JP2017125116A - Method for producing polyethylene resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polyethylene resin composition capable of producing a polyethylene resin composition excellent in transparency and workability.SOLUTION: There are provided: a method for producing a polyethylene resin composition which includes a step of bringing a nitrogen gas including water or a proton-donative substance, or steam into contact with an ethylene polymer obtained by blending a nucleator dissolved in an organic aluminum compound or a mixed solvent of the organic aluminum compound and an organic solvent, before or during polymerization and polymerizing an ethylene monomer; and a method for producing a polyethylene resin composition which includes a step of press-fitting a nitrogen gas including water or a proton-donative substance, or steam into an extruder, with respect to an ethylene polymer obtained by supplying a nucleator dissolved in an organic aluminum compound or a mixed solvent of the organic aluminum compound and an organic solvent, before or during polymerization and polymerizing an ethylene monomer, and melt-kneading the ethylene polymer.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a polyethylene resin composition, and more specifically, in an ethylene polymer obtained by polymerizing an ethylene monomer by supplying a nucleating agent dissolved in an organic aluminum compound or an organic aluminum compound and an organic solvent, The present invention relates to a method for producing a polyethylene resin composition excellent in transparency and workability by industrially simply and effectively regenerating a nucleating agent contained in an ethylene polymer.

  Polyolefin resins such as polyethylene are inexpensive and have excellent properties such as transparency, heat resistance, surface glossiness, oil resistance, and mechanical properties, so industrial materials, automotive materials, home appliance materials, packaging materials, etc. Used in a wide range of fields. Since it is an inexpensive product, alternatives to other resin materials are being studied.

  Polyolefin-based resins have a low crystallization rate after molding, so the molding cycle is low, and depending on the degree of crystallization after heat molding, large crystals are generated, and the transparency and strength of the molded product are insufficient. there were. These drawbacks are all derived from the crystallinity of the polyolefin-based resin, and it is known to be eliminated if the crystallization temperature of the olefin resin can be increased and fine crystals can be rapidly generated.

As a method of adding a nucleating agent before or during polymerization of an olefin monomer, for example, in Patent Document 1, after prepolymerization of propylene, aluminum-bis (p-tert-butylbenzoic acid) hydroxy or benzoic acid as a nucleating agent. A method for carrying out two-stage polymerization by adding an acid sodium salt has been proposed.
Patent Document 2 proposes a production method in which a nucleating agent is added to an olefin monomer for polymerization.

Patent 3044259 JP 2014-095046 A

  The method of adding a nucleating agent before or during polymerization provides the advantage that the step of blending the nucleating agent by melt kneading such as extrusion after polymerization can be omitted, but the nucleating agent has a catalytic activity of the polymerization catalyst. Problems have been pointed out, such as lowering or coloring the polymer by interaction with the metal of the polymerization catalyst, and there has been a problem that the selection and management of the polymerization conditions become complicated.

  The method described in Patent Document 1 is aimed at uniform dispersion of a nucleating agent and thereby improving the rigidity of the polymer, and is a polymerization method by two-stage polymerization, wherein the nucleating agent is obtained after one-stage polymerization of propylene. It is a method of adding. Patent Document 1 discloses any of the fact that the nucleating agent can affect the polymerization activity, masking the nucleating agent, and preventing adverse effects on the catalytic activity by masking the nucleating agent. It has not been. In the method described in Patent Document 1, no effect is obtained in the one-step polymerization in which the nucleating agent is directly brought into contact with the polymerization catalyst. Moreover, the nucleating agent described in Patent Document 1 does not dissolve in the organoaluminum compound and the organic solvent, and impairs the polymerization activity.

  Although the method described in Patent Document 2 shows that the nucleating agent used in the present application is added to the olefin monomer for polymerization, the addition to the ethylene monomer has not been specifically described.

  In general, the nucleating agent itself has poor fluidity and needs to be slurried with a solvent, but the solution diffusibility is poor, and the nucleating agent precipitates over time, resulting in a non-uniform concentration. The ethylene polymer polymerized by the method has a problem in that the nucleation effect is uneven.

  Then, the objective of this invention is providing the manufacturing method of the polyethylene resin composition which can manufacture the polyethylene resin composition excellent in transparency and workability.

As a result of intensive investigations to solve the above problems, the present inventors supplied an organoaluminum compound or a mixture of an organoaluminum compound and an organic solvent with a nucleating agent dissolved therein to polymerize the ethylene monomer. I came up with a way to do it.
Furthermore, the present inventors have not been able to fully exhibit the action and effect of the nucleating agent when the masked nucleating agent is blended in the ethylene polymer, and the transparency of the molded product obtained by molding the ethylene polymer is low. We found that it may be damaged. As a result of repeated studies on this point, the present inventors have found that the above problem can be solved by applying nitrogen gas containing moisture or a proton donating substance or steam, and have completed the present invention.
According to the study by the present inventors, regeneration of the nucleating agent dissolved in the organoaluminum compound or the mixed solvent of the organoaluminum compound and the organic solvent can be performed by contact with moisture or a proton donating substance. it can. When employing a technique for decomposing the polymerization catalyst in the water treatment step, it can be expected that the nucleating agent is regenerated by water treatment, but the amount of water in the ethylene polymer increases as the amount of treated water increases. When an ethylene polymer having a large amount of moisture is molded, there are problems such as a decrease in transparency of the molded product and formation of bubbles in the molded product. Furthermore, the increase in the water treatment process increases the energy required for the separation or drying process of water and the ethylene polymer, which is industrially disadvantageous. Accordingly, by applying nitrogen gas containing moisture or a proton donating substance or steam, it becomes possible to produce a polyethylene resin composition having excellent transparency and processability by an industrially advantageous method. .

  That is, the method for producing a polyethylene resin composition according to the present invention comprises polymerizing an olefin monomer by blending a nucleating agent dissolved in an organic aluminum compound or a mixed solvent of an organic aluminum compound and an organic solvent before or during the polymerization. The ethylene polymer obtained as described above is provided with a step of contacting water or nitrogen gas containing a proton donating substance or steam.

  In addition, the method for producing the polyethylene resin composition of the present invention comprises polymerizing an ethylene monomer by blending a nucleating agent dissolved in an organic aluminum compound or a mixed solvent of an organic aluminum compound and an organic solvent before or during the polymerization. It is characterized by comprising a step of melt-kneading the ethylene polymer by press-fitting nitrogen gas containing moisture or a proton donating substance or steam into the extruder to the ethylene polymer formed. .

（式中、Ｒ^１〜Ｒ^４は各々独立して、水素原子、直鎖又は分岐を有する炭素原子数１〜９のアルキル基を表し、Ｒ^５は水素原子又はメチル基を表し、ｍは１又は２を表し、ｍが１の場合、Ｍ^１は水素原子又はアルカリ金属原子を表し、ｍが２の場合、Ｍ^１は、二族元素、Ａｌ（ＯＨ）又はＺｎを表す。） In the present invention, the nucleating agent is preferably a compound represented by the following general formula (1).

(Wherein R ^{1 to} R ⁴ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms, R ⁵ represents a hydrogen atom or a methyl group, and m represents 1; Or when m is 1, M ¹ represents a hydrogen atom or an alkali metal atom, and when m is 2, M ¹ represents a group 2 element, Al (OH) or Zn.)

  In the present invention, the nucleating agent is preferably an amide compound.

  Moreover, in the manufacturing method of this invention, it is preferable that the said organoaluminum compound is a trialkylaluminum.

  Moreover, in the manufacturing method of this invention, it is preferable that the said organic solvent is a thing selected from an aliphatic hydrocarbon compound and an aromatic hydrocarbon compound.

  In the present invention, the proton donating substance is preferably selected from methanol and ethanol.

  In the present invention, the ethylene polymer is preferably polyethylene having a weight average molecular weight of 10,000 to 7000000.

  The polyethylene resin composition of the present invention is produced by the above-described method for producing a polyethylene resin composition of the present invention, and the amount of water contained is in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the ethylene polymer. It is characterized by being.

  Moreover, the molded article of the present invention is formed by molding the polyethylene resin composition.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the manufacturing method of the polyethylene resin composition which can manufacture the polyethylene resin composition excellent in transparency and workability, the polyethylene resin composition manufactured by it, and a molded article.

The method for producing the polyethylene resin composition of the present invention will be described in detail below.
The method for producing the polyethylene resin composition of the present invention comprises polymerizing an ethylene monomer by blending a nucleating agent dissolved in an organic aluminum compound or a mixed solvent of an organic aluminum compound and an organic solvent before or during polymerization. The resulting ethylene polymer is used.

Examples of the nucleating agent component used in the present invention include nucleating agents that dissolve in an organic aluminum compound or a mixed solvent of an organic aluminum compound and an organic solvent. Those that do not dissolve may have poor dispersibility in the resin, and the effects of the present invention may not be obtained. About the solubility of a nucleating agent component, it is necessary to confirm beforehand before implementing the manufacturing method of this invention. Whether or not to dissolve can be determined by dissolving a nucleating agent in an organic aluminum compound or a mixed solvent of an organic aluminum compound and an organic solvent and visually confirming whether a residue is generated.
Moreover, since the nucleating agent which decomposes | disassembles with an organoaluminum compound may color a polymer or may inhibit polymerization activity, it cannot employ | adopt for the manufacturing method of this invention.

