel, and a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. Or a blend of these polymers with another polyethylene resin. Further, a low molecular weight component made of an ethylene homopolymer and a high molecular weight component made of a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms are separately polymerized, and they are mixed at a predetermined blending ratio. By blending, a powder blend or pellet blend of high-density polyethylene resin may be produced. Alternatively, the high-density polyethylene resin is obtained by a multi-stage polymerization method in which two or more polymerization devices connected in series sequentially polymerize or a method in which two or more polymerization devices connected in parallel simultaneously polymerize. You may manufacture by the method of blending a component and a high molecular weight component in a slurry state etc. Here, the low molecular weight component and the high molecular weight component indicate the relative level of the weight average molecular weight of the two types of polyethylene, and are not in a numerical range.

(Production method of Ziegler type catalyst)
Next, a method for producing a Ziegler type catalyst will be described. The Ziegler-type catalyst is a polymerization catalyst containing a solid catalyst component [A] and an organoaluminum compound [B]. Although it does not specifically limit as a preparation method of solid catalyst component [A], Preferably, the following methods are mentioned. First, 1 mol of organomagnesium (i) soluble in a hydrocarbon solvent represented by the formula (1) and 0.01 to 100 mol of a chlorosilane compound (ii) having a Si—H bond represented by the formula (2) are reacted. To obtain a solid (A-1a).
(Al) _α (Mg) _β (R ¹¹ ) _p (R ¹² ) _q (OR ¹³ ) _r ... Formula (1)
In [Equation ^{(1), R 11, R} 12 and ^{R 13} is a hydrocarbon group having 2 to 20 carbon atoms, α, β, p, q and r is a number satisfying the following relationship. 0 ≦ α, 0 <β, 0 ≦ p, 0 ≦ q, 0 ≦ r, p + q> 0, 0 ≦ r / (α + β) ≦ 2, 3α + 2β = p + q + r]
H _a SiCl _b R ¹⁴ _{4- (a + b)} Formula (2)
Wherein ^{(2), R 14} is a hydrocarbon group having 1 to 20 carbon atoms, a and b are numbers which satisfy the following relationship. 0 <a, 0 <b, a + b ≦ 4]

Next, the solid (A-1a) is reacted with alcohol (A-2) in an amount of 0.05 to 20 mol with respect to 1 mol of the C—Mg bond contained in the solid (A-1a). (A-1b) is obtained. Further, the solid (A-1b) is reacted with the organometallic compound (A-3) represented by the formula (3) to obtain a solid (A-1c).
AlR ¹⁵ _s Q _3-s (3)
[In the formula (3), R ¹⁵ is a hydrocarbon group having 1 to 20 carbon atoms, and Q is selected from the group consisting of OR ¹⁶ , OSiR ¹⁷ R ¹⁸ R ¹⁹ , NR ²⁰ R ²¹ , SR ²² and halogen. R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² are hydrogen atoms or hydrocarbon groups, and s is a number that satisfies the following relationship. 0 <s <3]

  Finally, the solid (A-1c) and the titanium compound (A-4) are reacted in the presence of the component (A-3) to obtain the solid catalyst component [A].

The organomagnesium compound (i) represented by the formula (1) is preferably a complex compound of organomagnesium that is soluble in a hydrocarbon solvent, and all of R ₂ Mg and complexes of these with other metal compounds. It is included. The relational expression of the symbols α, β, p, q, and r: 3α + 2β = p + q + r indicates the stoichiometry between the valence of the metal atom and the substituent. Here, R is a hydrocarbon group having 2 to 20 carbon atoms.

In the formula (1), the hydrocarbon group having 2 to 20 carbon atoms represented by R ¹¹ and R ¹² is not particularly limited, and specific examples thereof include an alkyl group, a cycloalkyl group, and an aryl group. Examples include methyl, ethyl, propyl, butyl, sec-butyl, amyl (pentyl), hexyl, heptyl, octyl, decyl, cyclohexyl, and phenyl groups. Among these, R ¹¹ is preferably an alkyl group.

  In formula (1), the ratio β / α of magnesium to aluminum is not particularly limited, but is preferably 0.1 to 30, more preferably 0.5 to 10.

Further, when α = 0, R ¹¹ is preferably sec-butyl or the like, whereby the organomagnesium compound (i) tends to be more soluble in a hydrocarbon solvent. In the formula (1), when α = 0, R ¹¹ and R ¹² satisfy any one of the following three groups (1), (2), and (3): Is preferred.

The group ^{(1), R 11, R} 12 at least one of, preferably a secondary or tertiary alkyl group having 4 to 6 carbon ^atoms, R ^{11, R 12} are both -C 4 It is more preferable that at least one is a secondary or tertiary alkyl group.

In the group (2), R ¹¹ and R ¹² are preferably alkyl groups having different carbon atoms, R ¹¹ is an alkyl group having 2 or 3 carbon atoms, and R ¹² has 4 carbon atoms. More preferably, it is the above alkyl group.

The group ^(3), it is preferred that at least one of R ^{11, R 12} is a hydrocarbon group having 6 or more carbon ^atoms, R ^{11, R 12} are both alkyl groups having 6 or more carbon atoms More preferred.

  In the group (1), the secondary or tertiary alkyl group having 4 to 6 carbon atoms is not particularly limited. Specifically, sec-butyl, tert-butyl, 2-methylbutyl, 2-ethyl Examples include propyl, 2,2-dimethylpropyl, 2-methylpentyl, 2-ethylbutyl, 2,2-dimethylbutyl, and 2-methyl-2-ethylpropyl. Among these, sec-butyl is preferable.

  In group (2), examples of the alkyl group having 2 or 3 carbon atoms include an ethyl group and a propyl group. Among these, an ethyl group is preferable. Further, the alkyl group having 4 or more carbon atoms is not particularly limited, and specific examples thereof include a butyl group, an amyl group, a hexyl group, and an octyl group. Of these, a butyl group and a hexyl group are preferable.

  In group (3), the hydrocarbon group having 6 or more carbon atoms is not particularly limited, and specific examples include a hexyl group, an octyl group, a decyl group, and a phenyl group. Among these, an alkyl group is preferable and a hexyl group is more preferable.

  In general, increasing the number of carbon atoms in an alkyl group tends to make it more soluble in a hydrocarbon solvent, but the solution tends to increase in viscosity, and it is preferable in terms of handling to use an alkyl group having a chain length as necessary. The organomagnesium compound (i) is used in the form of a hydrocarbon solution, but the solution may contain a trace amount of a complexing agent such as ether, ester or amine. The hydrocarbon solvent in which the organomagnesium compound (i) is soluble is not particularly limited, and specific examples thereof include inert hydrocarbon media such as hexane, heptane, cyclohexane, benzene, and toluene.

Next, the alkoxy group (OR ¹³ ) will be described. R ¹³ is a hydrocarbon group having 2 to 20 carbon atoms. The R ^13, is not particularly limited, specifically, preferably an alkyl group or an aryl group having 3 to 10 carbon atoms. Although it does not specifically limit as a C3-C10 alkyl group or an aryl group, Specifically, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, amyl, hexyl, 2-methylpentyl, 2-ethylbutyl, 2-ethylpentyl, 2-ethylhexyl, 2-ethyl-4-methylpentyl, 2-propylheptyl, 2-ethyl-5-methyloctyl, n-octyl, n-decyl, and A phenyl group etc. are mentioned. Among these, n-butyl, iso-butyl, sec-butyl, 2-methylpentyl, and 2-ethylhexyl are more preferable.

These organomagnesium compounds (i) include organomagnesium complexes. The organomagnesium compound (i) is not particularly limited. Specifically, the organomagnesium compound represented by the formula (4) and the organoaluminum compound represented by the formula (5) are mixed with hexane, heptane, cyclohexane, benzene. Or it can obtain by making it react at room temperature-150 degreeC in inert hydrocarbon media, such as toluene. In addition, if necessary, following this reaction, the hydrocarbyloxymagnesium compound having a hydrocarbon group represented by R ¹³ that is soluble in an alcohol having a hydrocarbon group represented by R ¹³ or a hydrocarbon solvent. And one or more compounds selected from the group consisting of hydrocarbyloxyaluminum compounds having a hydrocarbon group represented by R ¹³ can also be reacted.
R ¹¹ MgX and / or R ¹¹ ₂ Mg Formula (4)
(R ¹¹ is the same as described above, and X is halogen.)
AlR ¹² ₃ and / or AlR ¹² ₂ H Formula (5)
(R ¹² is the same as described above.)

