JP7449705B2 - 4-Methyl-1-pentene resin composition and its uses - Google Patents

Description

The present invention relates to a 4-methyl-1-pentene resin composition having an antistatic effect, and molded articles and fibers containing the same.

4-Methyl-1-pentene/α-olefin copolymer whose main constituent monomer is 4-methyl-1-pentene has excellent heat resistance, mold releasability, transparency, and chemical resistance, so it can be used for various purposes. widely used. For example, films made of the above copolymers are used for FPC mold release films, composite material molding, mold release films, etc. due to their good mold release properties, and they also have excellent chemical resistance, water resistance, and transparency. Due to these characteristics, it is used in laboratory equipment and mandrels for manufacturing rubber hoses.

It is known that molded products made from 4-methyl-1-pentene/α-olefin copolymers may not have sufficient impact resistance, but the applicant has developed two specific types of 4-methyl-1-pentene/α-olefin copolymers. A 4-methyl-1-pentene resin composition has been proposed that has improved impact resistance by using a combination of methyl-1-pentene (co)polymers (see Patent Document 1).

On the other hand, molded bodies made of conventional resin compositions containing 4-methyl-1-pentene polymers have high insulation properties and are therefore very easily charged, compared to other polyolefin resins such as polypropylene. However, it is known that it is easily charged. In order to impart antistatic properties to the 4-methyl-1-pentene polymer, it is possible to add a conventionally known antistatic agent, but in order to impart sufficient antistatic properties, a large amount of antistatic agent must be added. This requires the addition of an agent and, for example, when attempting to form it into a fiber, thread breakage occurs, making it difficult to form into a fiber. Further, when a surfactant-based antistatic agent is used, there is a problem that the antistatic agent tends to bleed out onto the surface of the molded article, causing stickiness on the surface of the molded article.

For this reason, 4-methyl-1- The appearance of a resin composition containing a pentene polymer and a molded article thereof has been desired.

As a technique for imparting antistatic properties to a molded article made of a resin composition, for example, Patent Document 2 discloses an inclusion method containing cyclodextrin and polyolefin that exhibits a nucleating effect, an antistatic effect, a compatibility effect, etc. A synthetic resin composition in which a compound is added to a synthetic resin has been proposed. Patent Document 2 describes that various (co)polymers can be used as synthetic resins, and that a molded article having a quick crystallization start time and a fine crystalline state can be obtained. Further, Patent Document 3 describes a thermoplastic conductive resin composition containing carbon nanotubes and an olefin polymer, and teaches that conductivity is imparted by containing carbon nanotubes. However, Patent Documents 2 and 3 do not indicate how much antistatic property can be imparted to 4-methyl-1-pentene polymers that are particularly susceptible to charging.

Japanese Patent Application Publication No. 2008-162408 JP2008-266622A JP 2018-21117 Publication

As a result of extensive research in view of the above circumstances, the present inventors have found that an antistatic agent containing a specific boron compound has an excellent antistatic effect on a specific 4-methyl-1-pentene polymer in a small amount. The present inventors have discovered that it exhibits a preventive effect, and have completed the present invention. In addition, JP 2017-171884 proposes a resin composition and molded product in which the boron-based compound is added to polypropylene together with a nucleating agent, but it has higher insulating properties than polypropylene and generates electrical charge. There is no teaching on preventing the easy charging of 4-methyl-1-pentene polymers.
The present invention relates to a resin composition containing a 4-methyl-1-pentene polymer, which has excellent heat resistance, mold releasability, chemical resistance, etc., as well as antistatic property and moldability, and a molded product thereof. The challenge is to provide the following.

The present invention relates to, for example, the following items [1] to [7].
[1] A 4-methyl-1-pentene polymer (X) that satisfies the following requirements (X-1),
A 4-methyl-1-pentene polymer composition characterized by comprising an antistatic agent (Y) containing a boron-based compound having a structure represented by the following formula (1).
(X-1) The content of structural units derived from 4-methyl-1-pentene is 30.0 to 100.0 mol%, and ethylene and α-olefins having 3 to 20 carbon atoms (with the exception of 4-methyl- The total content of structural units derived from (excluding 1-pentene) is 0.0 to 70.0 mol%.