（式中、Ｒ^１〜Ｒ^４は各々独立して、水素原子又は分岐を有してもよい炭素原子数１〜９のアルキル基を表し、Ｒ^５は水素原子又はメチル基を表し、ｍは１又は２を表し、ｍが１の場合、Ｍ^１は水素原子又はアルカリ金属原子を表し、ｍが２の場合、Ｍ^１は、二族元素、Ａｌ（ＯＨ）又はＺｎを表す。）で表される化合物及びアミド化合物が好ましい。 In the present invention, preferable nucleating agent components include the following general formula (1),

(Wherein R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms which may have a branch, R ⁵ represents a hydrogen atom or a methyl group, and m represents 1 or 2, when m is 1, M ¹ represents a hydrogen atom or an alkali metal atom, and when m is 2, M ¹ represents a group II element, Al (OH) or Zn). And amide compounds are preferred.

Examples of the alkyl group having 1 to 9 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ in the general formula (1) include, for example, a methyl group, an ethyl group, a propyl group, and an isopropyl group. Butyl group, -sec-butyl group, tert-butyl group, isobutyl group, amyl group, isoamyl group, tert-amyl group, hexyl group, cyclohexyl group, heptyl group, isoheptyl group, tert-heptyl group, Among these, a methyl group, a tert-butyl group, and a tert-heptyl group are particularly preferable.

Examples of the second group element represented by M ¹ in the general formula (1) include beryllium, magnesium, calcium, strontium, barium, and radium. Among these, elements that are magnesium and calcium are nucleating. Since the nucleating agent effect of the agent component is remarkable, it is preferable.

As a nucleating agent component used by this invention, the compound shown below is mentioned, for example. However, the present invention is not limited by the following compounds.

（式中、Ｒ^６は水素原子、直鎖又は分岐を有する炭素原子数１〜１２のアルキル基、炭素数３〜１２のシクロアルキル基、炭素原子数６〜２０のアリール基を表し、複数あるＲ^６は各々異なるものであってもよい）で表されるカルバメート構造が炭素原子数１〜１０の炭化水素基を介して少なくとも４つ以上連結した構造を有する化合物、
下記一般式（３）、

（式中、Ｘ^１は、直鎖又は分岐を有する炭素原子数１〜５のアルキレン基であり、Ｒ^７〜Ｒ^１０は、各々、独立して、ハロゲン原子、置換基を有してもよく分岐を有してもよい炭素原子数１〜４のアルキル基、及び置換されていてもよく分岐を有してもよい炭素原子数１〜４のアルコキシ基よりなる群から選択されるものを表し、ｐ、ｑ、ｒ、ｓは各々独立して、０〜３の整数（ただし、ｐおよびｓは０ではない）を表す）で表される化合物、
下記一般式（４）、

（式中、Ｒ^１１及びＲ^１２は各々独立して、直鎖又は分岐を有する炭素原子数１〜１０のアルキル基、炭素原子数３〜１２のシクロアルキル基、又は炭素原子数６〜２０のアリール基を表し、Ｘ^２及びＸ^３は、各々独立して、単結合手、または、分岐を有してもよい炭素原子数１〜５のアルキレン基を表す。ただし、上記置換基は水酸基を除く）で表される化合物、
下記一般式（５）、

（式中、Ｒ^１３及びＲ^１４は各々独立して、水素原子、直鎖又は分岐を有する炭素原子数１〜１２のアルキル基、炭素原子数３〜１２のシクロアルキル基、又は、炭素原子数６〜２０のアリール基を表し、Ｘ^４は、直鎖又は分岐を有する炭素原子数１〜１０のアルキレン基、炭素原子数３〜１２のシクロアルキレン基、又は炭素原子数６〜２０のアリーレン基を表す。なお、Ｒ^１３およびＲ^１４が互いに結合して縮合環構造を形成してもよい）で表される化合物、
下記一般式（６）、

（式中、Ｒ^１５は、水素原子、直鎖又は分岐を有する炭素原子数１〜１２のアルキル基、炭素原子数３〜１２のシクロアルキル基、又は、炭素原子数６〜２０のアリール基を表し、Ｘ^５は、直鎖又は分岐を有する炭素原子数１〜１０のアルキレン基、炭素原子数３〜１２のシクロアルキレン基、又は炭素原子数６〜２０のアリーレン基を表す）で表される化合物、
下記一般式（７）、

（式中、Ｒ^１６及びＲ^１７は各々独立して、直鎖又は分岐を有するアルキル基を表す）で表される化合物、脂肪酸アミド化合物等が挙げられる。 Examples of the amide compound include the following general formula (2),

(In the formula, R ⁶ represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and there are a plurality thereof. R ⁶ may be different from each other) a compound having a structure in which at least four or more carbamate structures are linked via a hydrocarbon group having 1 to 10 carbon atoms,
The following general formula (3),

(In the formula, X ¹ is a linear or branched alkylene group having 1 to 5 carbon atoms, and R ^{7 to} R ¹⁰ may each independently have a halogen atom or a substituent. Represents one selected from the group consisting of an alkyl group having 1 to 4 carbon atoms which may have a branch and an alkoxy group having 1 to 4 carbon atoms which may be substituted and which may have a branch. , P, q, r, and s each independently represent a compound represented by an integer of 0 to 3 (provided that p and s are not 0),
The following general formula (4),

(Wherein R ¹¹ and R ¹² are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or 6 to 20 carbon atoms. Represents an aryl group, and X ² and X ³ each independently represent a single bond or an alkylene group having 1 to 5 carbon atoms which may have a branch, provided that the substituent is a hydroxyl group. A compound represented by
The following general formula (5),

(Wherein R ¹³ and R ¹⁴ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or the number of carbon atoms. Represents an aryl group having 6 to 20 and X ⁴ is a linear or branched alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, or an arylene group having 6 to 20 carbon atoms. Wherein R ¹³ and R ¹⁴ may combine with each other to form a condensed ring structure),
The following general formula (6),

(In the formula, R ¹⁵ represents a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or an aryl group having 6 to 20 carbon atoms. X ⁵ represents a linear or branched alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, or an arylene group having 6 to 20 carbon atoms). Compound,
The following general formula (7),

(Wherein, R ¹⁶ and R ¹⁷ each independently represents a linear or branched alkyl group), fatty acid amide compounds, and the like.

  The hydrocarbon group having 1 to 10 carbon atoms to which the carbamate structure represented by the general formula (2) is bonded represents a functional group composed of a carbon atom and a hydrogen atom, and its molecular structure includes alkane and alkene. , Cycloalkane, aromatic hydrocarbon and the like, and represents a hydrocarbon group in which at least 4 hydrogen atoms are substituted with a carbamate structure. The hydrocarbon group may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group, an imino group or an aryl group, and the hydrogen atom in the hydrocarbon group is substituted with the following substituent. It may be a thing. These interruptions or substitutions may be combined.

Examples of the linear or branched alkyl group having 1 to 12 carbon atoms represented by R ⁶ in the general formula (2) include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec -Group, tert-butyl group, isobutyl group, pentyl group, isopentyl group, tert-pentyl group, hexyl group, 2-hexyl group, 3-hexyl group, heptyl group, 2-heptyl group, 3-heptyl group, isoheptyl group Tert-heptyl group, n-octyl group, isooctyl group, tert-octyl group, nonyl group, isononyl group, decyl group, undecyl group, dodecyl group and the like. Of these, a hexyl group and an octyl group are preferable.
These alkyl groups may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group, an imino group or the following aryl group, and a hydrogen atom in the alkyl group is substituted with the following substituent. These interruptions or substitutions may be combined.

  Examples of the substituent that replaces the hydrogen atom of the alkyl group in the general formula (2) include a hydroxy group, a halogen atom, an amino group, a nitro group, a cyano group, an alkenyl group, an alkenyloxy group, an alkanoyloxy group, and an alkoxycarbonyl group. Chain aliphatic groups such as pyrrole, furan, thiophene, imidazole, pyridine, pyridazine, pyrimidine, pyrazine, piperidine, morpholine, 2H-pyran, phenyl, biphenyl, triphenyl, naphthalene, anthracene, pyrrolidine, pyridine , An indoline, an indole, an isoindole, an indazole, a purine, a quinolidine, a quinoline, an isoquinoline, or a cyclic aliphatic group such as a cycloalkyl group.

Examples of the cycloalkyl group having 3 to 12 carbon atoms represented by R ⁶ in the general formula (2) include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecyl group. A cyclohexyl group is preferable.
In addition, a hydrogen atom in the cycloalkyl group is substituted with a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, an alkenyloxy group, an alkoxyalkyl group, an alkanoyloxy group, an alkoxycarbonyl group, a nitrile group, or a cyano group. It may be.

In the aryl group having 6 to 20 carbon atoms represented by R ⁶ in the general formula (2), a hydrogen atom in the aryl group is a halogen atom, a nitro group, a cyano group, an alkyl group, an alkoxy group, an alkenyl group. A group, an alkenyloxy group, an alkoxyalkyl group, an alkanoyloxy group, or an alkoxycarbonyl group may be substituted. Examples of these aryl groups include phenyl group, 3,4,5-trimethoxyphenyl group, 4-tert-butylphenyl group, biphenyl group, naphthyl group, methylnaphthyl group, anthracenyl group, phenanthryl group, and the like. In the present invention, a phenyl group is preferred.