Among these, when the organomagnesium compound (i) soluble in the hydrocarbon solvent and the alcohol having a hydrocarbon group represented by R ¹³ are reacted, the addition method is carried out in a solution of the organomagnesium compound (i). Any of the method of adding the alcohol to the alcohol, the method of adding the organomagnesium compound (i) to the alcohol, or the method of adding both at the same time can be used. Soluble organomagnesium compound in a hydrocarbon in the present embodiment and (i), the mixture ratio of the reaction of an alcohol having a hydrocarbon group represented by R ¹³ is not particularly limited. In the obtained organomagnesium compound (i) containing an alkoxy group, the range of the molar composition ratio r / (α + β) of the alkoxy group with respect to all metal atoms is 0 ≦ r / (α + β) ≦ 2, and 0 ≦ r / (Α + β) <1 is more preferable.

(Chlorosilane compound (ii))
Next, the chlorosilane compound (ii) having an Si—H bond used in the preparation of the solid catalyst component [A] will be described.

The chlorosilane compound (ii) is not particularly limited as long as it is represented by the formula (2). Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁴ in formula (2) is not particularly limited, specifically, aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbons Examples thereof include a hydrogen group, and examples thereof include a methyl group, ethyl group, butyl group, amyl group, hexyl group, decyl group, cyclohexyl group, and phenyl group. Among these, a C1-C10 alkyl group is preferable and lower alkyl groups, such as methyl, ethyl, and propyl, are more preferable. Further, a and b are numbers larger than 0 satisfying the relationship of a + b ≦ 4, and it is particularly preferable that b is 2 or 3.

Such chlorosilane compound (ii), is not particularly limited, _{specifically, HSiCl 3, HSiCl 2 CH 3} , HSiCl 2 C 2 H 5, HSiCl 2 (n-C 3 H 7), HSiCl 2 ( _{iso-C 3 H 7),} HSiCl 2 (n-C 4 H 9), HSiCl 2 C 6 H 5, HSiCl 2 (4-Cl-C 6 H 4), HSiCl 2 CH = CH 2, HSiCl 2 (CH ₂ C ₆ H ₅ ), HSiCl ₂ (1-C ₁₀ H ₇ ), HSiCl ₂ CH ₂ CH═CH ₂ , H ₂ SiClCH ₃ , H ₂ SiClC ₂ H ₅ , HSiCl (CH ₃ ) ₂ , HSiCl (C _{2 H 5) 2, HSiClCH 3 (} iso-C 3 H 7), HSiClCH 3 (C 6 H 5), and HSiCl _{(C 6} H _{5) 2,} etc. Is mentioned. Among these, HSiCl ₃ , HSiCl ₂ CH ₃ , HSiCl (CH ₃ ) ₂ , and HSiCl ₂ C ₂ H ₅ are preferable, and HSiCl ₃ and HSiCl ₂ CH ₃ are more preferable. A chlorosilane compound (ii) may be used individually by 1 type, or may use 2 or more types together.

  Next, the reaction between the organomagnesium compound (i) soluble in the hydrocarbon solvent and the chlorosilane compound (ii) will be described. In the reaction, it is preferable to dilute the chlorosilane compound (ii) in an inert reaction solvent beforehand. Although it does not specifically limit as an inert reaction solvent body, Specifically, n-hexane and aliphatic hydrocarbons, such as n-heptane; Aromatic hydrocarbons, such as benzene, toluene, and xylene; Cyclohexane, and methyl Examples thereof include alicyclic hydrocarbons such as cyclohexane; chlorinated hydrocarbons such as 1,2-dichloroethane, o-dichlorobenzene, and dichloromethane; ether-based media such as ether and tetrahydrofuran; or a mixed medium thereof. Among these, an aliphatic hydrocarbon medium is preferable in terms of catalyst performance. Although the reaction temperature is not particularly limited, it is preferably carried out at a temperature not lower than the boiling point of chlorosilane or not lower than 40 ° C. for the progress of the reaction. The compounding ratio at the time of reaction of organomagnesium compound (i) and chlorosilane compound (ii) is not particularly limited, but is usually 0.01 to 100 mol of chlorosilane compound (ii) with respect to 1 mol of organomagnesium compound (i). Is in the range of 0.1 to 10 mol of chlorosilane compound (ii) with respect to 1 mol of organomagnesium compound (i).

  Although it does not specifically limit as a reaction method, Specifically, the method of simultaneous addition which reacts, introducing organomagnesium compound (i) and chlorosilane compound (ii) into a reaction system simultaneously; chlorosilane compound (ii) is made beforehand. There is a method in which the organomagnesium compound (i) is introduced into the reaction system and then reacted while being introduced into the reaction system; or a method in which the organomagnesium compound (i) is charged in advance and the chlorosilane compound (ii) is added. . Among these, a method in which the chlorosilane compound (ii) is charged into the reaction system in advance and then reacted while introducing the organomagnesium compound (i) into the reaction system gives preferable results. The solid component (A-1a) obtained by the above reaction is separated by filtration or decantation, and then sufficiently washed with an inert solvent such as n-hexane or n-heptane, It is preferable to remove by-products and the like.

  The solid (A-1a) obtained as described above is further reacted with the alcohol (A-2). Although it does not specifically limit as alcohol (A-2) used in this case, Specifically, a C1-C20 saturated or unsaturated alcohol can be illustrated. Although it does not specifically limit as C1-C20 saturated or unsaturated alcohol, Specifically, methyl alcohol, ethyl alcohol, propyl alcohol, iso-propyl alcohol, butyl alcohol, iso-butyl alcohol, sec-butyl Examples thereof include alcohol, tert-butyl alcohol, n-amyl alcohol, iso-amyl alcohol, sec-amyl alcohol, tert-amyl alcohol, hexyl alcohol, cyclohexanol, phenol, and cresol. Among these, C3-C8 linear alcohol, iso-butyl alcohol, and iso-amyl alcohol are preferable. Alcohol (A-2) may be used individually by 1 type, and may use 2 or more types together.

  Next, the usage-amount of alcohol (A-2) is 0.05-20 mol with respect to 1 mol of C-Mg bonds contained in solid (A-1a), Preferably it is 0.1-10 mol, More preferably, it is 0. The range is from 2 to 8 mol. The reaction of the solid (A-1a) and the alcohol (A-2) can be performed in the presence or absence of an inert reaction medium. As the inert reaction medium, any of the above-described aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, chlorinated hydrocarbons, ether-based media, or mixed media thereof may be used. The temperature during the reaction is not particularly limited, but it is preferably carried out at room temperature to 200 ° C.

  Next, the solid (A-1b) obtained by the reaction of the solid (A-1a) and the alcohol (A-2) is preferably further treated with an organometallic compound (A-3) represented by the formula (3). ) To obtain a solid (A-1c).

  The organometallic compound (A-3) is not particularly limited, but specifically, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triiso-butylaluminum, tri-n-amylaluminum. , Triiso-amyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, and tri-n-decyl aluminum, etc .; diethylaluminum chloride, ethylaluminum dichloride, diiso-butylaluminum chloride, ethylaluminum sesquichloride And aluminum halides such as diethylaluminum bromide; alkoxyalumines such as diethylaluminum ethoxide and diiso-butylaluminum butoxide Miniumu; dimethylhydrosiloxy aluminum dimethyl, ethyl methyl hydro siloxy aluminum diethyl, and siloxy alkylaluminum such as ethyl dimethylsiloxy aluminum diethyl; and a mixture thereof. Among these, aluminum halide is preferable, and dimethylaluminum chloride, methylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, dipropylaluminum chloride, and dibutylaluminum chloride are more preferable. An organometallic compound (A-3) may be used individually by 1 type, and may use 2 or more types together.