[2] The 4-methyl-1-pentene polymer according to [1] above, wherein the 4-methyl-1-pentene polymer (X) satisfies the following requirements (X-2) and (X-3). Coalescing composition.
(X-2) The intrinsic viscosity [η] measured in decalin at 135°C is in the range of 0.5 to 10.0 dl/g.
(X-3) At least one of the melting points (Tm) measured by DSC is 200°C or higher.

（式（２）中、Ｒ¹及びＲ²は、それぞれ独立して、Ｒ⁷ＣＯ－ＯＣＨ₂－又はＨＯＣＨ₂－で、かつ少なくとも一方がＲ⁷ＣＯ－ＯＣＨ₂－であり、Ｒ³及びＲ⁴は、それぞれ独立して、ＣＨ₃－、Ｃ₂Ｈ₅－、ＨＯＣＨ₂－、ＨＯＣ₂Ｈ₄－又はＨＯＣＨ₂ＣＨ（ＣＨ₃）－であり、Ｒ⁵は、－Ｃ₂Ｈ₄－又は－Ｃ₃Ｈ₆－であり、Ｒ⁶及びＲ⁷は、それぞれ独立して、炭素数１１～２１のアルキルである。）

（式（３）中、Ｒ¹及びＲ²は、それぞれ独立して、Ｒ⁷ＣＯ－ＯＣＨ₂－又はＨＯＣＨ₂－で、かつ少なくとも一方がＲ⁷ＣＯ－ＯＣＨ₂－であり、Ｒ³及びＲ⁴は、それぞれ独立して、ＣＨ₃－、Ｃ₂Ｈ₅－、ＨＯＣＨ₂－、ＨＯＣ₂Ｈ₄－又はＨＯＣＨ₂ＣＨ（ＣＨ₃）－であり、Ｒ⁵は、－Ｃ₂Ｈ₄－又は－Ｃ₃Ｈ₆－であり、Ｒ⁶及びＲ⁷は、それぞれ独立して、炭素数１１～２１のアルキルである。） [3] The antistatic agent (Y) containing the boron-based compound is obtained by reacting a semipolar organic boron compound as a donor component with a basic nitrogen compound as an acceptor component, and is obtained by the following formula (2) or The 4-methyl-1-pentene polymer composition according to [1] or [2] above, which is a donor-acceptor antistatic agent represented by formula (3).

(In formula (2), R ¹ and R ² are each independently R ⁷ CO-OCH ₂ - or HOCH ₂ -, and at least one is R ⁷ CO-OCH ₂ -, and R ³ and R ⁴ is each independently CH ₃ -, C ₂ H ₅ -, HOCH ₂ -, HOC ₂ H ₄ - or HOCH ₂ CH(CH ₃ )-, and R ⁵ is -C ₂ H ₄ - or -C ₃ H ₆ -, and R ⁶ and R ⁷ are each independently alkyl having 11 to 21 carbon atoms.)

(In formula (3), R ¹ and R ² are each independently R ⁷ CO-OCH ₂ - or HOCH ₂ -, and at least one is R ⁷ CO-OCH ₂ -, and R ³ and R ⁴ is each independently CH ₃ -, C ₂ H ₅ -, HOCH ₂ -, HOC ₂ H ₄ - or HOCH ₂ CH(CH ₃ )-, and R ⁵ is -C ₂ H ₄ - or -C ₃ H ₆ -, and R ⁶ and R ⁷ are each independently alkyl having 11 to 21 carbon atoms.)

[4] The 4-methyl-1-pentene type according to any one of [1] to [3] above, which contains 0.1 to 5.0% by mass of the antistatic agent (Y) containing the boron-based compound. Polymer composition.
[5] The haze of [1] to [4] above is 2.0 to 8.0% when measured according to JIS K 7136 using a 2 mm thick molded product obtained by injection molding as a test piece. 4-methyl-1-pentene polymer composition according to any one of the above.
[6] A molded article comprising the 4-methyl-1-pentene polymer composition according to any one of [1] to [5] above.
[7] A fiber comprising the 4-methyl-1-pentene-based tree polymer composition according to any one of [1] to [5] above.