（式中、Ｒ^１８は、上記一般式（２）中のＲ^６と同じものを表し、ｋは２〜１０の整数を表し、複数あるＲ^１８は各々異なるものであってもよい）で表される化合物、又は、下記一般式（９）、

（式中、Ｒ^１９は、上記一般式（２）中のＲ^６と同じものを表し、複数あるＲ^１９は各々異なるものであってもよい）で表される化合物を好ましく用いることができる。 Of the compounds represented by the general formula (2), the following general formula (8),

(In the formula, R ¹⁸ represents the same as R ⁶ in the general formula (2), k represents an integer of 2 to 10, and a plurality of R ¹⁸ may be different from each other). Or a compound represented by the following general formula (9),

(Wherein, R ¹⁹ represents the same as R ⁶ in the general formula (2), a plurality of R ¹⁹ may also is a in each different) can be preferably used a compound represented by.

Examples of the specific structure of the compound represented by the general formula (2) in the present invention include the following compounds. However, the present invention is not limited to the following compounds.

The linear or alkylene group having 1 to 5 carbon atoms having a branch of X ¹ in the general formula (3), a methylene group, an ethylene group, a propylene group, butylene group, isobutylene group, pentylene group and the like , _-CH 2 in these alkylene groups - is, -O -, - CO -, - COO- or -OCO- may be substituted with, also hydrogen atoms in the alkylene group, a halogen atom, an alkenyl group , An alkenyloxy group, an alkanoyloxy group, an alkoxycarbonyl group, a nitro group, a cyano group, an aryl group, or a saturated aliphatic ring.

Examples of the alkyl group having 1 to 4 carbon atoms having linear or branched R ^{7 to} R ¹⁰ in the general formula (3) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and tertiary butyl. These alkyl groups may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group, an imino group or the above aryl group, and the hydrogen atom in the alkyl group is It may be substituted with a substituent, and these interruptions or substitutions may be combined.

Examples of the alkoxy group having 1 to 4 carbon atoms of R ^{7 to} R ¹⁰ in the general formula (3) include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. These alkoxy groups may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group, an imino group or the above aryl group, and a hydrogen atom in the alkoxy group is substituted with the above substituent. These interruptions or substitutions may be combined.

Examples of the specific structure of the compound represented by the general formula (3) in the present invention include the following compounds. However, the present invention is not limited to the following compounds.

Among the compounds represented by the general formula (3), compounds in which R ⁷ and R ¹⁰ in the general formula (3) are in the ortho position of the benzene ring are preferably used.

  Moreover, the compound whose p and s in the said General formula (3) are 1 and q and r are 2 is used preferably.

Examples of the linear or branched alkyl group having 1 to 10 carbon atoms represented by R ¹¹ or R ¹² in the general formula (4) include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, Butyl, sec-butyl, tert-butyl, isobutyl, pentyl, isopentyl, tert-pentyl, hexyl, 2-hexyl, 3-hexyl, heptyl, 2-heptyl, 3- Examples include heptyl group, isoheptyl group, tert-heptyl group, n-octyl group, isooctyl group, tert-octyl group, nonyl group, isononyl group, decyl group, and the like. These alkyl groups are oxygen atom, sulfur atom, carbonyl group. , An ester group, an amide group, an imino group or the above aryl group may be interrupted, and the hydrogen atom in the alkyl group is substituted as described above. In may be substituted, these interruptions or substitutions may be combined.

The general formula (4) represented by ^{R 11} or ^{R 12} in, the cycloalkyl group having 3 to 12 carbon atoms include the same ^{R 6} in the general formula (2).

Examples of the aryl group having 6 to 20 carbon atoms represented by R ¹¹ or R ¹² in the general formula (4) include the same as R ⁶ in the general formula (2).

The linear or branched alkylene group having 1 to 5 carbon atoms represented by X ² or X ³ in the general formula (4) is the same as X ¹ in the general formula (3). Can be mentioned.

（式中、Ｒ^２０は、上記一般式（４）中のＲ^１１と同じものを表し、Ｒ^２１は、上記一般式（４）中のＲ^１２と同じものを表し、ｔは、０又は１を表す）のいずれかで表される化合物を好ましく用いることができる。 Of the compounds represented by the general formula (4), the following general formulas (10) to (12),

(In the formula, R ²⁰ represents the same as R ¹¹ in the general formula (4), R ²¹ represents the same as R ¹² in the general formula (4), and t is 0 or 1 Can be preferably used.

Examples of the specific structure of the compound represented by the general formula (4) in the present invention include the following compounds. However, the present invention is not limited to the following compounds.

Examples of the linear or branched alkyl group having 1 to 12 carbon atoms represented by R ¹³ and R ¹⁴ in the general formula (5) or R ¹⁵ in the general formula (6) include the above general formula. (2) the same thing can be mentioned as ^{R 6} in.

Examples of the cycloalkyl group having 3 to 12 carbon atoms represented by R ¹³ and R ¹⁴ in the general formula (5) or R ¹⁵ in the general formula (6) include those in the general formula (2). same as R ⁶ and the like.

The aryl group having 6 to 20 carbon atoms represented by R ¹³ and R ¹⁴ in the general formula (5) or R ¹⁵ in the general formula (6) is R in the general formula (2). ^The same thing as ⁶ is mentioned.

Examples of the linear or branched alkylene group having 1 to 10 carbon atoms represented by X ⁴ and X ⁵ in the general formula (5) or (6) include a methylene group, an ethylene group, a propylene group, and a methyl group. Ethylene group, butylene group, 1-methylpropylene group, 2-methylpropylene group, 1,2-dimethylpropylene group, 1,3-dimethylpropylene group, 1-methylbutylene group, 2-methylbutylene group, 3-methylbutylene Group, 1,3-dimethylbutylene group, pentylene group, hexylene group, heptylene group, octylene group and the like. These alkylene groups may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group, an ester group, an amide group, an imino group or the above aryl group, and the hydrogen atom in the alkylene group is substituted by the above substituent. These interruptions or substitutions may be combined.

Examples of the cycloalkylene group having 3 to 12 carbon atoms represented by X ⁴ and X ⁵ in the general formula (5) or (6) include a 1,2-cyclopropylene group, a 1,3-cycloheptylene group, Examples include trans-1,4-cyclohexylene group. The hydrogen atom in these cycloalkylene groups may be substituted with the above substituents.

Examples of the arylene group having 6 to 20 carbon atoms represented by X ⁴ and X ⁵ in the general formula (5) or (6) include a 1,4-phenylene group, a 1,3-phenylene group, Examples include 1,5-naphthylene group, 2,6-naphthylene group, 2,6-phenalene group, 1,6-phenanthrene group, 2,7-phenanthrene group, 2,6-anthracene group and the like. The hydrogen atom of these arylene groups may be substituted with the above substituent.

Further, when R ¹³ and R ¹⁴ in the general formula (5) or R ¹⁵ in the general formula (6) is an alkyl group, the nucleating agent for the olefin polymer is increased when the carbon number of the alkyl group is increased. However, in the present invention, R ¹³ , R ¹⁴ may deteriorate the heat resistance of the compound itself and may decompose and adversely affect the molded product when the olefin polymer is molded. , Or the number of carbon atoms of the alkyl group represented by R ¹⁵ is preferably within the range of 1 to 8, particularly preferably within the range of 1 to 5.

Examples of the specific structure of the compound represented by the general formula (5) in the present invention include the following compounds. However, the present invention is not limited to the following compounds.

Examples of the specific structure of the compound represented by the general formula (6) in the present invention include the following compounds. However, the present invention is not limited to the following compounds.

Examples of the alkyl group having 1 to 6 carbon atoms which may have a branch represented by R ¹⁶ and R ¹⁷ in the general formula (7) include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. , Isobutyl group, tertiary butyl group, pentyl group, isopentyl group, tertiary pentyl group, neopentyl group, hexyl group, isohexyl group and the like.

（式中、Ｒ^２２は、一般式（７）中のＲ^１６と同じものを表し、Ｒ^２３は一般式（７）中のＲ^１７と同じものを表す）、
又は、下記一般式（１４）、

（式中、Ｒ^２４は、一般式（７）中のＲ^１６と同じものを表し、Ｒ^２５は、一般式（７）中のＲ^１７と同じものを表す）で表される化合物を好ましく用いることができる。 Among the compounds represented by the general formula (7), the following general formula (13),

(Wherein R ²² represents the same as R ¹⁶ in general formula (7), and R ²³ represents the same as R ¹⁷ in general formula (7)),
Or the following general formula (14),

(In the formula, R ²⁴ represents the same as R ¹⁶ in the general formula (7), and R ²⁵ represents the same as R ¹⁷ in the general formula (7)). be able to.

Specific examples of the structure of the compound represented by the general formula (7) in the present invention include the following compounds. However, the present invention is not limited to the following compounds.

  Examples of the fatty acid amide compound include ethylene bisstearamide, ethylene bis (12-hydroxystearamide), stearic acid amide, and the like.