  For the reaction between the solid (A-1b) and the organometallic compound (A-3), an inert reaction medium can be preferably used. Such an inert reaction medium is not particularly limited, and specific examples thereof include aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as benzene and toluene; fats such as cyclohexane and methylcyclohexane. And cyclic hydrocarbons. Of these, aliphatic hydrocarbons are preferred. As for the usage-amount of an organometallic compound (A-3), 0.5 mol or less is preferable with respect to 1 mol of C-Mg bonds contained in a solid component (A-1b), More preferably, it is 0.1 mol or less. Although it does not restrict | limit especially about reaction temperature, It is preferable to carry out in the range of room temperature-150 degreeC.

Next, the titanium compound (A-4) will be described. As the titanium compound, a titanium compound represented by the following formula (6) can be used.
Ti (OR ²³ ) _u X _4-u (6)
[Wherein u is a number of 0 ≦ u ≦ 4, R ²³ is a hydrocarbon group, and X is a halogen. ]

In the formula, u is a number of 0 ≦ u ≦ 4, and u is preferably 0. Examples of the hydrocarbon group denoted by R ^23, is not particularly limited, specifically, methyl, ethyl, propyl, butyl, amyl, hexyl, 2-ethylhexyl, heptyl, octyl, decyl, and aliphatic and allyl Examples thereof include hydrocarbon groups; alicyclic hydrocarbon groups such as cyclohexyl, 2-methylcyclohexyl, and cyclopentyl; aromatic hydrocarbon groups such as phenyl and naphthyl. Among these, an aliphatic hydrocarbon group is preferable. The halogen represented by X is not particularly limited, and specific examples include chlorine, bromine, and iodine. Of these, chlorine is preferred. The said titanium compound (A-4) may be used individually by 1 type, and may use 2 or more types together.

  For the reaction of the solid (A-1c) and the titanium compound (A-4), an inert reaction medium can be used. The inert reaction medium used here is not particularly limited, and specifically, aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as benzene and toluene; fats such as cyclohexane and methylcyclohexane. And cyclic hydrocarbons. Of these, aliphatic hydrocarbons are preferred. As for the usage-amount of a titanium compound (A-4), 0.5 mol or less is preferable with respect to 1 mol of C-Mg bonds contained in solid (A-1c), More preferably, it is 0.1 mol or less. Although there is no restriction | limiting in particular about reaction temperature, It is preferable to carry out in the range of room temperature-150 degreeC. In this reaction, the organometallic compound (A-3) can be present. In this case, the order of addition is when adding the titanium compound (A-4) following the organometallic compound (A-3); adding the organometallic compound (A-3) following the titanium compound (A-4). Cases: Any order of adding both simultaneously is possible. Among these, it is preferable to add the titanium compound (A-4) following the organometallic compound (A-3). In this case, the molar ratio between the organometallic compound (A-3) and the titanium compound (A-4) is preferably in the range of 0.5-2.

  The solid catalyst component [A] thus obtained is used as a slurry solution with an inert solvent. Although it does not specifically limit as an inert solvent, Specifically, Aliphatic hydrocarbons, such as hexane and heptane; Aromatic hydrocarbons, such as benzene, toluene, and xylene; Alicyclic rings, such as cyclohexane and methylcyclohexane Formula hydrocarbons; halogenated hydrocarbons such as 1,2-dichloroethane, carbon tetrachloride, and chlorobenzene, and the like.

  The organoaluminum compound [B] used together with the solid catalyst component [A] is not particularly limited, and specifically, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triiso- Trialkylaluminum such as butylaluminum, tri-n-amylaluminum, triiso-amylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and tri-n-decylaluminum; diethylaluminum chloride, ethylaluminum dichloride, diiso- Aluminum halides such as butylaluminum chloride, ethylaluminum sesquichloride, and diethylaluminum bromide; diethylaluminum ethoxide and diiso-butyl Alkoxyaluminum such as rualuminum butoxide; siloxyalkylaluminum such as dimethylhydrosiloxyaluminum dimethyl, ethylmethylhydrosiloxyaluminum diethyl, and ethyldimethylsiloxyaluminum diethyl; and mixtures thereof are used, especially trialkylaluminum achieves high activity Therefore, it is preferable.

(Polymerization method using Ziegler type catalyst)
The olefin polymerized in the Ziegler type catalyst system is not particularly limited, and specific examples include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1 -Hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, vinylcyclohexane and the like. Ethylene can be homopolymerized, or some of them can be combined and copolymerized. The solid catalyst component [A] and the organoaluminum compound [B] may be added into the polymerization system, or may be mixed in advance prior to polymerization. The ratio of the solid catalyst component [A] to the organoaluminum compound [B] is defined by the molar ratio of Ti in the solid catalyst component [A] and Al in the organoaluminum compound [B], preferably Al /Ti=0.3-1000.

  Although it does not specifically limit as a polymerization solvent, The hydrocarbon solvent normally used for slurry polymerization can be used. Although it does not specifically limit as a hydrocarbon solvent, Specifically, Aliphatic hydrocarbons, such as hexane and heptane; Aromatic hydrocarbons, such as benzene, toluene, and xylene; Alicyclic rings, such as cyclohexane and methylcyclohexane Formula hydrocarbons; or mixtures thereof. The polymerization temperature can usually be in the range of room temperature to 100 ° C, preferably 50 ° C to 90 ° C. The polymerization pressure can be in the range of normal pressure to 100 atm. The molecular weight of the resulting polymer can be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature.

(Method for producing supported geometrically constrained single-site catalyst)
Next, the supported geometrically constrained single site catalyst will be described. The supported geometrically constrained single site catalyst (hereinafter also referred to as “metallocene supported catalyst”) used in the above polymerization method is (a) a carrier material, (b) organoaluminum, and (c) a cyclic η-binding anion. It is prepared from a transition metal compound having a ligand and (d) an activator capable of reacting with the transition metal compound having the cyclic η-bonding anion ligand to form a complex that exhibits catalytic activity. (U) The use of titanium as a transition metal atom in a transition metal compound having a cyclic η-bonding anion ligand is described in JP-A-11-166209.

The carrier substance (a) is not particularly limited and may be either an organic carrier or an inorganic carrier. The organic carrier is not particularly limited. Specifically, polyethylene, polypropylene, polybutene-1, ethylene / propylene copolymer, ethylene / hexene-1 copolymer, propylene / butene-1 copolymer, and Polymer of α-olefin having 2 to 20 carbon atoms such as ethylene / hexene-1 copolymer; aromatic unsaturated hydrocarbon copolymer such as polystyrene and styrene / divinylbenzene copolymer; polyacrylate, Examples thereof include polar group-containing polymer polymers such as polymethacrylic acid ester, polyacrylonitrile, polyvinyl chloride, polyamide, and polycarbonate. The inorganic carrier is not particularly limited, _{specifically, SiO 2, Al 2 O 3} , MgO, TiO 2, B 2 O 3, CaO, ZnO, BaO, ThO, SiO 2 -MgO, SiO 2 -Al Inorganic oxides such as ₂ O ₃ , SiO ₂ —MgO, and SiO ₂ —V ₂ O ₅ ; Inorganic halogen compounds such as MgCl ₂ , AlCl ₃ , MnCl ₂ ; Na ₂ CO ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) _{2 and} other inorganic carbonates, sulfates or nitrates; Mg (OH) ₂ , Al (OH) ₃ , Ca (OH) ) Hydroxides such as ₃ are exemplified. Among these, a more preferable carrier is SiO ₂ .

  The particle size of the carrier is not particularly limited, but is generally 1 μm to 3000 μm. From the viewpoint of particle dispersibility, the particle size distribution is preferably in the range of 10 to 1000 μm. The particle diameter can be measured with a laser diffraction particle size distribution measuring apparatus using a flow cell.

The carrier material is treated with (a) an organoaluminum compound as necessary. Although it does not specifically limit as an organoaluminum compound, Specifically, the linear polymer shown by following formula (7), a cyclic polymer, etc. are mentioned. Here, R is not particularly limited, and specific examples thereof include a methyl group, an ethyl group, and an isobutylethyl group. Examples of such (a) organoaluminum compounds include methylalumoxane, ethylalumoxane, and isobutylethylalumoxane.
(-Al (R) O-) _n (7)
[Wherein, R is a hydrocarbon group having 1 to 10 carbon atoms, including those partially substituted with a halogen atom and / or an RO group. n is the degree of polymerization and is 5 or more, preferably 10 or more. ]

  Furthermore, other (a) organoaluminum compounds are not particularly limited, and specifically, trialkylaluminum, dialkylhalogenoaluminum, sesquialkylhalogenoaluminum, armenylaluminum, dialkylhydroaluminum, sesquialkylhydroaluminum, and the like. Is mentioned.