According to the present invention, it is possible to exhibit sufficient antistatic properties by containing only a small amount of a specific antistatic agent, so that the heat resistance, mold releasability, chemical resistance, etc. inherent to 4-methyl-1-pentene polymers, etc. It is possible to provide a 4-methyl-1-pentene-based polymer composition that maintains these properties, has excellent antistatic properties and moldability, and can suitably provide molded articles such as fibers. Further, according to the present invention, the 4-methyl-1-pentene polymer retains its inherent properties such as heat resistance, mold release properties, and chemical resistance, and also has sufficient antistatic properties, and has an antistatic agent. It is possible to provide a molded article of fibers, etc., in which bleed-out is sufficiently suppressed.

The present invention will be explained in detail below. In the present invention, a polymer means both a homopolymer and a copolymer, unless otherwise specified.
<4-methyl-1-pentene polymer composition>
The 4-methyl-1-pentene polymer composition of the present invention contains a 4-methyl-1-pentene polymer (X) and an antistatic agent (Y) containing a specific boron compound.

4-methyl-1-pentene polymer (X)
The 4-methyl-1-pentene polymer (X) according to the present invention is a polymer or copolymer of monomers containing 4-methyl-1-pentene, and satisfies the requirement (X-1) described below. Fulfill. Furthermore, the 4-methyl-1-pentene polymer (X) according to the present invention preferably satisfies one or more, more preferably both, of requirements (X-2) and (X-3) described below. The 4-methyl-1-pentene polymer (X) may be a mixture of two or more 4-methyl-1-pentene polymers.

<Requirement (X-1)>
(X-1) The content of the structural unit derived from 4-methyl-1-pentene is 30.0 to 100.0 mol%, and the content of ethylene and an α-olefin having 3 to 20 carbon atoms (4-methyl-1 - The total content of structural units derived from (excluding pentene) is 0.0 to 70.0 mol%.

The 4-methyl-1-pentene polymer (X) is a homopolymer of 4-methyl-1-pentene (that is, a polymer having a content of 100 mol% of structural units derived from 4-methyl-1-pentene). or a copolymer of 4-methyl-1-pentene and a copolymerizable monomer such as α-olefin, which satisfies requirement (X-1).

The content of the structural unit derived from 4-methyl-1-pentene in the 4-methyl-1-pentene polymer (X) is preferably 40.0 to 99.5 mol%, more preferably 50.0 to 99.5 mol%. It is 0 to 99.0 mol%, more preferably 70.0 to 98.5 mol%. Further, the total content of structural units derived from at least one olefin selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is preferably 0.5 to The content is 60.0 mol%, more preferably 1.0 to 50.0 mol%, even more preferably 1.5 to 30.0 mol%.

Examples of the α-olefin include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, and 1-octadecene. - Examples include eicosene. The α-olefin can be appropriately selected depending on the intended use and required physical properties of the 4-methyl-1-pentene polymer composition. For example, the α-olefin is preferably an α-olefin having 8 to 18 carbon atoms, such as 1-octene, 1-decene, 1-decene, or At least one selected from -tetradecene, 1-hexadecene, 1-heptadecene and 1-octadecene is more preferred.

The 4-methyl-1-pentene polymer (X) may contain structural units other than the structural unit derived from 4-methyl-1-pentene and the α-olefin, within a range that does not impair the effects of the present invention. It may have a structural unit (hereinafter also referred to as "other structural unit"). The content of other structural units is, for example, 0 to 10.0 mol%.

Examples of monomers that lead to other structural units include cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, functional vinyl compounds, hydroxyl group-containing olefins, and halogenated olefins. Examples of cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, functional vinyl compounds, hydroxyl group-containing olefins, and halogenated olefins include those described in paragraphs [0035] to [0041] of JP-A No. 2013-169685. Compounds can be used.
When the 4-methyl-1-pentene polymer (X) has other structural units, only one type of other structural units may be included, or two or more types of other structural units may be included. .

<Requirement (X-2)>
(X-2) The intrinsic viscosity [η] measured in decalin at 135°C is in the range of 0.5 to 10.0 dl/g. The 4-methyl-1-pentene polymer (X) according to the present invention preferably satisfies this requirement (X-2).
The intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (X) measured in decalin at 135°C is more preferably 0.5 to 8.0 dl/g, and even more preferably 0.8. ~6.0 dl/g. It is preferable that the intrinsic viscosity [η] is within the above range from the viewpoint of resin fluidity during molding of the 4-methyl-1-pentene polymer composition.

The intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (X) can be adjusted within the above range by, for example, appropriately selecting the hydrogen concentration and pressure of the polymerization system. The 4-methyl-1-pentene polymer (X) may also be obtained by mixing 4-methyl-1-pentene polymers having different intrinsic viscosities [η] and adjusting the viscosity within the above range.

<Requirement (X-3)>
(X-3) At least one of the melting points (Tm) measured by DSC is 200°C or higher. The 4-methyl-1-pentene polymer (X) according to the present invention may have two or more melting points (Tm), and preferably satisfies this requirement (X-3). The melting point (Tm) of the 4-methyl-1-pentene polymer (X) measured by DSC (if it has two or more melting points (Tm), the highest temperature) is more preferably 210 to 260°C. , more preferably in the range of 220 to 250°C, still more preferably in the range of 225 to 245°C. When the melting point of the 4-methyl-1-pentene polymer (X) is within the above range, a molded article etc. obtained from the 4-methyl-1-pentene polymer composition will have excellent heat resistance.

The 4-methyl-1-pentene polymer (X) according to the present invention is a graft-modified polymer obtained by graft-modifying a 4-methyl-1-pentene (co)polymer with a polar monomer, as long as it satisfies the above requirements. It may also be a (co)polymer.

<Production method of 4-methyl-1-pentene polymer (X)>
The method for producing the 4-methyl-1-pentene polymer (X) is not particularly limited, but for example, the method described in WO 01/27124, WO 14/050817, etc. Can be adopted. In the method for producing the 4-methyl-1-pentene polymer (X), conventionally known polymerization catalysts can be used.

- Graft modification When the 4-methyl-1-pentene polymer (X) is a graft modified product, the graft modified product is obtained by grafting a polar monomer onto the 4-methyl-1-pentene polymer that is the target material. It can be produced by polymerization.

Examples of polar monomers used for graft modification include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids or derivatives thereof. , vinyl ester compounds, vinyl chloride, and carbodiimide compounds. Particularly preferred are unsaturated carboxylic acids or derivatives thereof. Examples of the unsaturated carboxylic acid or its derivative include an unsaturated compound having one or more carboxylic acid groups, an ester of a compound having a carboxylic acid group and an alkyl alcohol, and an unsaturated compound having one or more carboxylic anhydride groups. Examples of the unsaturated group include a vinyl group, a vinylene group, and an unsaturated cyclic hydrocarbon group.

Specifically, the polar monomers include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid [trademark] (endocys-bicyclo[2.2.1 ] Hept-5-ene-2,3-dicarboxylic acid) and derivatives of unsaturated carboxylic acids include, for example, acid halides, amides, imides, anhydrides, and esters. Specific examples of such derivatives include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate.

These unsaturated carboxylic acids and/or derivatives thereof may be used alone or in combination of two or more. Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred, and maleic acid, nadic acid, or their acid anhydrides are particularly preferred.

Modification is obtained by graft polymerizing a polar monomer to a (co)polymer to be modified. When a polar monomer is graft-polymerized to the object to be modified, the polar monomer is usually used in an amount of 1 to 100 parts by weight, preferably 5 to 80 parts by weight, based on 100 parts by weight of the object to be modified. This graft polymerization is usually carried out in the presence of a radical initiator.

As the radical initiator, organic peroxides, azo compounds, and the like can be used. The radical initiator can be used by being mixed with the substance to be modified and the polar monomer as it is, but it can also be used after being dissolved in a small amount of an organic solvent. As the organic solvent, any organic solvent that can dissolve the radical initiator can be used without particular limitation.

A reducing substance may be used when graft polymerizing the polar monomer onto the object to be modified. When a reducing substance is used, the amount of polar monomer grafted can be increased.
Graft modification of the object to be modified with a polar monomer can be carried out by a conventionally known method. For example, the object to be modified is dissolved in an organic solvent, then the polar monomer and a radical initiator are added to the solution, and the temperature is usually 70 to 200°C. , preferably at a temperature of 80 to 190°C, usually for 0.5 to 15 hours, preferably for 1 to 10 hours.

The modified 4-methyl-1-pentene polymer (X) can also be produced by reacting the modified product with a polar monomer using an extruder or the like. This reaction is usually carried out at a temperature above the melting point of the substance to be modified. Specifically, when modifying a thermoplastic resin, it is usually carried out at a temperature of 120 to 300°C, usually for 0.5 to 10 minutes, preferably at a temperature of 160 to 300°C, more preferably at a temperature of 180 to 250°C. It will be done.