  Examples of amide compounds other than those described above include 1,2,3-propanetricarboxylic acid tricyclohexylamide, 1,2,3-propanetricarboxylic acid tri (2-methylcyclohexylamide), 1,2,3- Propanetricarboxylic acid tri (3-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-methylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2,3-dimethylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-ethylcyclohexylamide) 1,2,3-propanetricarboxylic acid tri (3-ethylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-ethylcyclohexyl) Amide), 1,2,3-propanetricarboxylic acid Tri (2-n-propylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-n-propylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4-n-propylcyclohexylamide) 1,2,3-propanetricarboxylic acid tri (2-isopropylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-isopropylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (4- Isopropylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-n-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-n-butylcyclohexylamide) 1,2,3- Propane tricarboxylic acid tri (4-n-butylcyclohex Silamide), 1,2,3-propanetricarboxylic acid tri (2-isobutylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-isobutylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri ( 4-isobutylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-sec-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3-sec-butylcyclohexylamide), 1,2 , 3-propanetricarboxylic acid tri (4-sec-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (2-tert-butylcyclohexylamide), 1,2,3-propanetricarboxylic acid tri (3- tert-butylcyclohexylamide), 1, , 3-propanetricarboxylic acid tri (4-tert-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetracyclohexylamide, 1,2,3,4-butanetetracarboxylic acid tetra (2-methyl) Cyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3-methylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4-methylcyclohexylamide), 1,2, 3,4-butanetetracarboxylic acid tetra (2-ethylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3-ethylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid Tetra (4-ethylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra La (2-n-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3-n-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4- n-propylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (2-isopropylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3-isopropylcyclohexylamide), 1 , 2,3,4-Butanetetracarboxylic acid tetra (4-isopropylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (2-n-butylcyclohexylamide), 1,2,3,4 -Butanetetracarboxylic acid tetra (3-n-butylcyclohexylamide), 1,2,3,4-butante Tetracarboxylic acid tetra (4-n-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (2-isobutylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3 -Isobutylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4-isobutylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (2-sec-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (3-sec-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4-sec-butylcyclohexylamide), 1,2, 3,4-butanetetracarboxylic acid tetra (2-tert-butylcyclohexylamide), , 2,3,4-Butanetetracarboxylic acid tetra (3-tert-butylcyclohexylamide), 1,2,3,4-butanetetracarboxylic acid tetra (4-tert-butylcyclohexylamide), 1,3,5 Benzenetricarboxylic acid tris (benzylamide), 1,3,5-benzenetricarboxylic acid tris (cycloheptylamide), 1,3,5-benzenetricarboxylic acid tris (3-methylcyclohexylamide), 1,3,5- Benzenetricarboxylic acid tris (3,4-dimethylphenylamide), 1,3,5-benzenetricarboxylic acid tris (cyclododecylamide), 1,3,5-benzenetricarboxylic acid tris (tertiary octylamide), 1,3 , 5-Benzenetricarboxylic acid tris (S (+)-1-cyclohexylethyla ), 1,3,5-benzenetricarboxylic acid tris (R (−)-1-cyclohexylethylamide), 1,3,5-benzenetricarboxylic acid tris (cyclooctylamide), 1,3,5-benzenetricarboxylic acid Acid tris (2,3-dimethylcyclohexylamide), 1,3,5-benzenetricarboxylic acid tris (cyclooctylamide), 1,3,5-benzenetricarboxylic acid tris (n-butylamide), 1,3,5- Examples include benzenetricarboxylic acid tris (1,1,3,3-tetramethylbutyramide), 1,3,5-tris (2,2-dimethylpropionamide) benzene and the like.

  The range of the amount of the nucleating agent component used is preferably 0.001 to 0.5 parts by mass, preferably 0.005 to 0.3 parts by mass with respect to 100 parts by mass of the ethylene polymer obtained by polymerization. A range is more preferred. When the amount is less than 0.001 part by mass, the effect of the nucleating agent may not be obtained, and when 0.5 parts by mass or more is molded by the polyethylene resin composition obtained by the production method of the present invention alone, The addition effect may not be obtained, which is uneconomic.

  In the polymerization of the ethylene polymer used in the production method of the present invention, the nucleating agent component dissolved in an organic aluminum compound or organic aluminum and an organic solvent is added before or during the polymerization of the olefin monomer. However, the addition location is not particularly limited, and for example, it can be added to any of a polymerization system, a catalyst system, and a compounding tube.

  When the nucleating agent component is added before or during the polymerization of the ethylene monomer, it may be a mixture of the nucleating agent component and the organoaluminum compound, and the nucleating agent is dispersed in an organic solvent. In addition, an organoaluminum compound may be added to dissolve the nucleating agent component. Thereby, it is considered that the nucleating agent component is masked by the organoaluminum compound.

  As the organoaluminum compound, for example, alkylaluminum, alkylaluminum hydride and the like can be used, but alkylaluminum is preferable, and trialkylaluminum is particularly preferable, and specifically, trimethylaluminum, triethylaluminum, tri-n. -Propyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum and the like. Any of the above organoaluminum compounds can be used as a mixture. Moreover, the aluminoxane obtained by reaction of alkylaluminum or alkylaluminum hydride and water can be used similarly.

  In obtaining the ethylene polymer, it is preferable to use an organoaluminum compound that can be regenerated by treating a material masked with an organoaluminum compound with a hydrogen-donating compound such as water, alcohol, or acid.

  As a mixing ratio of the nucleating agent component and the organoaluminum compound, the molar ratio of aluminum in the nucleating agent component and the organoaluminum compound is preferably 1/1000 to 1 / 0.3. If the nucleating agent component is more than 1 / 0.3, the excess nucleating agent component may adversely affect the polymerization activity of the ethylene monomer. If the nucleating agent component is less than 1/1000, the organoaluminum compound after polymerization. May remain in the ethylene polymer, and the physical properties of the ethylene polymer may deteriorate, or the desired metal may not be polymerized due to the influence of the catalyst metal component.

Examples of the organic solvent include aliphatic and aromatic hydrocarbon compounds. Examples of the aliphatic hydrocarbon compound include saturated hydrocarbon compounds such as n-pentane, n-hexane, n-heptane, n-octane, isooctane and purified kerosene, and cyclic saturated hydrocarbons such as cyclopentane, cyclohexane and cycloheptane. Examples of the aromatic hydrocarbon compound include compounds such as benzene, toluene, ethylbenzene, and xylene. These organic solvents may be used individually by 1 type, and may use 2 or more types together.
Of the above organic solvents, n-hexane or n-heptane is preferably used. The concentration of the organoaluminum compound in the organic solvent is preferably in the range of 0.001 to 0.5 mol / L, particularly preferably 0.01 to 0.1 mol / L.

  The ethylene polymer in the present invention is an ethylene monomer homopolymer, a copolymer of 5 mol% or less α-olefin monomer, or 1 mol% having only carbon, oxygen and hydrogen atoms in the functional group. It may contain a copolymer with the following non-olefin monomer.

  Examples of the α-olefin monomer include propene, 1-butene, 1-hexene, methyl propenoate, ethyl propenoate, 3-methyl-1-butene, 3-methyl-1-pentene, and 4-methyl-1- Examples include pentene, vinylcycloalkane, vinylcycloalkane, and derivatives thereof. Examples of the non-olefin monomer include vinyl acetate, styrene, and derivatives thereof.

  Examples of the polyethylene include high-density polyethylene, low-density polyethylene, ultra-low density polyethylene, linear low-density polyethylene, and ultra-high molecular weight polyethylene, and can be used without particular limitation in the present invention. The production method of the present invention can also be used for a copolymer having polyethylene as a partial structure, such as an ethylene vinyl acetate copolymer.

Preferred density of the ethylene polymer according to the present invention is a 0.890~0.970g / cm ^3, more preferably 0.900~0.940g / cm ^3. The average molecular weight is preferably a weight average molecular weight in the range of 10,000 to 7000000.

  The production method of the present invention is obtained by polymerizing an ethylene monomer by blending a nucleating agent dissolved in an organic aluminum compound or an organic aluminum compound and an organic solvent before or during the polymerization of the ethylene monomer. An ethylene polymer is used. The ratio of the ethylene monomer and the nucleating agent component is adjusted so that the nucleating agent component is 0.001 to 0.5 parts by mass with respect to 100 parts by mass of the ethylene polymer obtained by polymerizing the ethylene monomer. Done.

  As a method of adjusting the amount of the nucleating agent component to the above-mentioned blending amount with respect to the ethylene polymer, the polymerization activity when polymerized without adding the nucleating agent component is obtained, and the desired polymer is obtained with respect to the obtained polymer. Add nucleating agent dissolved in organoaluminum compound or organoaluminum compound and organic solvent so that blending amount of nucleating agent component is added, and polymerize under the same conditions as when no nucleating agent component was added. The method can be adopted. Moreover, the apparatus which introduce | transduces the apparatus which adjusts the addition amount of each component into superposition | polymerization equipment, and may adjust and polymerize so that a nucleating agent component may become the said compounding quantity.

  The polymerization of the ethylene monomer can be performed in an inert gas atmosphere such as nitrogen in the presence of a polymerization catalyst, but may be performed in the above organic solvent. In addition, an active hydrogen compound, a particulate carrier, an organoaluminum compound, an ion exchange layered compound, and an inorganic silicate may be added as long as polymerization is not inhibited.

  The said polymerization catalyst is not specifically limited, A well-known polymerization catalyst can be utilized, For example, a transition metal (for example, titanium, zirconium, hafnium, vanadium, iron, nickel, periodic table group 3-11) Lead, platinum, yttrium, samarium, etc.), and typical examples include a Ziegler catalyst, a Ziegler-Natta catalyst comprising a titanium-containing solid transition metal component and an organometallic component, and at least one cyclopentadienyl. A metallocene catalyst, a chromium-based catalyst, or the like composed of a transition metal compound of Group 4 to Group 6 of the periodic table having a skeleton and a promoter component can be used.

