JP5286629B2 - Master batch for resin - Google Patents

Description

  The present invention relates to a method for producing a masterbatch for polyolefin resin or polystyrene resin, and the above-mentioned masterbatch for resin.

  In Patent Document 1, 0.01 to 1 part by weight of an antioxidant having a phosphite ester structure and a hindered phenol structure in the same molecule and 100% by weight of a hydrotalcite-based compound with respect to 100 parts by weight of a polyethylene resin. A polyethylene resin composition characterized by containing 0.01 to 1 part by weight and / or 0.01 to 1 part by weight of a Group II metal salt of a higher fatty acid periodic table is described.

［式中、Ｐｈ_１及びＰｈ’_１はフェニレン基を表し、該フェニレン基の水素原子はフェニル基、炭素数１〜８のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基又は炭素数７〜１２のアラルキル基で置換されていてもよい。
Ｘは単結合、硫黄原子又は−ＣＨＲ⁶−基を表す。Ｒ⁶は水素原子、炭素数１〜８のアルキル基又は炭素数５〜８のシクロアルキル基を表す。
Ｐｈ_２及びＰｈ’_２はフェニル基又はビフェニル基を表し、該フェニル基又はビフェニル基の水素原子は炭素数１〜８のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基又は炭素数７〜１２のアラルキル基で置換されていてもよい。
Ｐｈ_３はフェニル基又はビフェニル基を表し、該フェニル基又はビフェニル基の水素原子は炭素数１〜８のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基又は炭素数７〜１２のアラルキル基で置換されていてもよい。］ In addition, Patent Document 2 and the like have a partial structure represented by the following formula (I), (II) or (III) in the molecule as a stabilizer for preventing thermal degradation or oxidative degradation of polyolefin or polystyrene resin. Antioxidants are described.

[Wherein, Ph ₁ and Ph ′ ₁ represent a phenylene group, and the hydrogen atom of the phenylene group is a phenyl group, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 6 to 12 carbon atoms. Or an alkylcycloalkyl group or an aralkyl group having 7 to 12 carbon atoms.
X represents a single bond, a sulfur atom or a —CHR ⁶ — group. R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms.
Ph ₂ and Ph ′ ₂ represent a phenyl group or a biphenyl group, and the hydrogen atom of the phenyl group or biphenyl group is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a 6 to 12 carbon atom. It may be substituted with an alkylcycloalkyl group or an aralkyl group having 7 to 12 carbon atoms.
Ph ₃ represents a phenyl group or a biphenyl group, and the hydrogen atom of the phenyl group or biphenyl group is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkylcycloalkyl group having 6 to 12 carbon atoms. Alternatively, it may be substituted with an aralkyl group having 7 to 12 carbon atoms. ]

JP 2002-146121 A (refer to claims) Japanese Patent Laid-Open No. 10-273494 (refer to the claims)

When manufacturing a polyolefin resin or a polystyrene resin, a method of blending a master batch of an antioxidant with a pellet of a polyolefin resin or a polystyrene resin and kneading and molding is employed.
However, the masterbatch for polyolefin resin and polystyrene resin containing this relatively high concentration of antioxidant is easily hydrolyzed when the above-mentioned antioxidant is stored in a warehouse at high temperature and high humidity. When the masterbatch after long-term storage was used for polyolefin resin or polystyrene resin, the antioxidant performance was not sufficient.

In order to solve the above-mentioned problems, measures such as filling and storing a master batch for polyolefin resin or polystyrene resin in a moisture-proof packaging material have been taken. However, this method has a problem of increasing the cost. It was.
In addition, even if a moisture-proof packaging material is filled with a masterbatch for polyolefin resin or polystyrene resin and stored, it absorbs moisture once opened, and the antioxidant is easily hydrolyzed. Had to be used up at once.