The amount of modification (the amount of polar monomer grafted) of the modified product thus obtained is usually 0.1 to 50% by mass, preferably 0.2 to 30% by mass, when the modified product is 100% by mass. More preferably, it is 0.2 to 10% by mass.

In addition, a polar monomer is added to a composition containing an unmodified 4-methyl-1-pentene polymer, and the 4-methyl-1-pentene polymer in the composition is modified to produce a modified product. A 4-methyl-1-pentene polymer composition containing the 4-methyl-1-pentene polymer (X) can also be obtained. The content of the polar monomer when the polar monomer is contained is not particularly limited, but is preferably 0.001 to 50% by mass, more preferably 0.001 to 10% by mass, and even more preferably 0.001 to 5% by mass. %, most preferably 0.01 to 3% by weight. The content of the polar monomer can be easily determined depending on the purpose, for example, by appropriately selecting grafting conditions.

Further, the 4-methyl-1-pentene polymer (X) may be a polymer obtained by graft-modifying a modified object using a silane coupling agent. Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltrichlorosilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N- -(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3 -aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane , 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-(1,3-dimethylbutylidene)-3- (Triethoxysilyl)-1-propanamine, N,N'-bis(3-(trimethoxysilyl)propyl)ethylenediamine, polyoxyethylenepropyltrialkoxysilane, polyethoxydimethylsiloxane, p-styryltrimethoxysilane, 3 -acryloxypropyltrimethoxysilane.

When performing graft modification (crosslinking) using a silane coupling agent, either a dry treatment method or a wet (slurry method) treatment method may be used. Since the 4-methyl-1-pentene polymer (X), which is a crosslinked product using a silane coupling agent, has a uniform crosslinked state, a polymer composition containing this polymer (X) It is suitable for use in applications where strength and durability are required, such as industrial wires and pipes.

When a modified product is used as the 4-methyl-1-pentene polymer (X), it has excellent adhesion and compatibility with other resins, and the wettability of the surface of the obtained molded product may be improved. . Furthermore, by using a modified material, it may be possible to add compatibility or adhesiveness with materials other than resin (glass, metal, wood, etc.).

Furthermore, by setting the grafting amount of the polar monomer (for example, unsaturated carboxylic acid and/or its derivative) within the above range, the resulting 4-methyl-1-pentene polymer (X) containing 4-methyl- The 1-pentene copolymer composition exhibits high adhesive strength to polar group-containing resins (eg, polyester, polyvinyl alcohol, ethylene/vinyl alcohol copolymer, polyamide, PMMA, polycarbonate, etc.).

Antistatic agent (Y) containing boron-based compound
The antistatic agent (Y) used in the present invention is an antistatic agent containing a boron-based compound having a structure represented by the following formula (1).

Preferably, the antistatic agent (Y) containing a boron-based compound according to the present invention has a semipolar organic boron compound having a structure represented by the above formula (1) in its molecule as a donor component, and a basic nitrogen compound as a donor component. It is a donor-acceptor type antistatic agent obtained by reacting the two as an acceptor component. Such a donor-acceptor type antistatic agent can be obtained by uniformly mixing at least one of the donor components and at least one of the acceptor components.

Such a donor-acceptor type antistatic agent is preferably a combination of compounds in which both the donor compound and the acceptor compound have one or more linear hydrocarbon groups. In this case, in the 4-methyl-1-pentene polymer composition, the antistatic agent (Y) containing a boron-based compound and the 4-methyl-1-pentene polymer (X) may be multiplexed. It is thought that the antistatic effect is sustained because the Coulomb force-expressing portion, which is responsible for the antistatic effect of the antistatic agent, remains stable for a long time due to the Van der Waals force acting on the antistatic agent. Although donor-acceptor hybrid type compounds based on electron conduction have been known for a long time, they have a completely different mechanism and structure from the donor-acceptor type antistatic agent used in the present invention.