  Examples of the polymerization method of the ethylene monomer include aliphatic hydrocarbons such as butane, pentane, hexane, heptane and isooctane, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, and aromatics such as toluene, xylene and ethylbenzene. Slurry polymerization, which is polymerization in an inert solvent such as hydrocarbons, gasoline fractions, hydrogenated diesel fractions, etc., gas phase polymerization methods in which polymerization is carried out in the gas phase, bulk weight using ethylene monomer itself as the solvent A method of producing an ethylene homopolymer by polymerizing an ethylene monomer by a combination method, a solution polymerization method for producing a polymer in a liquid state, a polymerization method combining these, a single-stage polymerization method or a multi-stage polymerization method, propylene and carbon At least one selected from the group consisting of ethylene units having 2 to 12 atoms. Olefins (excluding propylene) polymerization process of a method for producing a copolymer to copolymer units may be mentioned, also, there is a batch type, a continuous type production system.

  In the present invention, in a polymerization facility having a bulk polymerization method, a gas phase polymerization method, or a combination thereof, the present invention can be applied as it is with a conventional polymerization facility. This is preferable because it is advantageous. The present invention can also be used in a slurry polymerization method, a solution polymerization method, etc., but these polymerization methods are not preferable from the viewpoint of labor saving because they require a drying step of an ethylene polymer.

The production method of the present invention comprises a step of bringing water or a nitrogen gas containing a proton donating substance or steam into contact with the ethylene polymer obtained as described above. .
In addition, according to another production method of the present invention, an ethylene polymer obtained by press-fitting nitrogen gas or steam containing moisture or a proton donating substance into an extruder into the ethylene polymer obtained as described above. It is characterized by comprising a step of melt-kneading.
Thereby, it is considered that the nucleating agent dissolved in the organic aluminum compound or the organic aluminum compound and the organic solvent can be regenerated.

In the production method of the present invention, when nitrogen gas containing water or a proton donating substance is used, the volume ratio with respect to nitrogen 1 is preferably 1.0 × 10 ^{−6 to} 2.5 × 10 ⁻² , More preferably, nitrogen gas comprising 1.0 × 10 ^{−3 to} 1.5 × 10 ⁻² of water is preferable. If the volume ratio to nitrogen 1 is less than 1.0 × 10 ⁻⁶ , it takes time to regenerate the nucleating agent, and if it exceeds 2.5 × 10 ⁻² , the resulting ethylene polymer contains water. The amount increases, and foaming may occur during the molding process.

  In the case where the step of contacting water or a nitrogen gas containing a proton donating substance or steam with the ethylene polymer obtained as described above corresponds to a continuous production system, the ethylene polymer May be used in a tank that is intermittently or continuously supplied, and a facility capable of bringing the nitrogen gas or steam into contact with the ethylene polymer may be used. For example, in a cylindrical column, ethylene polymer is supplied intermittently or continuously from the top of the column, nitrogen gas or steam is supplied from the bottom of the column, or ethylene polymer is supplied from the top of the tank, What is necessary is just to be able to discharge the ethylene polymer containing the regenerated nucleating agent, such as a type in which the nitrogen gas is supplied from below. Specific examples of the tank include a purge column and a steamer.

  Examples of the proton donating substance include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, ethylene glycol, glycerin, phenolic substances, Although mineral acids, such as hydrochloric acid and a sulfuric acid, are mentioned, In this invention, methanol and ethanol are used preferably.

  When the ethylene polymer obtained as described above is melt-kneaded with an extruder, it comprises a step of press-fitting nitrogen gas containing water or a proton donating substance or steam into the extruder. In the method for producing a polyethylene resin composition, when the ethylene polymer is melt-kneaded, it is contained in the ethylene polymer by bringing water or a nitrogen gas containing a proton donating substance or steam into contact with the ethylene polymer. It becomes possible to regenerate the nucleating agent component. Install an extruder that melts and kneads the ethylene polymer with other additives if necessary, and introduces nitrogen gas or steam containing water or a proton-donating substance into the extruder. This is preferable because there is no need for new capital investment.

  The extruder can be used without any distinction between single-screw, twin-screw, and multi-screw extrusion methods, and can be any one that can melt and knead the ethylene polymer and introduce steam into the extruder.

  In the method for producing a polyethylene resin composition of the present invention, the amount of water contained in the obtained polyethylene resin composition is in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the ethylene polymer. preferable. If the moisture content is less than 0.1 parts by mass with respect to 100 parts by mass of the ethylene polymer, the nucleating agent may not be sufficiently regenerated. If the moisture content is more than 5 parts by mass, foaming occurs during the molding of the polyethylene resin composition. May occur and the appearance of the molded product may be impaired.

  In the present invention, as long as it does not adversely affect the polymerization, other additives usually used for polyethylene resins can be added as necessary when the ethylene monomer is polymerized. When adding at the time of superposition | polymerization of an ethylene monomer, you may use what mixed and stirred the other additive, the nucleating agent, and the organoaluminum compound. Moreover, the method of supplying what suspended and mixed the additive and the solvent (slurry) can be used. A solvent is not specifically limited, For example, what was mentioned above is mentioned. You may mix | blend an additive after superposition | polymerization.

  In the reaction by this method, when the by-product compound does not affect the polymer, it can be used as it is. However, when the by-product compound has an adverse effect on the polymer, the compound is removed by distillation under reduced pressure or the like. It is preferable to use after using.

  Moreover, even if other additives have a negative effect on the polymerization when added directly, if the influence on the polymerization can be suppressed by masking with an organoaluminum compound, the method for producing the olefin resin composition of the present invention Can be used.

  Examples of the other additives include phenolic antioxidants, phosphorus antioxidants, ultraviolet absorbers, hindered amine compounds, heavy metal deactivators, nucleating agents, flame retardants, metal soaps (aliphatic carboxylate metal) Salt), hydrotalcite, filler, lubricant, antistatic agent, pigment, dye, plasticizer and the like.

Examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrenated phenol, 2,2′-methylenebis ( 4-ethyl-6-tert-butylphenol), 2,2′-thiobis- (6-tert-butyl-4-methylphenol), 2,2′-thiodiethylenebis [3- (3,5-di-tert -Butyl-4-hydroxyphenyl) propionate], 2-methyl-4,6-bis (octylsulfanylmethyl) phenol, 2,2'-isobutylidenebis (4,6-dimethylphenol), isooctyl-3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [3 (3,5-di-tert-v-butyl-4-hydroxyphenyl) propionamide, 2,2′-oxamido-bis [ethyl-3- (3,5-di-tertbutyl-4-hydroxyphenyl) Propionate], 2-ethylhexyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate, 2,2′-ethylenebis (4,6-di-tertbutylphenol), 3, Polymer of 5-bis (1,1-dimethylethyl) -4-hydroxy-benzenepropanoic acid and C13-15 alkyl, 2,5-di-tert-amylhydroquinone, hindered phenol (product of Adeka Palmalol) Name AO.OH.98), 2,2′-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2-tert Tyl-6- (3-tertbutyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-tertpentylphenyl) ethyl] -4 , 6-Di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-tert-butylbenz [d, f ] [1,3,2] -dioxaphosphobin, hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, bis [monoethyl (3,5-di-tert -Butyl-4-hydroxybenzyl) phosphonate calcium salt, 5,7-bis (1,1-dimethylethyl) -3-hydroxy-2 (3H) -ben Reaction product of zofuranone and o-xylene, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol, DL- a-tocophenol (vitamin E), 2,6-bis (α-methylbenzyl) -4-methylphenol, bis [3,3-bis- (4′-hydroxy-3′-tert-butyl-phenyl) butane Acid] glycol ester, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate Distearyl (3,5-di-tertbutyl-4-hydroxybenzyl) phosphonate, tridecyl-3,5-di-tert-butyl-4- Droxybenzylthioacetate, thiodiethylenebis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 4,4′-thiobis (6-tert-butyl-m-cresol), 2-octylthio -4,6-di (3,5-di-tertbutyl-4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tertbutylphenol), bis [3,3-bis (4-Hydroxy-3-tertbutylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (2,6-di-tert-butylphenol), 4,4′-butylidenebis (6-tert-butyl-3) -Methylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 1, , 3-Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methyl) Benzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3 ′, '-Di-tert-butyl-4'-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3 , 9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5 ] Undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], stearyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propion Acid amide, palmityl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, 3 such as listyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, lauryl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide -(3,5-dialkyl-4-hydroxyphenyl) propionic acid derivatives and the like.
The usage-amount of the said phenolic antioxidant is 0.001-10 mass parts with respect to the ethylene polymer obtained, More preferably, it is 0.01-0.5 mass part.

Examples of the phosphorus antioxidant include triphenyl phosphite, diisooctyl phosphite, heptakis (dipropylene glycol) triphosphite, triisodecyl phosphite, diphenylisooctyl phosphite, diisooctylphenyl phosphite, Diphenyl tridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tris (dipropylene glycol) phosphite, diisodecyl pentaerythritol diphosphite, dioleyl hydrogen phosphite, trilauryl trithiophosphite, Bis (tridecyl) phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, diphenyldecylphosphite, dinonylpheny Bis (nonylphenyl) phosphite, poly (dipropylene glycol) phenyl phosphite, tetraphenyldipropyl glycol diphosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,4-di-tert-butyl-5-methylphenyl) phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methyl Phenyl] phosphite, tri (decyl) phosphite, octyldiphenyl phosphite, di (decyl) monophenyl phosphite, distearyl pentaerythritol diphosphite, a mixture of distearyl pentaerythritol and calcium stearate, alkyl ( 10) Bisphenol A phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2 , 6-Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl) ) Pentaerythritol diphosphite, tetraphenyl-tetra (tridecyl) pentaerythritol tetraphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, tetra (tridecyl) isopropylidene dipheno Diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4) -Hydroxy-5-tert-butylphenyl) butanetriphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide, (1-methyl-1-propenyl-3-ylidene) tris (1,1-dimethylethyl) -5-methyl-4,1-phenylene) hexatridecyl phosphite, 2,2′-methylenebis ( 4,6-di-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylene (4,6-di-tert-butylphenyl) -octadecyl phosphite, 2,2′-ethylidenebis (4,6-di-tert-butylphenyl) fluorophosphite, 4,4′-butylidenebis (3- Methyl-6-tert-butylphenylditridecyl) phosphite, tris (2-[(2,4,8,10-tetrakis-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine Pin-6-yl) oxy] ethyl) amine, 3,9-bis (4-nonylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphesspiro [5,5] undecane, 2 , 4,6-Tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly 4,4′-isopropylidenediphenol C 2-15 alcohol phosphite, and the like.
The preferable usage-amount of phosphorus antioxidant is 0.001-10 mass parts with respect to 100 mass parts of ethylene polymers, More preferably, it is 0.01-0.5 mass part.