An object of the present invention is to provide a masterbatch for polyolefin resin or polystyrene resin having improved hydrolysis resistance.
Moreover, the objective of this invention is providing the manufacturing method of said masterbatch for resin.
Furthermore, another object of the present invention relates to a method of applying the masterbatch for polyolefin resin or polystyrene resin to the polyolefin resin or polystyrene resin.
This inventor repeated earnest examination in order to provide the masterbatch for polyolefin resin or polystyrene resin excellent in hydrolysis resistance. As a result, from a group II metal salt of a periodic table of hydrotalcite compounds and higher fatty acids, a masterbatch of polyolefin resin or polystyrene resin containing an antioxidant represented by the following formula (1) at a relatively high concentration A masterbatch for polyolefin resin or polystyrene resin containing a specific amount of one or more selected compounds is improved in hydrolysis resistance of the antioxidant (1) in the masterbatch. After storage in a warehouse, the inventors have found that the hydrolysis resistance of the antioxidant in the polyolefin resin or polystyrene resin is improved, and have completed the present invention.

（１）
［式中、Ｒ^１、Ｒ^２、Ｒ^４及びＲ^５はそれぞれ独立に水素原子、炭素数１〜８のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基又はフェニル基を表し、Ｒ^３は水素原子又は炭素数１〜８のアルキル基を表す。Ｘは単結合、硫黄原子又は−ＣＨＲ⁶−基を表す。Ｒ⁶は水素原子、炭素数１〜８のアルキル基又は炭素数５〜８のシクロアルキル基を表す。
Ａは炭素数２〜８のアルキレン基又は＊−ＣＯＲ⁷−基を表す。Ｒ⁷は単結合又は炭素数１〜８のアルキレン基を表し、＊印を付した−ＣＯＲ⁷−基は式（１）におけるフォスファイト構造の酸素原子と結合していることを表す。上記の炭素数２〜８のアルキレン基における炭素−炭素結合は、酸素原子、硫黄原子、−ＮＨ−、−ＯＣＯ−又は−ＣＯＯ−で中断されていてもよい。
Ｙ及びＺは、いずれか一方がヒドロキシル基、炭素数１〜８のアルコキシ基又は炭素数７〜１２のアラルキルオキシ基を表し、他方が水素原子又は炭素数１〜８のアルキル基を表す。但し、Ｙがヒドロキシル基であるときは、Ｒ^４及びＲ^５の一方は炭素数３〜８のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基又はフェニル基を表す。
また、式（１）における２個のＲ^１は互いに同一でもよく、異なってもよい。さらに、式（１）における２個のＲ^２は互いに同一でもよく、異なってもよい。そして、式（１）における２個のＲ^３は互いに同一でもよく、異なってもよい。］ That is, the present invention is selected from the group consisting of a polyolefin resin, 1.5 parts by weight to 100 parts by weight of the following (A), and the following (B) and (C) per 100 parts by weight of the polyolefin resin. And 0.01 to 1 part by weight of one or more kinds of compounds. A masterbatch for polyolefin resins is provided.
(A) Antioxidant represented by the following formula (1) (B) Hydrotalcite compound (C) Group II metal salt of higher fatty acid periodic table

(1)
[Wherein R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkylcycloalkyl having 6 to 12 carbon atoms. group, an aralkyl group or a phenyl group having 7 to 12 carbon atoms, R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. X represents a single bond, a sulfur atom or a —CHR ⁶ — group. R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms.
A represents an alkylene group or a * -COR ⁷ 2 to 8 carbon atoms - group. R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and the —COR ⁷ — group marked with * represents that it is bonded to the oxygen atom of the phosphite structure in formula (1). The carbon-carbon bond in the alkylene group having 2 to 8 carbon atoms may be interrupted by an oxygen atom, a sulfur atom, -NH-, -OCO- or -COO-.
One of Y and Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. However, when Y is a hydroxyl group, one of R ⁴ and R ⁵ is an alkyl group having 3 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, carbon It represents an aralkyl group or a phenyl group of formula 7-12.
Further, two R ^{1 s} in the formula (1) may be the same or different. Further, the two R ² in the formula (1) may be the same or different. And two R < ³ > in Formula (1) may mutually be same, and may differ. ]