The semipolar organic boron compound preferably used as a donor component in the present invention refers to the remaining adjacent hydroxyl group of an ester between a polyhydric alcohol and a straight-chain fatty acid with adjacent hydroxyl groups remaining. or react boric acid or a boric acid ester of a lower alcohol to a linear hydrocarbon compound having an adjacent hydroxy group, or react a boric acid or a boric acid ester of a lower alcohol to a linear hydrocarbon compound having adjacent hydroxy groups, It is obtained by reacting a linear fatty acid with the hydroxyl group remaining after reacting a trivalent or higher polyhydric alcohol having a group with boric acid or a boric acid ester of a lower alcohol, The product obtained by this reaction is characterized by being a solid with strong van der Waals forces.

Preferred examples of polyhydric alcohols or fatty acid partial esters of polyhydric alcohols used for preparing the semipolar organic boron compound (boric acid ester type complex) constituting the antistatic agent (Y) containing a boron-based compound according to the present invention include: , polyglycerin such as glycerin, diglycerin, triglycerin, tetraglycerin, 1,2-alkanediol having 14 to 24 carbon atoms, sorbitol, sorbitan, sucrose, polypentaerythritol such as pentaerythritol, dipentaerythritol, tripentaerythritol Polyhydric alcohols such as erythritol, trimethylolethane, trimethylolpropane, polyoxyethylene glycerin, polyoxyethylene sorbitan, glycerin higher fatty acid monoester, diglycerin higher fatty acid monoester, triglycerin higher fatty acid monoester, tetraglycerin higher fatty acid monoester Polyglycerin higher fatty acid monoesters such as esters, sorbitol higher fatty acid monoesters, sorbitan higher fatty acid monoesters, sucrose higher fatty acid monoesters, pentaerythritol higher fatty acid mono- or diesters, dipentaerythritol higher fatty acid mono- or diesters, tripentaerythritol higher fatty acid monoesters, etc. Polypentaerythritol higher fatty acid mono- or diester such as fatty acid mono- or diester, trimethyloleethane higher fatty acid monoester, trimethylolpropane higher fatty acid monoester, polyoxyethylene glycerin higher fatty acid monoester, polyoxyethylene sorbitan higher fatty acid monoester, etc. Higher fatty acid partial esters of polyhydric alcohols (higher fatty acids include hexanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, montanic acid, oleic acid, erucic acid, etc.) can be exemplified. Particularly preferred are glycerin higher fatty acid monoester and pentaerythritol higher fatty acid mono- or diester.

In addition, basic nitrogen compounds suitable for constituting the antistatic agent (Y) containing a boron-based compound according to the present invention include N-alkyl-substituted primary and secondary compounds having at least one straight-chain hydrocarbon group. and tertiary amine as it is, or ethylene oxide is added to primary and secondary amines having at least one linear hydrocarbon group to bond an N-hydroxyethyl substituent, or the terminal A linear 2-hydroxy aliphatic amine produced by reacting a hydroxyl group with a linear fatty acid, or a linear 2-hydroxy aliphatic amine produced by reacting ammonia with an epoxidized product of a linear hydrocarbon, or a primary and ethylene oxide is added to a secondary linear 2-hydroxy aliphatic amine to bond an N-hydroxyethyl substituent, or a polyalkylene polyamine with one amino group remaining. Polyalkylene polyamine and linear fatty acid are reacted in a molar ratio such that all other amino groups are converted into fatty acid amides.Like the semi-polar organic compounds mentioned above, they are characterized by van der Waals force. It is a strong solid.

Examples of basic nitrogen compounds (aliphatic amines) suitable for constituting the antistatic agent (Y) containing a boron-based compound according to the present invention include the following.
Octylamine, laurylamine, myristylamine, palmitylamine, stearylamine, oleylamine, cocoaamine, tallowamine, soyamine, N,N-dicocoamine, N,N-ditallowamine, N,N-disoyamine, N-lauryl-N,N- Dimethylamine, N-myristyl-N,N-dimethylamine, N-palmityl-N,N-dimethylamine, N-stearyl-N,N-dimethylamine, N-coco-N,N-dimethylamine, N-tallow -N,N-dimethylamine, N-soy-N,N-dimethylamine, N-methyl-N,N-ditallowamine, N-methyl-N,N-dicocoamine, N-oleyl-1,3-diaminopropane, N-tallow-1,3-diaminopropane, hexamethylene diamine,