Examples of the thioether-based antioxidant include tetrakis [methylene-3- (laurylthio) propionate] methane, bis (methyl-4- [3-n-alkyl (C12 / C14) thiopropionyloxy] 5-tert-butyl. Phenyl) sulfide, ditridecyl-3,3′-thiodipropionate, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipro Pionate, lauryl / stearyl thiodipropionate, 4,4′-thiobis (6-tert-butyl-m-cresol), 2,2′-thiobis (6-tert-butyl-p-cresol), distearyl- Disulfide is mentioned.
The preferable usage-amount of a thioether type | system | group antioxidant is 0.001-10 mass parts with respect to 100 mass parts of obtained ethylene polymers, More preferably, it is 0.01-0.5 mass part.

Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methyl) Phenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- ( 2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3,5-dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-tert -Octyl-6-benzotriazolylphenol), 2- (2-hydroxy) Polyethylene glycol ester of 3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3- (2-acryloyloxyethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy -3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3- tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2- Hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyloxymethyl) phenyl] benzotriazole, 2- [ 2- (2-hydroxy) such as 2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) phenyl] benzotriazole Phenyl) benzotriazoles Phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy) benzoate , Dodecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, tetradecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, hexadecyl (3,5-di-tert-butyl-4) Benzoates such as -hydroxy) benzoate, octadecyl (3,5-di-tert-butyl-4-hydroxy) benzoate, behenyl (3,5-di-tert-butyl-4-hydroxy) benzoate; 2-ethyl-2 '-Ethoxyoxanilide, 2-ethoxy-4'-dodecyl Substituted oxanilides such as oxanilide; cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; various metal salts; Alternatively, metal chelates, particularly nickel, chromium salts, chelates and the like can be mentioned.
The preferable usage-amount of the said ultraviolet absorber is 0.001-5 mass parts with respect to 100 mass parts of obtained ethylene polymers, More preferably, it is 0.005-0.5 mass part.

  Examples of the flame retardant include aromatic phosphoric acid such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-xylenyl phosphate, and resorcinol bis (diphenyl phosphate). Phosphonates such as esters, divinyl phenylphosphonate, diallyl phenylphosphonate and phenylphosphonic acid (1-butenyl), phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phospha Phosphonic acid esters such as phenanthrene-10-oxide derivatives, phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicresyl phosphazene, melamine phosphate, melamine pyrophosphate, Melamine phosphate, melam polyphosphate, ammonium polyphosphate, phosphorus-containing vinylbenzyl compounds and phosphorus-based flame retardants such as red phosphorus, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol A type epoxy resin, bromine Phenol novolac epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclo Octane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene and 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, tribromophenyl Reimido, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, pentabromobenzyl acrylate, and include brominated flame retardants such as brominated styrene and the like.

Examples of the hindered amine compound include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6. -Tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2, 3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6) -Tetramethyl-4-piperidyl) -di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-pi Lysyl) -di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) -2-butyl-2- (3,5 -Di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6 -Bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis (2,2,6, 6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N- Butyl-N- 2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2 , 4-Bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8-12 tetraaza Dodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] amino Undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] Aminoundecane, bis {4- (1-octyloxy-2,2,6, 6-tetramethyl) piperidyl} decanedionate, bis {4- (2,2,6,6-tetramethyl-1-undecyloxy) piperidyl) carbonate, TINUVIN NOR 371 manufactured by Ciba Specialty Chemicals It is done.
The preferable usage-amount of the said hindered amine compound is 0.001-5 mass parts with respect to 100 mass parts of obtained ethylene polymer, More preferably, it is 0.005-0.5 mass part.

Examples of the flame retardant include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, resorcinol bis (diphenyl phosphate), (1-methylethylidene) ) -4,1-phenylenetetraphenyl diphosphate, 1,3-phenylenetetrakis (2,6-dimethylphenyl) phosphate, trade name ADEKA STAB FP-500 manufactured by ADEKA Corporation, trade name ADEKA STAB FP-600 manufactured by ADEKA Corporation, ADEKA Co., Ltd. product name Adeka Stub FP-800 and other aromatic phosphates, phenylphosphonic acid divinyl, phenylphosphonic acid diallyl, phenylphosphonic acid (1-butenyl) and other phosphonic acid esters Phosphinic acid esters such as phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, bis (2-allylphenoxy) phosphazene, dicresyl phosphazene, etc. Phosphazene compounds, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing vinylbenzyl compounds and phosphorus-based flame retardants such as red phosphorus, Metal hydroxide such as magnesium hydroxide and aluminum hydroxide, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylene vinyl (Pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, bromination Polyphenylene ether, brominated polystyrene and 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate , Pentabromobenzyl acrylate, and brominated flame retardants such as brominated styrene. These flame retardants are preferably used in combination with anti-drip agents such as fluororesins, and flame retardant aids such as polyhydric alcohols and hydrotalcite.
The preferable usage-amount of the said flame retardant is 1-50 mass parts with respect to 100 mass parts of obtained ethylene polymers, More preferably, it is 10-30 mass parts.

The lubricant is added for the purpose of imparting lubricity to the surface of the molded body and enhancing the effect of preventing damage. Examples of the lubricant include unsaturated fatty acid amides such as oleic acid amide and erucic acid amide; saturated fatty acid amides such as behenic acid amide and stearic acid amide, butyl stearate, stearyl alcohol, stearic acid monoglyceride, sorbitan monopalmititate, Examples include sorbitan monostearate, mannitol, stearic acid, hydrogenated castor oil, stearic acid amide, oleic acid amide, ethylene bis stearic acid amide and the like. These may be used alone or in combination of two or more.
The preferable usage-amount of the said lubricant is 0.03-2 mass parts with respect to 100 mass parts of obtained ethylene polymers, More preferably, it is 0.01-0.5 mass part.

Examples of the filler include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, Examples thereof include dolomite, mica, silica, alumina, potassium titanate whisker, wollastonite, fibrous magnesium oxysulfate, and the like. be able to. Moreover, what was surface-treated as needed can be used for a filler.
The preferable usage-amount of the said filler is 0.01-80 mass parts with respect to 100 mass parts of obtained ethylene polymers, More preferably, it is 1-50 mass parts.

（式中Ｒ^２６は、分岐鎖を有してもよく、ヒドロキシル基及びシクロアルキル基から選ばれる１種以上の置換基を有してもよい炭素原子数１〜３０の脂肪族基を表し、Ｍ^２は、金属原子を表し、ｎは、１〜４の整数であって、Ｍ２の金属原子の価数を表す）で表される化合物が挙げられる。 Examples of the aliphatic carboxylic acid metal salt include the following general formula (15),

(In the formula, R ²⁶ represents an aliphatic group having 1 to 30 carbon atoms which may have a branched chain and may have one or more substituents selected from a hydroxyl group and a cycloalkyl group; M ² represents a metal atom, and n is an integer of 1 to 4, and represents a valence of the metal atom of M 2).

In the general formula (15), R ²⁶ is an aliphatic group having 1 to 30 carbon atoms, may have a hydroxyl group, may have a cycloalkyl group, or may have a branch. Examples of the aliphatic group include hydrocarbon groups such as an alkyl group, an alkenyl group, and an alkyl group into which two or more unsaturated bonds are introduced. Specific examples of the aliphatic carboxylic acid represented by the general formula (15) include acetic acid, propionic acid, lactic acid, butyric acid, valeric acid, caproic acid, 2-ethylhexanoic acid, enanthic acid, pelargonic acid, caprylic acid, Neodecylic acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid, succinic acid , Lindelic acid, Tuzuic acid, Palmitoleic acid, Myristoleic acid, Petrothelic acid, Oleic acid, Elaidic acid, Vaccenoic acid, Linoleic acid, Linoleic acid, γ-Linolenic acid, Linolenic acid, Ricinoleic acid, Naphthenic acid, Abietic acid , Hydroxyacetic acid, lactic acid, β-hydroxypropionic acid, 2-methyl Examples include ru-β-hydroxypropionic acid, α-hydroxybutyric acid, β-hydroxybutyric acid, γ-hydroxybutyric acid, monomethylolpropionic acid, dimethylolpropionic acid, and 12-hydroxystearic acid. Among these, those having an aliphatic group having 12 to 22 carbon atoms are preferable because the effect of improving the physical properties of the olefin resin is increased, and myristic acid, stearic acid, 12-hydroxystearic acid, and the like are particularly preferable.