  More specifically, as the other (a) organoaluminum compounds, trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, and trioctylaluminum; dimethylaluminum chloride and diethylaluminum chloride Dialkyl halogeno aluminums such as sesquimethyl aluminum chloride and sesquialkyl halogeno aluminums such as sesquiethyl aluminum chloride; armenyl aluminums such as ethyl aluminum dichloride; Sesquialkyl such as hydride It can be exemplified Hydro Aluminum. Among these, trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminum hydride, and diisobutylaluminum hydride are more preferable.

The supported catalyst is not particularly limited. Specifically, the supported catalyst may include (c) a transition metal compound having a cyclic η-bonding anion ligand represented by the following formula (8).
L ₁ MX _p X ′ _q (8)

In the formula (8), M is a group 4 transition metal of a long-period periodic table having an oxidation number of +2, +3, or +4 and having an η ⁵ bond with one or more ligands L. Titanium is preferred as the transition metal.

  In formula (8), L is a cyclic η-bonding anion ligand, and is not particularly limited. Specifically, each of them independently represents a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, a fluorenyl group. , Tetrahydrofluorenyl group, and octahydrofluorenyl group. These groups are hydrocarbon groups containing up to 20 non-hydrogen atoms, halogens, halogen-substituted hydrocarbon groups, aminohydrocarbyl groups, hydrocarbyloxy groups, dihydrocarbylamino groups, dihydrocarbylphosphino groups, silyl groups. , An aminosilyl group, a hydrocarbyloxysilyl group, and a halosilyl group, each of which may optionally have 1 to 8 substituents, and further, two L's may contain up to 20 non-hydrogen atoms. It may be bound by a divalent substituent such as carbadiyl, halohydrocarbadiyl, hydrocarbyleneoxy, hydrocarbyleneamino, diladiyl, halosiladiyl, and aminosilane.

  In the formula (8), each X is independently a monovalent anionic σ-bonded ligand having up to 60 non-hydrogen atoms; Or a divalent anion σ-bonded ligand that binds to M and L with one valence each.

  In Formula (8), X ′ is a neutral Lewis base coordination compound selected from the group consisting of phosphine, ether, amine, olefin, and conjugated diene each independently having 4 to 40 carbon atoms.

  In the formula (8), l is an integer of 1 or 2. p is an integer of 0, 1 or 2, and X is a monovalent anionic σ-bonded ligand or a divalent anionic σ-bonded coordination which binds to M and L each with a single valence. When it is a child, p is 1 or more less than the formal oxidation number of M; or when X is a divalent anionic σ-bonded ligand that binds to M in a divalent manner, p is the formal oxidation number of M. It is preferable that it is less than 1 + 1. Q is 0, 1 or 2. The transition metal compound (c) is preferably 1 = 1 in the formula (8).

For example, a suitable example of the transition metal compound (c) is represented by the formula (9).

  In the formula (9), M is titanium, zirconium or hafnium having a formal oxidation number of +2, +3 or +4, and titanium is particularly preferable.

In formula (9), each R ³ is independently hydrogen, a hydrocarbon group, a silyl group, a germyl group, a cyano group, a halogen, or a composite group thereof, each having up to 20 non-hydrogen atoms. be able to. Further, adjacent R ³ may be cyclic by forming a divalent derivative such as hydrocarbadiyl, diradii, or germaniyl.

  In formula (9), each X ″ is independently a halogen, a hydrocarbon group, a hydrocarbyloxy group, a hydrocarbylamino group, or a silyl group, each having up to 20 non-hydrogen atoms, and two X "May form a neutral conjugated diene having 5 to 30 carbon atoms, or a divalent derivative.

In the formula (9), Y is, -O -, - S -, - NR * -, - PR * - a and, Z is ^{_{SiR * 2, CR * 2,}} SiR * 2 SiR * 2, CR * 2 CR ^* ₂ , CR ^* = CR ^* , CR ^* ₂ SiR ^* ₂ or GeR ^* ₂ . Here, each R ^* is independently an alkyl group or aryl group having 1 to 12 carbon atoms. N is an integer of 1 to 3.

Furthermore, as a transition metal compound (c), a more suitable example is represented by following formula (10) and following formula (11).

In formulas (10) and (11), each R ³ is independently hydrogen, a hydrocarbon group, a silyl group, a germyl group, a cyano group, a halogen, or a composite group thereof, each of up to 20 non-hydrogen atoms. Can have. The transition metal M is titanium, zirconium or hafnium, with titanium being preferred.

  In the formulas (10) and (11), the definitions of Z, Y, X and X ′ are as described above. In formulas (10) and (11), p is 0, 1 or 2, and q is 0 or 1. However, when p is 2 and q is 0, the oxidation number of M is +4, and X is halogen, hydrocarbon group, hydrocarbyloxy group, dihydrocarbylamino group, dihydrocarbyl phosphide group, hydrocarbyl sulfide group, silyl group A group or a combination thereof, having up to 20 non-hydrogen atoms.

  In the formulas (10) and (11), when p is 1 and q is 0, the oxidation number of M is +3, and X is an allyl group, 2- (N, N-dimethylaminomethyl) phenyl group Or a stabilized anionic ligand selected from 2- (N, N-dimethyl) -aminobenzyl groups, or an oxidation number of M of +4 and X is a derivative of a divalent conjugated diene. Alternatively, it is preferable that M and X together form a metallocyclopentene group.

In the formulas (10) and (11), when p is 0 and q is 1, the oxidation number of M is +2, and X ′ is a neutral conjugated or non-conjugated diene and is arbitrarily selected. It may be substituted with the above hydrocarbons, and X ′ may contain up to 40 carbon atoms and forms a π-type complex with M. Furthermore, in this embodiment, the most suitable example as a transition metal compound (c) is represented by the following formula (12) and the following formula (13).

In formulas (12) and (13), each R ³ is independently hydrogen or an alkyl group having 1 to 6 carbon atoms. Further, M is titanium, Y is ^{-O -, - S -, -} NR * -, - PR * - a and, ^{Z *} is _{^{SiR * 2, CR * 2,}} SiR * 2 SiR * 2, CR * ₂ CR ^* ₂ , CR ^* = CR ^* , CR ^* ₂ SiR ₂ or GeR ^* ₂ , wherein R ^* is independently hydrogen, or a hydrocarbon group, a hydrocarbyloxy group, a silyl group, a halogenated alkyl group, A halogenated aryl group or a composite group thereof. The R ^* may have up to 20 non-hydrogen atoms, even it the R ^* is an annular R ^* and in Y medium Z ^* 2 one R ^* s or Z Medium ^* optionally Good.

  In the formulas (12) and (13), p is 0, 1 or 2, and q is 0 or 1. However, when p is 2 and q is 0, the oxidation number of M is +4, and X is each independently a methyl group or a hydrobenzyl group.

  In the formulas (12) and (13), when p is 1 and q is 0, whether the oxidation number of M is +3 and X is a 2- (N, N-dimethyl) -aminobenzyl group Or the oxidation number of M is +4 and X is 2-butene-1,4-diyl.

  In the formulas (12) and (13), when p is 0 and q is 1, the oxidation number of M is +2, and X ′ is 1,4-diphenyl-1,3-butadiene or 1,3 -Pentadiene.

  The dienes are examples of asymmetric dienes that form metal complexes, and are actually mixtures of geometric isomers.

  Further, the metallocene-supported catalyst includes (d) an activator capable of forming a complex that reacts with a transition metal compound and exhibits catalytic activity. Usually, in a metallocene supported catalyst, the complex formed by the transition metal compound (c) and the activator (d) exhibits a high olefin polymerization activity as a catalytically active species.

Examples of the activator (d) include a compound represented by the following formula (14).
[L−H] ^{d +} [M _m Q _t ] ^d− (14)
However, in formula (14), [L-H] ^{d +} is a proton-provided Bronsted acid, and L is a neutral Lewis base. Also, [M _m Q _t] ^d- is a noncoordinating anion compatible, M is a metal or metalloid selected from the 5 to Group 15 of the periodic table, Q is each hydrido independently, dialkyl An amide group, a halide, an alkoxide group, an allyloxide group, a hydrocarbon group, and a substituted hydrocarbon group having up to 20 carbon atoms; Moreover, Q which is a halide is 1 or less. m is an integer of 1 to 7, t is an integer of 2 to 14, d is an integer of 1 to 7, and t−m = d.