Further, the present invention is selected from the group consisting of a polystyrene resin, 1.5 parts by weight to 100 parts by weight of the above (A), and (B) and (C) per 100 parts by weight of the polystyrene resin. A masterbatch for polystyrene resin is provided, comprising 0.01 to 1 part by weight of one or more compounds.
Next, the present invention is 1 selected from the group consisting of 1.5 parts by weight to 100 parts by weight of the above (A) and (B) and (C) above per 100 parts by weight of the polyolefin resin and the polyolefin resin. Provided is a method for producing a masterbatch for polyolefin resin, which comprises blending 0.01 to 1 part by weight of at least one compound and melt-kneading. Further, the present invention is selected from the group consisting of 1.5 parts by weight to 100 parts by weight of the above (A) and the above (B) and (C) per 100 parts by weight of the polystyrene resin and the polystyrene resin. Provided is a method for producing a masterbatch for polystyrene resin, which is prepared by blending 0.01 to 1 part by weight of one or more compounds and melt-kneading.
Furthermore, this invention provides the polyolefin resin manufactured by mix | blending polyolefin resin and the masterbatch for polyolefin resins, and melt-kneading. And this invention provides the polystyrene-type resin manufactured by mix | blending a polystyrene-type resin and the masterbatch for polystyrene-type resin resins, and melt-kneading. Moreover, this invention provides the masterbatch mentioned above.

  According to the masterbatch for polyolefin resin of the present invention and its production method, and the masterbatch for polystyrene resin and its production method, the hydrolysis resistance of the antioxidant (1) in the masterbatch is improved. After the batch is stored in the warehouse, the hydrolysis resistance of the antioxidant in the polyolefin resin or polystyrene resin is improved. Moreover, as a result of improving the hydrolysis resistance of the antioxidant (1), deterioration due to oxidation of the polyolefin resin during melt kneading of the polyolefin and the master batch for polyolefin resin is prevented. Similarly, deterioration due to oxidation of the polystyrene resin at the time of melt-kneading the polystyrene resin and the master batch for polystyrene resin is prevented.

Hereinafter, the present invention will be described in detail.
Examples of the polyolefin resin in the present invention include homopolymers such as ethylene, propylene, vinyl acetate, α-olefin and MMA (methyl methacrylate); block copolymers; random copolymers and copolymers of three or more. Is mentioned.
Examples of the polystyrene-based resin in the present invention include homopolymers such as styrene, acrylonitrile, butadiene, isoprene and MMA; block copolymers; copolymers of ternary or higher, and mixtures of the above polymers. It is done.

In the present invention, polyethylene (for example, HD-PE, LD-PE or LLDPE); polypropylene (for example, homopolymer, block copolymer, random copolymer or terpolymer); EVA resin; EMMA resin; ABS resin; HI-PS resin; -PS resin; SIBS resin; SBS resin; SIS resin; MS resin; AS resin and the like are preferably used.
The manufacturing method of said polyolefin resin or polystyrene-type resin is not specifically limited, What was manufactured by the well-known method etc. can be used.

  In the masterbatch for polyolefin resin and the masterbatch for polystyrene resin of the present invention, the following compound (1) is used as an antioxidant.

（１）
上式（１）におけるＲ^１、Ｒ^２、Ｒ^４及びＲ^５はそれぞれ独立に水素原子、炭素数１〜８のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基又はフェニル基を表す。
Ｒ^３は水素原子又は炭素数１〜８のアルキル基を表す。Ｘは単結合、硫黄原子又は−ＣＨＲ⁶−基を表す。Ｒ⁶は水素原子、炭素数１〜８のアルキル基又は炭素数５〜８のシクロアルキル基を示す。Ａは炭素数２〜８のアルキレン基又は＊−ＣＯＲ⁷−基を表す。
上記の炭素数２〜８のアルキレン基における炭素−炭素結合は、酸素原子、硫黄原子、−ＮＨ−、−ＯＣＯ−又は−ＣＯＯ−で中断されていてもよい。Ｒ⁷は単結合又は炭素数１〜８のアルキレン基を表す。上記−ＣＯＲ⁷−基における＊印は、式（１）中のフォスファイト構造の酸素原子に結合していることを示す。
Ｙ及びＺは、いずれか一方がヒドロキシル基、炭素数１〜８のアルコキシ基又は炭素数７〜１２のアラルキルオキシ基を表し、他方が水素原子又は炭素数１〜８のアルキル基を表す。
但し、Ｙがヒドロキシル基であるときは、Ｒ^４及びＲ^５の一方は炭素数３〜８のアルキル基、炭素数５〜８のシクロアルキル基、炭素数６〜１２のアルキルシクロアルキル基、炭素数７〜１２のアラルキル基又はフェニル基を表す。