In the general formula (15), the metal atom represented by M ² includes alkali metal, magnesium, calcium, strontium, barium, titanium, manganese, iron, zinc, silicon, zirconium, yttrium, barium, hafnium, and the like. It is done. Among these, alkali metals such as sodium, lithium, and potassium are preferable, and sodium and lithium are particularly preferably used because the crystallization temperature of the ethylene polymer becomes good.
The amount of the aliphatic carboxylic acid metal salt used is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the obtained ethylene polymer.

ここで、一般式（１６）中、ｘ１及びｘ２はそれぞれ下記式、
０≦ｘ２／ｘ１＜１０，２≦ｘ１＋ｘ２≦２０
で表される条件を満たす数を表し、ｐは０又は正の数を表す。

ここで、一般式（１７）中、Ａ^q-は、ｑ価のアニオンを表し、ｐは０又は正の数を表す。
また、前記ハイドロタルサイト類における炭酸アニオンは、一部を他のアニオンで置換したものでもよい。 The hydrotalcite is a complex salt compound composed of magnesium, aluminum, hydroxyl group, carbonate group and any crystal water known as a natural product or synthetic product, and part of magnesium or aluminum may be alkali metal, zinc, etc. And those obtained by substituting hydroxyl groups and carbonate groups with other anionic groups. Specifically, for example, the hydrotalcite metal represented by the following general formula (16) is used as an alkali metal. Substituted ones are mentioned. In addition, as the Al—Li-based hydrotalcite, a compound represented by the following general formula (17) can also be used.

Here, in the general formula (16), x1 and x2 are respectively the following formulas:
0 ≦ x2 / x1 <10, 2 ≦ x1 + x2 ≦ 20
And p represents 0 or a positive number.

Here, in general formula (17), A ^q− represents a q-valent anion, and p represents 0 or a positive number.
The carbonate anion in the hydrotalcite may be partially substituted with another anion.

  The hydrotalcites may be those obtained by dehydrating crystal water, higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal oleate, and organic sulfonic acids such as alkali metal dodecylbenzenesulfonate. It may be coated with a metal salt, higher fatty acid amide, higher fatty acid ester or wax.

The hydrotalcites may be natural products or synthetic products. As methods for synthesizing the compounds, Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. 3-36839, Japanese Patent Publication No. 61-174270, Known methods described in, for example, Kaihei No. 5-179052. Further, the hydrotalcites can be used without being limited by their crystal structure, crystal particles and the like.
The preferable usage-amount of the said hydrotalcites is 0.001-5 mass parts with respect to 100 mass parts of obtained ethylene polymers, More preferably, it is 0.05-3 mass parts.

Examples of the antistatic agent include cationic antistatic agents such as fatty acid quaternary ammonium ion salts and polyamine quaternary salts; higher alcohol phosphate esters, higher alcohol EO adducts, polyethylene glycol fatty acid esters, anionic type Anionic antistatic agents such as alkyl sulfonates, higher alcohol sulfates, higher alcohol ethylene oxide adduct sulfates, higher alcohol ethylene oxide adduct phosphates; polyhydric alcohol fatty acid esters, polyglycol phosphates, poly Nonionic antistatic agents such as oxyethylene alkyl allyl ether; amphoteric antistatic agents such as amphoteric alkylbetaines such as alkyldimethylaminoacetic acid betaine and imidazoline type amphoteric activators. Such antistatic agents may be used alone, or two or more kinds of antistatic agents may be used in combination.
The preferable usage-amount of the said antistatic agent is 0.01-20 mass parts with respect to 100 mass parts of obtained ethylene polymers, More preferably, it is 3-10 mass parts.

  As the pigment, commercially available pigments can also be used. For example, Pigment Red 1, 2, 3, 9, 10, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; Pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50 and the like.

  Examples of the dye include an azo dye, anthraquinone dye, indigoid dye, triarylmethane dye, xanthene dye, alizarin dye, acridine dye, stilbene dye, thiazole dye, naphthol dye, quinoline dye, nitro dye, indamine dye, oxazine dye, phthalocyanine Examples thereof include dyes and dyes such as cyanine dyes, and a plurality of these may be used in combination.

Examples of the filler include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, Dolomite, mica, silica, alumina, potassium titanate whisker, wollastonite, fibrous magnesium oxysulfate and the like are preferable. Among these fillers, those having an average particle diameter (spherical or flat) or an average fiber diameter (needle or fiber) of 5 μm or less are preferable.
The preferable usage-amount of the said filler is 0.01-50 mass parts with respect to 100 mass parts of obtained ethylene polymers, More preferably, it is 1-30 mass parts.

  In addition, the usage-amount of each additive shown above shows the usage-amount of each additive in the molded article shape | molded using the masterbatch produced with the manufacturing method of this invention.

  When the nucleating agent master batch obtained by the production method of the present invention is applied to a polyethylene resin, the kneading of the polyethylene resin and the master batch is performed by a kneader, a roll mill, a single screw extruder, a twin screw extruder, a multi screw extruder, or the like. Although usable, a single screw extruder and a twin screw extruder are preferable in terms of operability. When using a twin-screw extruder, the screw rotation direction can be used without distinction between the same direction and different directions. Moreover, it is preferable to deaerate by replacement with an inert gas or single-stage and multistage vents in order to improve the quality and working environment.

  Moreover, the said other additive can be mix | blended and melt-kneaded with a polyethylene resin with the masterbatch obtained with the manufacturing method of this invention.

  When blending the other additive to the polyethylene resin composition obtained by the production method of the present invention, after mixing the ethylene polymer and the other additive, kneader, roll mill, single screw extruder, Examples thereof include a melt kneading method using a processing machine such as a twin screw extruder or a multi screw extruder, and a single screw extruder or a twin screw extruder is preferable in terms of operability. When using a twin-screw extruder, the screw rotation direction can be used without distinction between the same direction and different directions. Moreover, it is preferable to deaerate by replacement with an inert gas or single-stage and multistage vents in order to improve the quality and working environment.

  The polyethylene resin composition obtained by the production method of the present invention can be molded by a known molding method such as extrusion molding, injection molding, hollow molding, blow molding, compression molding, etc., for food containers, cosmetics and clothing. Containers, food bottles, beverage bottles, edible oil bottles, seasoning bottles and other bottles, food packaging materials, wrapping materials, packaging materials for transport packaging materials, sheets / films, fibers, daily goods, toys, etc. The molded product can be easily obtained. Moreover, it is good also as a fiber reinforced plastic by mix | blending glass fiber, carbon fiber, etc.

  EXAMPLES Hereinafter, although a manufacture example, an Example, and a comparative example are given and this invention is demonstrated further more concretely, this invention is not restrict | limited at all by the following examples.

(Preliminary polymerization)
In order to adjust the blending amount of the nucleating agent in the olefin polymer, the polymerization activity when the nucleating agent solution was not added was determined. The polymerization conditions were as follows.

(Preliminary polymerization)
A Ziegler catalyst was sequentially added and stirred in a nitrogen-substituted autoclave so that 600 ml of heptane, 152 mg of triethylaluminum, and a Ziegler catalyst had a heptane slurry of 0.007 mmol in terms of Ti. The inside of the autoclave is replaced with an ethylene atmosphere, and a pressure of 1 kgf / cm ² G is applied, the temperature is raised to 70 ° C., a pressure of 6 kgf / cm ² G is applied to the autoclave with ethylene, and a polymerization reaction is performed at 70 ° C. for 1.5 hours. went. After replacing the system with nitrogen gas, 5 ml of ethanol was added at 40 ° C. to stop the polymerization reaction, and then the solvent was removed under reduced pressure at 50 ° C. Then, the polymer was dried at 40 ° C. in vacuum for 5 hours A polymer was obtained. The polymerization activity of the obtained polymer was 12.0 kg per 1 g of the catalyst.

(Preparation of solution of nucleating agent component)
Prepare a solution of the nucleating agent component with a nucleating agent component of 20 mg / ml by adding heptane to the nucleating agent component to the flask purged with nitrogen and adding dropwise heptane to the nucleating agent component with stirring. did.

化合物１：ヒドロキシ−２，２’−メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェニル）ホスフェート
化合物２：３，３’−（メチレンビス（２，６−ジエチル−４，１−フェニレン））ビス（１−（ｏ−トリイル）プロパン−２−オン）
化合物３：安息香酸ソジウム塩

Compound 1: Hydroxy-2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate Compound 2: 3,3 ′-(methylenebis (2,6-diethyl-4,1-phenylene)) bis ( 1- (o-triyl) propan-2-one)
Compound 3: Sodium benzoate salt

(polymerization)
Under the prepolymerization conditions, immediately before adding the Ziegler catalyst, 100 parts by mass of the ethylene polymer obtained by polymerization is added so that the nucleating agent component solution has the blending amount shown in Table 2, and the autoclave Polymerization was carried out under the same conditions as the above prepolymerization except that the amount of heptane was added so that the total amount of the solution was 600 ml. Ethanol was not added.
However, when the mixture C was supplied to the polymerization of the ethylene monomer, the polymerization activity was low, and an amount of ethylene polymer necessary for the molding process could not be obtained.

[Example 1-1]
A commercially available high-purity nitrogen gas was passed through water to obtain a nitrogen gas having a water content of 1.2 × 10 −3 by volume with respect to nitrogen 1. Next, each ethylene polymer obtained by the above production method was transferred to a purge column while containing a solvent, and the solvent was transferred to a flare line in a nitrogen atmosphere to remove the solvent. The nitrogen polymer was passed from the bottom of the cylindrical container at a flow rate of 100 ml / min for 2 hours to remove the solvent from the ethylene polymer, thereby regenerating the nucleating agent component contained in the ethylene polymer.