N-lauryl-N,N,N-trimethylammonium chloride, N-palmityl-N,N,N-trimethylammonium chloride, N-stearyl-N,N,N-trimethylammonium chloride, N-docosyl-N,N, N-trimethylammonium chloride, N-coco-N,N,N-trimethylammonium chloride, N-tallow-N,N,N-trimethylammonium chloride, N-soy-N,N,N-trimethylammonium chloride, N- Lauryl-N,N-dimethyl-N-benzylammonium chloride, N-myristyl-N,N-dimethyl-N-benzylammonium chloride, N-stearyl-N,N-dimethyl-N-benzylammonium chloride, N-coco- N,N-dimethyl-N-benzylammonium chloride, N,N-dioleyl-N,N-dimethylammonium chloride, N,N-dicoko-N,N-dimethylammonium chloride, N,N-ditallow-N,N- Dimethylammonium chloride, N,N-disoy-N,N-dimethylammonium chloride, N,N-bis(2-hydroxyethyl)-N-lauryl-N-methylammonium chloride, N,N-bis(2-hydroxyethyl) )-N-stearyl-N-methylammonium chloride, N,N-bis(2-hydroxyethyl)-N-oleyl-N-methylammonium chloride, N,N-bis(2-hydroxyethyl)-N-coco- N-methylammonium chloride, N,N-bis(polyoxyethylene)-N-lauryl-N-methylammonium chloride, N,N-bis(polyoxyethylene)-N-stearyl-N-methylammonium chloride, N, N-bis(polyoxyethylene)-N-oleyl-N-methylammonium chloride, N,N-bis(polyoxyethyln)-N-coco-N-methylammonium chloride,

N,N-bis(2-hydroxyethyl)laurylaminobetaine, N,N-bis(2-hydroxyethyl)tridecylaminobetaine, N,N-bis(2-hydroxyethyl)myristylaminobetaine, N,N- Bis(2-hydroxyethyl)pentadecylaminobetaine, N,N-bis(2-hydroxyethyl)palmitylaminobetaine, N,N-bis(2-hydroxyethyl)stearylaminobetaine, N,N-bis(2 -Hydroxyethyl)oleylaminobetaine, N,N-bis(2-hydroxyethyl)dococylaminobetaine, N,N-bis(2-hydroxyethyl)octacosylaminobetaine, N,N-bis(2-hydroxy ethyl) cocoaminobetaine, N,N-bis(2-hydroxyethyl) tallowaminobetaine,

Hexamethylenetetramine, N-(2-hydroxyethyl)laurylamine, N-(2-hydroxyethyl)tridecylamine, N-(2-hydroxyethyl)myristylamine, N-(2-hydroxyethyl)pentadecylamine, N-(2-hydroxyethyl)palmitylamine, N-(2-hydroxyethyl)stearylamine, N-(2-hydroxyethyl)oleylamine, N-(2-hydroxyethyl)docosylamine, N-(2-hydroxyethyl) ) Octacosylamine, N-(2-hydroxyethyl)cocoamine, N-(2-hydroxyethyl)tallowamine, N-methyl-N-(2-hydroxyethyl)laurylamine, N-methyl-N-(2-hydroxy ethyl)tridecylamine, N-methyl-N-(2-hydroxyethyl)myristylamine, N-methyl-N-(2-hydroxyethyl)pentadecylamine, N-methyl-N-(2-hydroxyethyl)pal Mythylamine, N-methyl-N-(2-hydroxyethyl)stearylamine, N-methyl-N-(2-hydroxyethyl)oleylamine, N-methyl-N-(2-hydroxyethyl)docosylamine, N-methyl- N-(2-hydroxyethyl)octacosylamine, N-methyl-N-(2-hydroxyethyl)cocoamine, N-methyl-N-(2-hydroxyethyl)tallowamine, N,N-bis(2-hydroxyethyl) ) laurylamine, N,N-bis(2-hydroxyethyl)tridecylamine, N,N-bis(2-hydroxyethyl)myristylamine, N,N-bis(2-hydroxyethyl)pentadecylamine, N, N-bis(2-hydroxyethyl)palmitylamine, N,N-bis(2-hydroxyethyl)stearylamine, N,N-bis(2-hydroxyethyl)oleylamine, N,N-bis(2-hydroxyethyl) ) docosylamine, N,N-bis(2-hydroxyethyl)octacosylamine, N,N-bis(2-hydroxyethyl)cocoamine, N,N-bis(2-hydroxyethyl)tallowamine, etc. (2-hydroxyethyl) aliphatic amine;