(1)
R ¹ , R ² , R ⁴ and R ⁵ in the above formula (1) are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkyl having 6 to 12 carbon atoms. It represents a cycloalkyl group, an aralkyl group having 7 to 12 carbon atoms, or a phenyl group.
R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. X represents a single bond, a sulfur atom or a —CHR ⁶ — group. R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms. A represents an alkylene group or a * -COR ⁷ 2 to 8 carbon atoms - group.
The carbon-carbon bond in the alkylene group having 2 to 8 carbon atoms may be interrupted by an oxygen atom, a sulfur atom, -NH-, -OCO- or -COO-. R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms. The * mark in the -COR ⁷ -group indicates that it is bonded to the oxygen atom of the phosphite structure in the formula (1).
One of Y and Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
However, when Y is a hydroxyl group, one of R ⁴ and R ⁵ is an alkyl group having 3 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, carbon It represents an aralkyl group or a phenyl group of formula 7-12.

Among the antioxidants (A) represented by the above formula (1), R ¹ , R ² , R ⁴ and R ⁵ are each independently a methyl group, a t-butyl group, a t-pentyl group or a t-octyl group. Certain compounds are preferred. R ³ is preferably a hydrogen atom or a methyl group. X is preferably a single bond, a methylene group or an ethylidene group. A is preferably a compound having an alkylene group having 2 to 4 carbon atoms or a * —COR ⁷ — group.
When the carbon-carbon bond in the alkylene group having 2 to 8 carbon atoms is interrupted, the interrupting group is preferably —OCO— or —COO—. R ⁷ is preferably an alkylene group having 1 to 4 carbon atoms. When Y is a hydroxyl group, Z is preferably a hydrogen atom or a methyl group, and one of R ⁴ and R ⁵ is preferably a t-butyl group. Further, Z is, when a hydroxyl group, R ⁵ is a methyl group, Y is a hydrogen atom, and it is preferred that R ⁴ is a t- butyl group.

Of the compound (1), particularly preferred compounds are exemplified below.
6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] di Oxaphosphepine [A1], 6- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphepine, 6- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propoxy] -4,8-di-tert-butyl-2,10 -Dimethyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, 6- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -4, 8-di-t-butyl-2,10-dimethyl-12H-dibenzo [d, g] [1,3,2] dioxaphospho Emissions, and the like.

  In the polyolefin resin masterbatch or polystyrene resin masterbatch of the present invention, the content of the antioxidant (1) is from 1.5 parts by weight to 100 parts by weight per 100 parts by weight of the polyolefin resin or polystyrene resin. It is a range. The content of the antioxidant (1) is more preferably in the range of 1.5 to 50 parts by weight, particularly preferably in the range of 2 to 20 parts by weight.

  The polyolefin resin masterbatch or polystyrene resin masterbatch containing 100 parts by weight of polyolefin resin or polystyrene resin and less than 1.5 parts by weight of the antioxidant (1) is a hydrotalcite compound (B ) And the higher fatty acid periodic group II metal salt (C), the hydrolysis resistance of the antioxidant (I) in the masterbatch described above is at a level that causes no practical problems. Moreover, it is economically disadvantageous to add a hydrotalcite-based compound or a Group II metal salt of a higher fatty acid to such a masterbatch.

  On the other hand, the polyolefin resin masterbatch or polystyrene resin masterbatch containing 100 parts by weight of the polyolefin resin or polystyrene resin and 100 parts by weight of the antioxidant (1) is deteriorated in physical properties and handling. May cause trouble.