A more preferred example of the activator (d) is a compound represented by the following formula (15).
[L−H] ^{d +} [M _m Q _w (G _u (T−H) _r ) _z ] ^d− (15)
However, in formula (15), [L-H] ^{d +} is a proton-provided Bronsted acid, and L is a neutral Lewis base. _{Also, [M m Q w (G} u (T-H) r) z] is a non-coordinating anion of ^d- is compatible metal or metalloid M is selected from the 5 to Group 15 of the periodic table And Q is each independently a hydride, dialkylamide group, halide, alkoxide group, allyloxide group, hydrocarbon group, substituted hydrocarbon group having up to 20 carbon atoms, and Q which is a halide is 1 or less. G is a polyvalent hydrocarbon group having a valence of r + 1 bonded to M and T, T is O, S, NR or PR, and R is a hydrocarbyl group, a trihydrocarbylsilyl group, a trihydrocarbylgermanium group. Or hydrogen. Moreover, m is an integer of 1-7, w is an integer of 0-7, u is an integer of 0 or 1, r is an integer of 1-3, z is an integer of 1-8. , W + z−m = d.

A more preferred example of the activator (d) is a compound represented by the following formula (16).
[L-H] ⁺ [BQ ₃ Q ^* ] ⁻ (16)

However, in formula (16), [L-H] ^{d +} is a proton-provided Bronsted acid, and L is a neutral Lewis base. [BQ ₃ Q ^* ] ⁻ is a compatible non-coordinating anion, B is a boron atom, Q is a pentafluorophenyl group, and Q ^* has 6 to 6 carbon atoms having one OH group as a substituent. 20 substituted aryl groups.

  Although it does not specifically limit as a non-coordinating anion, Specifically, a triphenyl (hydroxyphenyl) borate, a diphenyl- di (hydroxyphenyl) borate, a triphenyl (2, 4- dihydroxyphenyl) borate, a tri (p -Tolyl) phenyl (hydroxyphenyl) borate, tris (pentafluorophenyl) (hydroxyphenyl) borate, tris (2,4-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5-dimethylphenyl) (hydroxyphenyl) Borate, tris (3,5-di-trifluoromethylphenyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (2-hydroxyethyl) borate, tris (pentafluorophenyl) (4-hydroxybutyl) borate Tris (pentafluorophenyl) (4-hydroxy-cyclohexyl) borate, tris (pentafluorophenyl) (4- (4′-hydroxyphenyl) phenyl) borate, and tris (pentafluorophenyl) (6-hydroxy-2-naphthyl) ) Borate and the like. Of these, tris (pentafluorophenyl) (hydroxyphenyl) borate is more preferable.

  Other preferable compatible non-coordinating anions are not particularly limited, and specific examples include borates in which the hydroxy group of the borate exemplified above is replaced with NHR. R is preferably a methyl group, an ethyl group or a tert-butyl group.

  Further, the proton-providing Bronsted acid is not particularly limited, but specifically, triethylammonium, tripropylammonium, tri (n-butyl) ammonium, trimethylammonium, tributylammonium, tri (n-octyl) ammonium. , Diethylmethylammonium, dibutylmethylammonium, dibutylethylammonium, dihexylmethylammonium, dioctylmethylammonium, didecylmethylammonium, didodecylmethylammonium, ditetradecylmethylammonium, dihexadecylmethylammonium, dioctadecylmethylammonium, diico Trialkyl group-substituted ammonium such as silmethylammonium and bis (hydrogenated tallow alkyl) methylammonium And N, N-, such as N, N-dimethylanilinium, N, N-diethylanilinium, N, N-2,4,6-pentamethylanilinium, N, N-dimethylbenzylanilinium and the like. Dialkylanilinium cations are preferred.

(Polymerization method using supported geometrically constrained single-site catalyst)
The olefin that is polymerized in the supported geometrically constrained single site catalyst system is not particularly limited, and specific examples include ethylene and α-olefins having 3 to 20 carbon atoms. Although it does not specifically limit as a C3-C20 alpha-olefin, Specifically, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1- pentene, 1-octene, 1 -Decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, vinylcyclohexane and the like can be mentioned, and some of them can be combined and copolymerized.

  As the polymerization solvent, a hydrocarbon solvent usually used in slurry polymerization can be used. Specifically, aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as benzene, toluene and xylene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; or a mixture thereof is used. . The polymerization temperature can be in the range of room temperature to 100 ° C, preferably 50 ° C to 90 ° C. The polymerization pressure can be in the range of normal pressure to 100 atm. The molecular weight of the resulting polymer can be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature.

  In this embodiment, it is preferable to use a high density polyethylene resin polymerized by a supported geometrically constrained single site catalyst rather than a Ziegler type catalyst.

[Layered silicate]
The high-density polyethylene resin composition of the present embodiment preferably contains 0.1% by mass or more and 20% by mass or less of layered silicate. The “layered silicate” used in the present embodiment refers to a silicate in which a sheet in which metal ions and silicic acid are connected is formed in a layer shape. The layered silicate is not particularly limited, but specifically, kaolin, lizardite, amesite, keriaite, burcherin, greenerite, nepoite, brindriaite, fraponite, odynite, cronstedite, percolite, kaori. Knight, Dickite, Nacrite, Halloysite, Antigolite, Chrysotile, Talc, Willemsite, Pyrophyllite, Saponite, Hectorite, Sauconite, Stevensite, Sinholderite, Montmorillonite, Bidelite, Nontrolite, Volconcoreite, Vermiculite , Biotite, phlogopite, iron mica, east knight, sericite, polylysionite, muscovite, sericite, celadonite, tobe mica, soda mica, and the like. The layered silicate often contains water between the layers, but is preferably subjected to a baking treatment. Among these, the layered silicate preferably contains kaolin.

  Further, the layered silicate is preferably pulverized after firing, in particular, the average particle size after pulverization is preferably 0.2 μm or more and 5.0 μm or less, and 0.5 μm or more and 2.0 μm or less. Some are more preferable, and those having a thickness of 1.0 μm to 2.0 μm are more preferable. When it is 0.2 μm or more, the transparency tends to be more excellent, and when it is 5.0 μm or less, the inhibition of transparency by the particles of the silicate itself also tends to be reduced. A more preferable form is one obtained by baking and pulverizing hydrous kaolin. The average particle diameter can be measured using a laser diffraction scattering method.

  The content of the layered silicate in the high-density polyethylene resin composition is preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 10% by mass or less, Preferably they are 1 mass% or more and 5 mass% or less. When the content is 0.1% by mass or more, the effect of improving transparency tends to appear more. When the content is 20% by mass or less, a decrease in transparency due to the particles of the layered silicate itself tends to be suppressed. .

[Maximum size of spherulites]
The high density polyethylene resin composition of the present embodiment has spherulites of a high density polyethylene resin, and the maximum size of the spherulites is 0.1 μm or more and 5 μm or less. When the maximum size of the spherulites is 5 μm or less, the scattering of visible light can be suppressed and transparency can be imparted. The size of the spherulite is preferably 0.5 μm or more and 4 μm or less, more preferably 1 μm or more and 3 μm or less.

  In the growth process of high-density polyethylene resin spherulites, after nucleation, the spherulites grow, and when they hit the next spherulites, the spherulite growth stops and another spherulite fills the gap. The spherulite size is not uniform. Further, in press molded products, injection molded products, and the like, the spherulite size is different between the vicinity of the surface of the molded product and the central part, and the spherulite size of the central part that is gradually cooled tends to increase. Transparency is affected by the maximum size of the spherulite in the molded product, so the spherulite size is observed by observing the central part of the molded product with a polarizing microscope and obtaining the maximum spherulite size. Do. In more detail, the maximum size of the spherulite can be obtained by the method described in the examples.