[Example 1-2]
In Example 1-1, nitrogen gas having a volume ratio of 1.2 × 10 −3 with respect to nitrogen 1 and a volume ratio of 1.0 × 10 −2 with respect to nitrogen 1 was used. This was carried out in the same manner as in Example 1 except that the nitrogen gas was changed.

[Example 1-3]
The same operation as in Example 1 was performed except that water was replaced with methanol in Example 1-1.

[Example 1-4]
The same operation as in Example 1 was performed except that water was replaced with ethanol in Example 1-1.

[Example 1-5]
The ethylene polymer obtained in Production Example 1-1 was transferred to a purge column while containing a solvent, and the solvent was transferred to a flare line under nitrogen to remove the solvent. Next, 5 kPa of steam was allowed to flow at a flow rate of 100 ml / min for 2 hours from below the column on the cylinder of the purge column to contact the ethylene polymer.

[Comparative Example 1-1]
In Example 1-1, the same procedure as in Example 1 was performed except that nitrogen gas was used as it was without passing through water.

[Comparative Example 1-2]
In Example 1-1, the procedure was performed in the same manner as in Example 1-1 except that water (not steam) was used instead of nitrogen gas containing moisture.

(Evaluation)
Tetrakis [methylene-3- (3 ′, 5′-ditertiarybutyl-4′-hydroxyphenyl) propionate] methane as a phenolic antioxidant for 100 parts by mass of each obtained ethylene polymer. 03 parts by mass, as phosphorus-based antioxidant, 0.03 parts by mass of tris (2,4-ditert-butylphenyl) phosphite, as hydrotalcite, Kyowa Chemical Industry Co., Ltd. trade name: DHT-4A0.05 0.13 parts by mass of sodium stearate as an aliphatic carboxylic acid metal salt are added, and each additive is added and mixed, and a small injection molding machine for laboratory (Compounder 15, Injection molder 12 manufactured by DSM Xplore) And kneaded at 260 ° C. to obtain a strand. After the pellets were pelletized, the above small laboratory injection molding machine was used for injection molding under conditions of an injection temperature of 260 ° C. and a mold temperature of 40 ° C. to obtain a flat test piece of 50 mm × 50 mm × 1 mm.

(Cloudy)
The state of the obtained flat test piece was visually observed. These results are shown in Table 2 below.

(Volatilization amount)
The obtained strand was cut out, weighed to 5 mg, and used as a measurement sample. The amount of volatilization was Rigaku Co., Ltd. Thermo Plus 2 / (TG-DTA series), under a nitrogen atmosphere (flow rate: 200 ml / min), measurement sample: 5 mg, heating rate: 50 ° C./min. The weight loss when the temperature reached 150 ° C. from room temperature was measured, and the volatilization amount (%) was calculated by the following formula.
Volatilization amount (%) = (weight reduction amount) / (measurement sample weight−weight reduction amount) × 100
These results are shown in Table 2 below.

  From Comparative Example 1-1 of Table 2, when no nitrogen gas containing water or a proton-donating substance and steam were not introduced, regeneration of the nucleating agent was insufficient, and the transparency of the molded article was sufficient It was not something. Further, from Comparative Example 1-2, when the ethylene polymer was treated with water that was not steam, the transparency of the molded product was improved, but the water content of the ethylene polymer was large, and a foaming phenomenon occurred during the molding process. The molding process was not stable.

  On the other hand, from Examples 1-1 and 1-2, the molded article of the polyethylene resin composition produced by the method of the present invention in which nitrogen gas containing water is brought into contact with the ethylene polymer is excellent in transparency and molded. No foaming phenomenon was observed during processing. In addition, from Examples 1-3 and 1-4, it was confirmed that the effects of the present invention can be obtained when proton-donating substances such as methanol and ethanol are used instead of water. Moreover, from Example 1-5, it was confirmed that the effect of the present invention was also obtained when steam was brought into contact with the ethylene polymer.

[Example 2-1]
As a phenolic antioxidant, 100 parts by mass of an ethylene polymer obtained by polymerizing an ethylene monomer by supplying a compound 1 dissolved in an organoaluminum compound at the time of polymerization to a blending amount shown in Table 3 is used. , Tetrakis [methylene-3- (3 ′, 5′-ditertiarybutyl-4′-hydroxyphenyl) propionate] methane 0.03 parts by mass, as a phosphorus-based antioxidant, tris (2,4-ditertiary Butylphenyl) phosphite 0.03 parts by mass, hydrotalcite, Kyowa Chemical Industry Co., Ltd. trade name: DHT-4A 0.05 parts by mass, aliphatic carboxylic acid metal salt 0.13 sodium stearate A mass part is mix | blended, each additive is added and mixed, and a twin screw extruder (Ikegai-made PCM-30, extrusion temperature: 260 degreeC, screw rotational speed 50rpm) In was granulated. During granulation, the ethylene polymer is run under nitrogen until the ethylene polymer is fed to the twin screw extruder, and the ethylene polymer is drawn while venting is performed near the head of the twin screw extruder and the center of the screw. From the feed port to the vent, steam was pressed into the barrel at a pressure of 15 kPa and a flow rate of 100 ml / min to obtain pellets.

[Example 2-2]
In Example 2-1, in place of steam introduction, Example 2-1, except that 1.0 × 10 −3 nitrogen gas was introduced at a flow rate of 100 ml / min in a volume ratio with respect to nitrogen 1. It carried out similarly and obtained the pellet.

[Example 2-3]
In Example 2-1 above, pellets were obtained in the same manner as in Example 2-1 except that the nucleating agent was changed to the ethylene polymer which was compound 2 instead of compound 1.

[Example 2-4]
Example 2-2 was carried out in the same manner as in Example 2-2 except that the nucleating agent was changed to an ethylene polymer that was compound 2 instead of compound 1.

[Comparative Example 2-1]
In Example 2-1 above, pellets were obtained in the same manner as in Example 2-1 except that steam introduction and vent drawing were not performed during the granulation of the ethylene polymer.

[Comparative Example 2-2]
In Example 2-3, pellets were obtained in the same manner as in Example 2-3 except that steam was not introduced and vent was not drawn during the granulation of the ethylene polymer.

[Evaluation]
The pellets obtained in each of the above Examples and Comparative Examples were injection molded under the conditions of an injection temperature of 260 ° C. and a mold temperature of 40 ° C. using a small laboratory injection molding machine (Compounder 15, Injection molder 12 manufactured by DSC Xplore). A flat test piece of 50 mm × 50 mm × 1 mm was obtained.

  In the obtained flat test piece, the presence or absence of cloudiness was confirmed. These results are shown in Table 3.

  From Comparative Examples 2-1 and 2-2 in Table 3, the molded article of the ethylene polymer that did not use the production method of the present invention could not obtain sufficient transparency. On the other hand, from Examples 2-1 to 2-4, it was confirmed that the molded article using the ethylene polymer obtained by the production method of the present invention has good transparency.

  From the above, the present invention provides a molded article exhibiting excellent transparency by granulating the ethylene polymer by pressing water or nitrogen gas containing a proton donating substance or steam into the extruder. It was confirmed that it was obtained.

Claims (10)

  Before or during the polymerization, water or proton is used for the ethylene polymer obtained by polymerizing the ethylene monomer by blending the nucleating agent dissolved in the organic aluminum compound or the mixed solvent of the organic aluminum compound and the organic solvent. A process for producing a polyethylene resin composition, comprising a step of contacting nitrogen gas containing a donating substance or steam.   Water or proton donation to an ethylene polymer obtained by polymerizing an ethylene monomer by supplying a nucleating agent dissolved in an organoaluminum compound or a mixed solvent of an organoaluminum compound and an organic solvent before or during the polymerization A process for producing a polyethylene resin composition, comprising a step of press-fitting nitrogen gas containing a chemical substance or steam into an extruder and melt-kneading an ethylene polymer. The method for producing a polyethylene resin composition according to claim 1 or 2, wherein the nucleating agent is a compound represented by the following general formula (1).

(Wherein R ^{1 to} R ⁴ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms, R ⁵ represents a hydrogen atom or a methyl group, and m represents 1; Or when m is 1, M ¹ represents a hydrogen atom or an alkali metal atom, and when m is 2, M ¹ represents a group 2 element, Al (OH) or Zn.)   The method for producing a polyethylene resin composition according to claim 1 or 2, wherein the nucleating agent is an amide compound.   The method for producing a polyethylene resin composition according to any one of claims 1 to 3, wherein the organoaluminum compound is trialkylaluminum.   The method for producing a polyethylene resin composition according to any one of claims 1 to 5, wherein the organic solvent is selected from an aliphatic hydrocarbon compound and an aromatic hydrocarbon compound.   The method for producing a polyethylene resin composition according to any one of claims 1 to 6, wherein the proton donating substance is selected from methanol and ethanol.   The method for producing a polyethylene resin composition according to any one of claims 1 to 7, wherein the ethylene polymer is polyethylene having a weight average molecular weight of 10,000 to 7000000.   It is the polyethylene resin composition obtained with the manufacturing method of the polyethylene resin composition as described in any one of Claims 1-8, Comprising: The moisture content contained is 0.1 mass with respect to 100 mass parts of ethylene polymers. A polyethylene resin composition characterized by being in the range of ˜5 parts by mass.   A molded article obtained by molding a polyethylene resin composition obtained by the method for producing a polyethylene resin composition according to any one of claims 1 to 9.