As the hydrotalcite compound used in the masterbatch for polyolefin resin or the masterbatch for polystyrene resin of the present invention, for example, the hydrotalcite compound described in paragraph No. 0055 of JP-A No. 2002-146121, And hydrotalcites described in paragraph No. 0050 of Kaihei 10-273494.
In the present invention, preferred hydrotalcite compounds include, for example, hydrotalcites represented by the following formula.
Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · pH ₂ O
(In the formula, x represents a numerical value of 0 to 0.5, and p represents a numerical value of 0 to 2.)
Specific examples of the hydrotalcite compound include synthetic hydrotalcite DHT-4A [B1] manufactured by Kyowa Chemical Industry Co., Ltd.

  Examples of Group II metal salts of higher fatty acids used in the polyolefin resin masterbatch and polystyrene resin masterbatch of the present invention include calcium stearate [C1], zinc stearate [C2], and magnesium stearate [ C3] and calcium laurate [C4].

The hydrotalcite compound and the higher fatty acid Group II metal salt of the higher fatty acid in the polyolefin resin masterbatch and polystyrene resin masterbatch of the present invention may be used alone or in combination.
The total content of the hydrotalcite compound and the Group II metal salt of the higher fatty acid is in the range of 0.01 to 1 part by weight per 100 parts by weight of the polyolefin resin or polystyrene resin. The preferred total content of the hydrotalcite compound and the higher fatty acid Group II metal salt of the higher fatty acid is in the range of 0.05 to 0.5 parts by weight per 100 parts by weight of the polyolefin resin or polystyrene resin. is there.
When the total content of the hydrotalcite compound and the higher fatty acid Group II metal salt is less than 0.01 parts by weight per 100 parts by weight of the polyolefin resin or polystyrene resin, a masterbatch for polyolefin resin or polystyrene The hydrolysis resistance of the antioxidant (1) in the masterbatch for resin-based resins is not sufficient, and when the masterbatch is stored in a warehouse and applied to a polyolefin resin or polystyrene-based resin, Stabilizing effect is not enough.
On the other hand, when the total amount of the hydrotalcite compound and the higher fatty acid Group II metal salt exceeds 1 part by weight per 100 parts by weight of the polyolefin resin or polystyrene resin, the antioxidant (1) Compared with the case where the hydrolysis resistance is 1 part by weight, no improvement is observed, which is economically disadvantageous.

The polyolefin resin masterbatch or polystyrene resin masterbatch of the present invention contains an antioxidant (1) and a hydrotalcite compound or a group II metal salt of a higher fatty acid in the periodic table. In addition, other neutralizers, other antioxidants, light stabilizers, lubricants, antistatic agents, pigments, antiblocking agents, and the like can be blended to form a composite masterbatch.
When producing the masterbatch for polyolefin resin or the masterbatch for polystyrene resin of the present invention, the polyolefin resin or polystyrene resin is added to the Periodic Table II of the antioxidant (1), hydrotalcite compound and higher fatty acid. What is necessary is just to melt-knead after mix | blending a metal salt, and the apparatus and melt-kneading method used at the time of melt-kneading are not limited. For example, polyolefin resin or polystyrene resin, antioxidant (1), hydrotalcite compound and Group II metal salt of the periodic table, and other antioxidants used as necessary [for example, stearyl Phenolic antioxidants such as 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]; light stabilizers; lubricants; antistatic agents; pigments and antiblocking agents such as tumbler blenders and Henschel A method such as a method of melt-kneading and granulating with a single-screw extruder or a multi-screw extruder after being uniformly mixed in advance by a mixer such as a mixer or a super mixer, or using an extruder after melt-kneading with a kneader or Banbury mixer. The method of granulating etc. is mentioned.
The masterbatch for polyolefin resin or the masterbatch for polystyrene resin of the present invention is usually stored in a factory warehouse or the like, and then in accordance with the production time of the polyolefin resin or polystyrene resin product, the present invention is applied to the polyolefin or polystyrene resin. After blending a master batch for polyolefin or polystyrene resin, it is melt-kneaded and processed into a desired polyolefin or polystyrene product.
As a method for producing a desired polyolefin resin or polystyrene resin product by blending the polyolefin resin masterbatch or polystyrene resin masterbatch of the present invention, the polyolefin resin masterbatch or polystyrene resin of the present invention is used. There is no particular limitation on the apparatus and method as long as it is a method capable of blending a master batch, melt-kneading and then processing into a desired product. Specifically, the polyolefin resin or polystyrene resin and the masterbatch of the present invention are optionally mixed with another masterbatch, such as a pigment masterbatch or an antiblocking agent masterbatch, for example, a tumbler blender. , Mixed in advance with a mixer such as a Henschel mixer or super mixer, and then melt-kneaded with a single screw extruder or multi-screw extruder to process a T-die film or an inflation film. Can be processed.