  The maximum size of the spherulite is not particularly limited, but can be controlled by the cooling rate of the high-density polyethylene resin composition or the molded body made of the high-density polyethylene resin composition. Specifically, when the cooling rate is decreased, the maximum size of the spherulites tends to increase, and when the cooling rate is increased, the maximum size of the spherulites tends to decrease. In the so-called film having a thickness of several hundred μm or less, spherulites can be refined by rapid cooling throughout, but the resin thickness is reduced to 100 μm in compression molding, injection molding, other extrusion molding, blow molding, etc. Therefore, since polyethylene resin has poor thermal conductivity, it tends to be gradually cooled at the center of the wall thickness to increase spherulites.

〔transparency〕
The transparency of the high-density polyethylene resin composition and the molded product thereof can be evaluated by the parallel light transmittance (τp) and haze (H). Specifically, a flat plate obtained by compression-molding the high-density polyethylene resin composition and the molded body thereof to a thickness of 0.7 mm according to JIS K7151 can be measured with a haze meter. More specifically, it can be measured by the method described in the examples.

In the high density polyethylene resin composition, the haze is preferably 90 or less, more preferably 88 or less, still more preferably 86 or less, and particularly preferably 80 or less. In the high-density polyethylene resin composition, the parallel light transmittance is preferably 8 or more, more preferably 10 or more, still more preferably 13 or more, and particularly preferably 15 or more.
H ≦ 99
τp ≧ 1

In the molded article of the high-density polyethylene resin composition, the haze and parallel light transmittance preferably satisfy the following formula. In the molded article of the high-density polyethylene resin composition, the haze is preferably 87 or less, more preferably 85 or less, still more preferably 83 or less, and particularly preferably 80 or less. In the molded article of the high-density polyethylene resin composition, the parallel light transmittance is preferably 10 or more, more preferably 13 or more, and further preferably 15 or more.
H ≦ 87
τp ≧ 10

  High-density polyethylene resin is generally opaque because spherulites due to crystals grow large, and generally has a haze of 90 or more and a parallel light transmission of less than 10. Furthermore, since the crystallinity increases as the density of the polyethylene resin increases, the haze increases and the parallel light transmission amount tends to decrease as the density increases.

However, the parallel light transmittance of the high-density polyethylene resin before adding the layered silicate is (τp ₀ ), the haze is (H ₀ ), the parallel light transmittance after the addition is (τp), and the haze is (H ), It is preferable that the relationship between the parallel light transmittance and the haze before and after the addition satisfy the following relationship.
H−H ₀ ≦ −1
τp−τp ₀ ≧ 1

In general, when an opaque layered silicate is added to a polyethylene resin, the parties understand that the haze is worse than the original polyethylene resin and the parallel light transmittance is reduced, and H−H ₀ ≧ 0 and τp−τp ₀ ≦ Should be zero. However, when the specific high-density polyethylene resin and layered silicate described in this embodiment are used, the transparency is improved, the haze is lowered, and the parallel light transmittance is increased. Further, when comparing before and after the addition of the specific layered silicate, it is preferable that H−H ₀ ≦ −1, τp−τp ₀ ≧ 1, and more preferably H−H ₀ ≦ −4, τp. −τp ₀ ≧ 3, more preferably H−H ₀ ≦ −7, τp−τp0 ≧ 6, and particularly preferably H−H ₀ ≦ −10 and τp−τp ₀ ≧ 8.

  As described above, it is generally known that the high density polyethylene resin is opaque at a certain thickness or more, but the haze is reduced and the parallel light transmittance is improved by the present embodiment, so that the distant through the flat plate can be improved. Since it becomes visibility and becomes a polyethylene resin composition which has transparency, it is preferred.

(Other additives)
In the resin composition of the present embodiment, an antioxidant, an antiblocking agent, an antistatic agent, a lubricant, a weathering agent, a light stabilizer, an ultraviolet ray, and the like, which are usually blended as additives in the resin composition as necessary. It may contain known additives such as an absorbent, an inorganic / organic filler, an organic peroxide, and a neutralizing agent.

  Although it does not specifically limit as antioxidant, Specifically, a hindered phenol type compound, a phosphorus type compound, a sulfur type compound, etc. are mentioned.

  Although it does not specifically limit as an antiblocking agent, Specifically, inorganic solid fine powders, such as a talc, a silica, and kaolinite, etc. are mentioned.

  The antistatic agent is not particularly limited, and specifically, nonionic antistatic agents such as alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type cationic antistatic agents, polyoxyethylene sorbitan monostearate and the like. Agents, betaine amphoteric antistatic agents, and the like.

  The lubricant is not particularly limited, and specifically, fatty acid hydrocarbon lubricants such as ethylene bissteramide, butyl stearate, polyethylene wax, paraffin wax, higher fatty acid lubricants, fatty acid amide lubricants, fatty acid ester lubricants, etc. Is mentioned.

  The weathering agent is not particularly limited, and specific examples include resorcinol compounds, salicylate compounds, benzotriazole compounds, benzophenone compounds, hindered amine compounds, and the like.

  The light stabilizer is not particularly limited, and specific examples include hindered amine compounds, benzotriazole compounds, triazine compounds, benzophenone compounds, benzoate compounds, and the like.

  Although it does not specifically limit as a ultraviolet absorber, Specifically, a benzotriazole type compound, a triazine type compound, a benzophenone type compound etc. are mentioned.

  Although it does not specifically limit as an inorganic filler, Specifically, a fibrous, powder particle form, plate shape, and a hollow filler are used.

  The fibrous filler is not particularly limited, and specifically, glass fiber, carbon fiber, silicone fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, Furthermore, inorganic fibers, such as metal fibers, such as stainless steel, aluminum, titanium, copper, and brass, are mentioned. In addition, whiskers such as potassium titanate whisker and zinc oxide whisker having a short fiber length are included.

  The powder particulate filler is not particularly limited, and specifically, silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, clay, diatomaceous earth, wollastonite such as silicate, oxidation Metal oxides such as iron, titanium oxide and alumina, metal sulfates such as calcium sulfate and barium sulfate, carbonates such as magnesium carbonate and dolomite, other silicon carbide, silicon nitride, boron nitride, various metal powders, etc. .

  The plate filler is not particularly limited, and specific examples include mica, glass flakes, and various metal foils.

  Although it does not specifically limit as a hollow filler, Specifically, a glass balloon, a silica balloon, a shirasu balloon, a metal balloon etc. are mentioned. These fillers can be used alone or in combination of two or more. These fillers can be used either surface-treated or unsurface-treated, but in some cases, surface-treated ones are preferable from the viewpoint of smoothness of the molding surface and mechanical properties. A conventionally well-known thing can be used as a surface treating agent. For example, various coupling treatment agents such as silane, titanate, aluminum, and zirconium can be used. Specifically, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, isopropyl trisstearoyl titanate, diisopropoxyammonium ethyl acetate, n-butyl zirconate, etc. Can be mentioned.

  The organic filler is not particularly limited, and specific examples thereof include raw starch, processed starch, pulp, chitin / chitosan, coconut shell powder, bamboo powder, bark powder, and powders such as kenaf and straw.

  The organic peroxide is not particularly limited, and specific examples thereof include diacyl peroxides, ketone peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, and peroxycarbonates. And the like.

  Although it does not specifically limit as a neutralizing agent, Specifically, various stearic acid metal salts, hydrotalcite, etc. are mentioned.

[Method for producing high-density polyethylene resin composition]
The manufacturing method of the high-density polyethylene resin composition of this embodiment includes the process of melt-kneading a high-density polyethylene resin and a layered silicate. The melt-kneading method is not particularly limited, and usual mixing methods such as a powder state, a slurry state, and a pellet state are used. Kneading is performed with a single-screw or twin-screw extruder, a kneader, or the like, but it is preferable to use a twin-screw extruder from the viewpoint of dispersibility.

[Molded body]
The high-density polyethylene resin composition of this embodiment can be made into various molded products. For example, the molded body according to this embodiment includes a press-molded product formed by press-molding the high-density polyethylene resin composition, or an injection-molded product formed by injection-molding the high-density polyethylene resin composition.

  Further, the molded body of the present embodiment includes a high-density polyethylene resin and a layered silicate, the content of the layered silicate is 0.1 to 20% by mass, and the maximum spherulite size is 0.1 μm or more. It can also consist of the said high-density polyethylene resin composition which is 5 micrometers or less. When the maximum size of the spherulites is 5 μm or less, the scattering of visible light can be suppressed and transparency can be imparted. The size of the spherulite is preferably 0.5 μm or more and 4 μm or less, more preferably 1 μm or more and 3 μm or less.