In blending the masterbatch of the present invention with a polyolefin resin or a polystyrene resin, (X) parts by weight of the masterbatch of the present invention is used with respect to (100-X) parts by weight of the polyolefin resin or polystyrene resin. be able to. X described above is preferably in the range of 0.1 to 33, particularly preferably in the range of 0.5 to 10.
When X is less than 0.1, the stabilization effect of the obtained polyolefin resin or polystyrene resin may be insufficient. On the other hand, when X is larger than 33, the handling amount of the master batch is increased, which is economically disadvantageous.

  Hereinafter, although a reference example, a comparative example, an example, etc. explain the present invention still in detail, the present invention is not limited by these examples.

[Example of production of master batch for polyolefin resin]
Toyo Seiki Seisakusho Co., Ltd. accurately weighed 0.8 g of the antioxidant A1 (see paragraph 0016) and 40 mg of the compound C1 (calcium stearate; see paragraph 0021) into 40 g of unstabilized polyethylene. Using a lab plast mill C type manufactured by Kyushu, the mixture was kneaded for 3 minutes at a rate of 10 revolutions per minute at 160 ° C. in a nitrogen stream. The obtained composition was taken out with a spatula and immediately pressed to be stretched into a sheet having a thickness of about 1 mm. This sheet was cut into pellets to produce a masterbatch for polyethylene resin.

[Method for evaluating storage stability]
The master batch for resin immediately after production obtained in the above production example and the master batch after storage at 50 ° C. under conditions of 80% relative humidity were extracted by Soxhlet extraction to extract the antioxidant A1, and liquid chromatography was performed. The content of the antioxidant A1 in the masterbatch was analyzed by graphy. The content of A1 before storage was set to 100, and the content of A1 was traced over time.

[Production of resin composition from master batch after storage]
The master batch obtained in the above production example was stored at 50 ° C. for 2 weeks under the condition of 80% relative humidity. 0.8g of the master batch after storage was accurately weighed in 39.2g of unstabilized polyethylene, 24mg of the compound C1 (calcium stearate; see paragraph 0021) and 24mg of B1 (hydrotalcite; see paragraph 0020). Then, using a lab plast mill type C manufactured by Toyo Seiki Seisakusho Co., Ltd., the mixture was kneaded for 3 minutes at a rate of 10 revolutions per minute at 160 ° C. in a nitrogen stream. The obtained composition was taken out with a spatula and immediately pressed to be stretched into a sheet having a thickness of about 1 mm. This sheet was cut to obtain a pellet-shaped polyethylene resin composition. The polyethylene resin composition obtained in this production example contains 0.06 parts by weight of calcium stearate, 0.06 parts by weight of hydrotalcite and 0.1 parts by weight of antioxidant A1 with respect to 100 parts by weight of polyethylene. Including.

[Stability of resin composition]
Using a DSC (differential scanning calorimeter; 210 ° C., in an air atmosphere), the time until the start of heat generation in the polyethylene resin composition obtained in the production example was measured. The longer the time until the start of heat generation, the higher the stability of the resin composition against thermal oxidation.

Examples 1 to 5, Comparative Example 1 and Reference Example 1
In Examples 1 to 5, Comparative Example 1 and Reference Example 1, a master batch obtained according to the above production example was used. In Tables 1 and 2 below, the retention rate (%) of the antioxidant (A1) in hydrolysis resistance is described. In Tables 1 and 2, PE represents polyethylene, and the addition ratio of the antioxidant (A1) and other compounds was represented by the number of parts (parts by weight) with respect to 100 parts by weight of polyethylene. N. in Table 1 D indicates that data is not acquired.