[Molding method of molded body]
There is no restriction | limiting in particular as a shaping | molding method at the time of shape | molding the resin composition of this embodiment to a container etc., The method generally known can be used. As such a molding method, for example, molding methods such as water-cooled or air-cooled inflation molding, blow molding, extrusion molding, rotational molding, injection molding, injection blow molding, and biaxial stretch blow molding are used.

  The method obtained by rolling a high-density polyethylene resin, which is a conventional technology, is limited to a thin sheet, and a molded product having a complicated shape such as a container could not be obtained. By using a product, it has become possible to obtain molded articles such as containers having transparency.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples and the like. In the present invention, the following examples, and comparative examples, the symbols and measurement methods shown are as follows.

(1) MFR (MFRD) of code D:
The MFR of the polyethylene resin represents the melt index, and was measured according to JIS K7210 at a temperature of 190 ° C. and a load of 2.16 kg. The unit is g / 10 min.

(2) Density:
The density of the polyethylene resin was measured according to JIS K7112. The unit is kg / m ³ .

(3) Tensile modulus:
The tensile elastic modulus is obtained by molding a high-density polyethylene resin or a high-density polyethylene resin composition into a 0.7 mm-thick compression molded plate at 190 ° C. in accordance with JIS K7151, and from this compression-molded plate in accordance with JIS K7161. A dumbbell specimen was prepared and measured. The unit is MPa.

(4) Haze:
Haze was measured according to JIS K7136 using the compression molded plate produced in (3) above and using Murakami Color Research Laboratory Haze Meter HM-500. The unit is%. In addition, the haze of the high density polyethylene resin was expressed as H _0, and the haze of the high density polyethylene resin composition was expressed as H. In Tables 2 and 3, the difference between the haze of the high-density polyethylene resin and the haze of the high-density polyethylene resin composition is indicated by “H−H ₀ ”.

(5) Parallel light transmittance (τp):
The parallel light transmittance was measured according to JIS K7105, using the compression molded plate prepared in (3) above, using the same apparatus as in (4) above. The unit is%. The parallel light transmittance of the high-density polyethylene resin was expressed as τp _0, and the parallel light transmittance of the high-density polyethylene resin composition was expressed as τp. In Tables 2 and 3, the difference between the parallel light transmittance of the high-density polyethylene resin and the parallel light transmittance of the high-density polyethylene resin composition is indicated by “τp−τp ₀ ”.

(6) Maximum spherulite size:
Using the compression molded plate molded in (3) above, a thin film was cut out from the central portion of the thickness of the cross section of the compression molded plate. The thin film was observed at 400 times using an optical polarization microscope. Ten thin films in the center were observed, and the diameter of the largest spherulite was measured in the observation range to obtain the largest spherulite size.

(7) Distant visibility:
A photograph was taken of a fluorescent lamp 2 meters ahead through the compression-molded plate molded in (3) above. When the shape of the fluorescent lamp is clearly understood, it is assumed that there is far visibility (○). When the shape is not clear, it is not far visibility (×). When the shape is known but cannot be clearly seen, the far visibility is incomplete. (△).

[High-density polyethylene resin A]
6.2 g (8.8 mmol) of triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate was added to 4 L of toluene and stirred at 90 ° C. for 30 minutes. Next, 40 mL of a 1 mol / L trihexylaluminum toluene solution was added to this solution and stirred at 90 ° C. for 1 minute. On the other hand, silica (Japan, manufactured by Fuji Silysia Co., Ltd .: trade name P-10) was treated with a nitrogen stream at 500 ° C. for 3 hours, and the treated silica was placed in 1.7 L of toluene and stirred. The toluene solution of triethylammonium tris (pentafluorophenyl) (4-hydroxyphenyl) borate and trihexylaluminum was added to the silica slurry solution and stirred at 90 ° C. for 3 hours.

Next, 206 mL of a 1 mol / L trihexylaluminum toluene solution was added to the silica slurry solution, and the mixture was further stirred at 90 ° C. for 1 hour. Thereafter, the supernatant was decanted with 90 ° C. toluene to remove excess trihexylaluminum. 0.218 mol / L of deep purple titanium (N-1,1-dimethylethyl) dimethyl (1- (1,2,3,4,5, -eta) -2,3,4,5-tetramethyl- 2,4-cyclopentadien-1-yl) silanaminate) ((2-) N)-(η ⁴ -1,3-pentadiene) (USA, Exxon Chemical Co., Ltd., trade name: ISOPARME) 20 mL of the solution was added to the above mixture. In addition, the mixture was stirred for 3 hours to obtain a green supported catalyst. A part of the obtained supported catalyst was put into a 1.5 L reactor together with 0.8 L of hexane dehydrated and deoxygenated. The temperature inside the container was set to 77 ° C. and the mixed gas ratio of ethylene, 1-butene and hydrogen was adjusted, the ratio of 1-butene was 0.43%, hydrogen was 2600 ppm, and the total pressure was 0.8 MPa. By supplying a mixed gas having the above composition, polymerization was carried out for 2 hours while maintaining a total pressure of 0.8 MPa to obtain a high-density polyethylene resin A powder. Evaluation of said (1)-(7) was performed about the obtained powder. The evaluation results are shown in Table 1.

[High-density polyethylene resin B]
Polymerization is carried out in the same manner as in the above high-density polyethylene resin A except that the temperature in the container is 70 ° C., 1-butene is 0.2%, and hydrogen is 2690 ppm. It was. Evaluation of said (1)-(7) was performed about the obtained powder. The evaluation results are shown in Table 1.

[High-density polyethylene resin C]
(1) Synthesis of magnesium-containing solid by reaction with chlorosilane compound 2740 mL of trichlorosilane (HSiCl ₃ ) as a 2 mol / L n-heptane solution was charged into a 15 L reactor sufficiently purged with nitrogen and stirred at 65 ° C. to keep, n- heptane solution 7L (magnesium composition formula _{AlMg 6 (C 2 H 5)} 3 (n-C 4 H 9) 10.8 (on-C 4 H 9) organomagnesium compound represented by _1.2 5 mol in terms of conversion) was added over 1 hour, and the mixture was further reacted with stirring at 65 ° C. for 1 hour. After completion of the reaction, the supernatant was removed and washed 4 times with 7 L of n-hexane to obtain a solid material slurry. As a result of separating, drying and analyzing this solid, it contained Mg 8.62 mmol, Cl 17.1 mmol, and n-butoxy group (On-C ₄ H ₉ ) 0.84 mmol per gram of the solid.

(2) Preparation of solid catalyst The slurry containing 500 g of the above-mentioned magnesium-containing solid was reacted with 2160 mL of n-butyl alcohol 1 mol / L n-hexane solution at 50 ° C. for 1 hour with stirring. After completion of the reaction, the supernatant was removed and washed once with 7 L of n-hexane. This slurry was kept at 50 ° C., and 970 mL of 1 mol / L n-hexane solution of diethylaluminum chloride was added with stirring and reacted for 1 hour. After completion of the reaction, the supernatant was removed and washed twice with 7 L of n-hexane. This slurry was kept at 50 ° C., 270 mL of n-hexane solution of 1 mol / L of diethylaluminum chloride and 270 mL of n-hexane solution of 1 mol / L of titanium tetrachloride were added and reacted for 2 hours. After completion of the reaction, the supernatant was removed, and the solid catalyst component was washed four times with 7 L of n-hexane while maintaining the internal temperature at 50 ° C. to obtain a solid catalyst component as a hexane slurry solution. The chlorine ion concentration in the supernatant of the solid catalyst slurry solution was 2.5 mmol / L, and the aluminum ion concentration was 4.5 mmol / L.

In the continuous slurry polymerization using the solid catalyst obtained above, an ethylene homopolymer was obtained as a low molecular weight component (MFR 300 g / 10 min), and then a copolymer of ethylene and 1-butene as a high molecular weight component. To obtain a high-density polyethylene resin C. Polymerization was performed so that the content of the high molecular weight component in the high-density polyethylene resin C was 40% by mass. Moreover, MFR of high density polyethylene resin C was 5.0 g / 10min, and the density was 962 kg / m < ³ >. MFR adjusted the amount of hydrogen and the density adjusted the amount of comonomer. The above-mentioned (1) to (7) were evaluated for the high density polyethylene resin C powder. The evaluation results are shown in Table 1.

[High-density polyethylene resin D]
As a high-density polyethylene resin D, Suntec (registered trademark) -HD J340 manufactured by Asahi Kasei Chemicals Corporation was used. The above-mentioned (1) to (7) were evaluated for the high-density polyethylene resin D powder. The evaluation results are shown in Table 1.

[High-density polyethylene resin E]
As a high-density polyethylene resin E, Suntec (registered trademark) -HD J311 manufactured by Asahi Kasei Chemicals Corporation was used. The above-mentioned (1) to (7) were evaluated for the high-density polyethylene resin E powder. The evaluation results are shown in Table 1.

[High-density polyethylene resin F]
A high density polyethylene resin F having an MFR of 0.40 g / 10 min and a density of 948 kg / cm ³ was obtained using the same catalyst as the polyethylene resin C, using 1-butene as a comonomer in single-stage polymerization. MFR adjusted the amount of hydrogen and the density adjusted the amount of comonomer. The above-mentioned (1) to (7) were evaluated for the high density polyethylene resin F powder. The evaluation results are shown in Table 1.

[Example 1]
To 100 parts of high-density polyethylene resin A, add 1 part of kaolin (BASF Japan KK: Satinton W (registered trademark)) and 800 ppm of calcium stearate as an additive, blend in a Henschel mixer, Using an extruder (manufactured by Nippon Steel Co., Ltd .; TEX30-α), extrusion was performed while kneading under the conditions of a cylinder temperature of 200 ° C. and an extrusion rate of 35 kg / hour to obtain pellets of the high-density polyethylene resin composition of Example 1. Each physical property value and evaluation data were obtained based on the measurement method described above. The results are shown in Table 2.

[Example 2]
Except for changing kaolin to 3 parts outside, the same treatment as in Example 1 was performed to obtain pellets of the high-density polyethylene resin composition of Example 2. The evaluation results are shown in Table 2.

[Example 3]
The high-density polyethylene resin composition of Example 3 was treated in the same manner as in Example 1 except that kaolin was replaced by Chinese kaolin (manufactured by Sabae Seishin Mineral Co., Ltd .: NM-70 (registered trademark)). A product pellet was obtained. The evaluation results are shown in Table 2.

[Example 4]
The high-density polyethylene resin composition of Example 4 was treated in the same manner as in Example 2, except that kaolin was replaced with kaolin made in China (manufactured by Sabae Seishin Mineral Co., Ltd .: NM-70 (registered trademark)). A product pellet was obtained. The evaluation results are shown in Table 2.

[Example 5]
Example 1 except that the high-density polyethylene resin A is replaced with the high-density polyethylene resin B and the kaolin is replaced with kaolin made in China (manufactured by Sabae Minshu Mineral Co., Ltd .: NM-70 (registered trademark)). Processing was performed to obtain pellets of the high-density polyethylene resin composition of Example 5. The evaluation results are shown in Table 2.

[Comparative Example 1]
Except having replaced the high density polyethylene resin A with the high density polyethylene resin C, the process similar to Example 3 was performed and the pellet of the high density polyethylene resin composition of the comparative example 1 was obtained. The evaluation results are shown in Table 3.

[Comparative Example 2]
Except having replaced the high density polyethylene resin A with the high density polyethylene resin D, the process similar to Example 3 was performed and the pellet of the high density polyethylene resin composition of the comparative example 2 was obtained. The evaluation results are shown in Table 3.

[Comparative Example 3]
Except having replaced the high density polyethylene resin A with the high density polyethylene resin E, the process similar to Example 3 was performed and the pellet of the high density polyethylene resin composition of the comparative example 3 was obtained. The evaluation results are shown in Table 3.

[Comparative Example 4]
Except having replaced the high density polyethylene resin A with the high density polyethylene resin F, the process similar to Example 4 was performed and the pellet of the high density polyethylene resin composition of the comparative example 4 was obtained. The evaluation results are shown in Table 3.

[Comparative Example 5]
The high-density polyethylene resin composition of Comparative Example 5 was subjected to the same treatment as in Example 1 except that kaolin was replaced with basic magnesium sulfate (manufactured by Ube Materials Co., Ltd .: Mosheidi A-1 (registered trademark)). Pellets were obtained. The evaluation results are shown in Table 3.

[Comparative Example 6]
The high-density polyethylene resin composition of Comparative Example 6 was subjected to the same treatment as in Example 2 except that kaolin was replaced with basic magnesium sulfate (manufactured by Ube Materials Co., Ltd .: Mosheidi A-1 (registered trademark)). Pellets were obtained. The evaluation results are shown in Table 3.

[Comparative Example 7]
The same treatment as in Example 1 was performed except that kaolin was replaced with hydrophilic fumed silica (manufactured by Nippon Aerosil Co., Ltd .: Aerosil 200 (registered trademark)) to obtain pellets of the high-density polyethylene resin composition of Comparative Example 7. It was. The evaluation results are shown in Table 3.

[Comparative Example 8]
The same treatment as in Example 1 was performed except that kaolin was replaced with silica (manufactured by AGC S-Tech Co., Ltd .: H31 (registered trademark)) to obtain pellets of the high-density polyethylene resin composition of Comparative Example 8. The evaluation results are shown in Table 3.

[Comparative Example 9]
The same treatment as in Example 1 was performed except that kaolin was replaced with magnesium hydroxide (UD-653 (registered trademark) manufactured by Ube Materials Co., Ltd.), and pellets of the high-density polyethylene resin composition of Comparative Example 9 were used. Obtained. The evaluation results are shown in Table 3.

[Comparative Example 10]
Except having added 25 parts of kaolin outside, the process similar to Example 1 was performed and the pellet of the high density polyethylene resin composition of the comparative example 10 was obtained. The evaluation results are shown in Table 3.

  The result of the distance visibility test of the compression molding board shape | molded with the high density polyethylene resin A and B and the compression molding board shape | molded with the high density polyethylene resin composition of Examples 1-5 is shown in FIG. Moreover, the result of the far visibility test of the compression molding board shape | molded with the high density polyethylene resin C-F and the compression molding board shape | molded with the high density polyethylene resin composition of Comparative Examples 1-9 is shown in FIG. Comparing compression molded plates molded with high density polyethylene resins A to F with compression molded plates molded with the high density polyethylene resin compositions of Examples 1 to 5 and Comparative Examples 5 to 9, It turns out that the molded object excellent in transparency can be shape | molded from a density polyethylene resin composition (Examples 1-5). Moreover, it turns out that it is excellent in transparency if it is a molded object (Examples 1-5) which has a predetermined | prescribed spherulite size from the result of Examples 1-5 and Comparative Examples 1-4.

  The high-density polyethylene resin composition of the present invention and a molded article comprising the same have transparency, have rigidity when used as a bottle or container, and have excellent visibility of contents. Therefore, it is suitable as a material for containers and is suitable for medical containers for storing liquid solutions such as infusions, drugs, blood, etc., food containers, and the like. Further, it is suitable for an infrared sensor window or the like because it transmits infrared rays well, has visibility and is rigid.

Claims (7)

Including high density polyethylene resin and layered silicate,
A high-density polyethylene resin composition, wherein the maximum size of spherulites of the high-density polyethylene resin is 0.1 μm or more and 5 μm or less.   The high-density polyethylene resin composition according to claim 1, comprising 0.1 to 20% by mass of the layered silicate.   The high-density polyethylene resin composition according to claim 1 or 2, wherein the layered silicate contains kaolin.   A press-molded product obtained by press-molding the high-density polyethylene resin composition according to any one of claims 1 to 3.   An injection-molded product obtained by injection-molding the high-density polyethylene resin composition according to any one of claims 1 to 3.   A high-density polyethylene resin and a layered silicate are included, the content of the layered silicate is 0.1 to 20% by mass, and the maximum spherulite size is 0.1 to 5 μm. The molded object which consists of a high-density polyethylene resin composition of any one of these.   The manufacturing method of the high density polyethylene resin composition of any one of Claims 1-3 including the process of melt-kneading a high density polyethylene resin and layered silicate.