Examples 6 to 10, Comparative Examples 2 to 3, and Reference Example 2
In Examples 6 to 10, Comparative Examples 2 to 3, and Reference Example 2, master batches obtained according to Examples 1 to 5, Comparative Example 1 and Reference Example 1 were used. Moreover, about the stability with respect to the thermal oxidation of a resin composition, it carried out according to Examples 1-5, the comparative example 1, and the reference example 1. FIG.
The composition of the masterbatch is shown in Table 2 below. Moreover, the product polyethylene was obtained from this master batch and raw material polyethylene (PE). The composition of the raw polyethylene is shown in Table 3 below. Hereinafter, the master batch may be abbreviated as MB.

Example 11
A master batch for polystyrene resin was produced in the same manner as in the above production example except that the polyethylene in the polyolefin resin production example was changed to polystyrene (PS) and the kneading temperature in the lab plast mill was changed to 200 ° C. The master batch for polystyrene resin was stored at 50 ° C. and a relative humidity of 80% for 2 weeks. A polystyrene resin composition was produced in the same manner as described above, except that the laboplast mill kneading temperature in the production example of the resin composition from the master batch after storage was changed to 200 ° C. The stability of the obtained polystyrene resin composition was measured in the same manner as in the case of the polyethylene resin composition.

The master batch for resin obtained by the present invention is one in which the hydrolysis resistance of the antioxidant (1) is improved. Moreover, the polyolefin resin and polystyrene-type resin obtained using the said masterbatch show the antioxidant performance outstanding at the time of melt-kneading.

Claims (7)

0 of at least one compound selected from the group consisting of the polyolefin resin, 2 to 10 parts by weight of the following (A), and the following (B) and (C) per 100 parts by weight of the polyolefin resin: 0.05 to 0.2 part by weight of a polyolefin resin masterbatch.
(A) Antioxidant represented by the following formula (1) (B) Hydrotalcite compound (C) Group II metal salt of higher fatty acid periodic table

(1)
[ Wherein R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alkylcycloalkyl having 6 to 12 carbon atoms. group, an aralkyl group or a phenyl group having 7 to 12 carbon atoms, R ³ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. X represents a single bond, a sulfur atom or a —CH 2 R ⁶ — group. R ⁶ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms.
A is an alkylene group, or * -CO ^{R 7} 2 to 8 carbon atoms - group. R ⁷ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and the —CO R ⁷ — group marked with * represents that it is bonded to the oxygen atom of the phosphite structure in formula (1). The carbon-carbon bond in the alkylene group having 2 to 8 carbon atoms may be interrupted by an oxygen atom, a sulfur atom, -NH-, -OCO- or -COO-.
One of Y and Z represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms, and the other represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. However, when Y is a hydroxyl group, one of R ⁴ and R ⁵ is an alkyl group having 3 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylcycloalkyl group having 6 to 12 carbon atoms, carbon It represents an aralkyl group or a phenyl group of formula 7-12.
Further, two R ^{1 s} in the formula (1) may be the same or different. Further, the two R ² in the formula (1) may be the same or different. And two R < ³ > in Formula (1) may mutually be same, and may differ. ]   The antioxidant represented by the formula (1) is 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [ The masterbatch for polyolefin resins according to claim 1, which is d, f] [1,3,2] dioxaphosphepine.   The masterbatch for polyolefin resins according to claim 1 or 2, wherein (C) is calcium stearate. 1 selected from the group consisting of a polyolefin resin, 2 to 10 parts by weight of (A) according to claim 1, and (B) and (C) according to claim 1 per 100 parts by weight of the polyolefin resin. The manufacturing method of the masterbatch for polyolefin resin characterized by mix | blending 0.05-0.2 weight part of a compound more than a seed | species, and melt-kneading.   The masterbatch for resin manufactured by the method of Claim 4.   The polyolefin resin composition manufactured by mix | blending polyolefin resin and the masterbatch for polyolefin resins of Claim 1, and melt-kneading.   The polyolefin resin composition according to claim 6, wherein the polyolefin resin master batch is in the range of 0.1 to 50 parts by weight per 100 parts by weight of the polyolefin resin.