Mono- or diester of the N,N-bis(2-hydroxyethyl) aliphatic amine and fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, polyoxyethylene lauryl amino ether, polyoxyethylene aliphatic amino ether such as polyoxyethylene stearyl amino ether, polyoxyethylene oleylamino ether, polyoxyethylene cocoa amino ether, polyoxyethylene tallow amino ether, said polyoxyethylene aliphatic amino ether and said fatty acid mono- or diester with;

N-(lauroyloxyethyl)-N-(stearoyloxyethoxyethyl)stearylamine, N,N,N',N'-tetra(2-hydroxyethyl)-1,6-diaminohexane, N-lauryl-N, N',N'-tris(2-hydroxyethyl)-1,3-diaminopropane, N-stearyl-N,N',N'-tris(2-hydroxyethyl)-1,3-diaminopropane, N- Coco-N,N',N'-tris(2-hydroxyethyl)-1,3-diaminopropane, N-tallow-N,N',N'-tris(2-hydroxyethyl)-1,3-diamino Propane, N,N-dicoco-N',N'-bis(2-hydroxyethyl)-1,3-diaminopropane, N,N-ditallow-N',N'-bis(2-hydroxyethyl)-1 , 3-diaminopropane, N-coco-N,N',N'-tris(2-hydroxyethyl)-1,6-diaminohexane, N-tallow-N,N',N'-tris(2-hydroxy ethyl)-1,6-diaminohexane, N,N-dicoko-N',N'-bis(2-hydroxyethyl)-1,6-diaminohexane, N,N-ditallow-N',N'-bis (2-hydroxyethyl)-1,6-diaminohexane, N-(2-hydroxyethyl)-2-hydroxylaurylamine, N-(2-hydroxyethyl)-2-hydroxymyristylamine, N-(2-hydroxyethyl)-2-hydroxymyristylamine, ethyl)-2-hydroxypalmitylamine, N-(2-hydroxyethyl)-2-hydroxystearylamine, N,N-bis(2-hydroxyethyl)-2-hydroxylaurylamine, N,N-bis(2-hydroxyethyl)-2-hydroxylaurylamine, -hydroxyethyl)-2-hydroxymyristylamine, N,N-bis(2-hydroxyethyl)-2-hydroxypalmitylamine, N,N-bis(2-hydroxyethyl)-2-hydroxystearylamine, 2, 2'-bis(lauric acid amide) diethylamine, 2,2'-bis(myristic acid amide) diethylamine, 2,2'-bis(palmitic acid amide) diethylamine, 2,2'-bis(stearic acid amide) diethylamine, N-(2-(lauric acid amide))ethyl-N-(2'-(stearic acid amide))ethylamine, N-(2-(myristic acid amide))ethyl-N-(2'-(stearic acid amide) )) Ethylamine, N-(3-(lauric acid amide)) propyl-N,N-dimethylamine, N-(3-(myristic acid amide)) propyl-N,N-dimethylamine, N-(3-( palmitic acid amide)) propyl-N,N-dimethylamine, N-(3-(stearic acid amide)) propyl-N,N-dimethylamine, N-(3-(lauroyloxy)) propyl-N,N- Dimethylamine, N-(3-(myristoyloxy))propyl-N,N-dimethylamine, N-(3-(palmitoyloxy))propyl-N,N-dimethylamine, N-(3-(stearoyloxy)) ) Propyl-N,N-dimethylamine, N,N-bis(3-(laurateamide)propyl)methylamine, N,N-bis(3-(myristateamide)propyl)methylamine, N,N- Bis(3-(palmitamide)propyl)methylamine, N,N-bis(3-(stearamide)propyl)methylamine.

More preferable examples of the basic nitrogen compound include aliphatic amines represented by the following formula (2') or (3').

（式（２'）および（３'）中、Ｒ³及びＲ⁴は、それぞれ独立して、ＣＨ₃－、Ｃ₂Ｈ₅－、ＨＯＣＨ₂－、ＨＯＣ₂Ｈ₄－又はＨＯＣＨ₂ＣＨ（ＣＨ₃）－であり、Ｒ⁵は、－Ｃ₂Ｈ₄－又は－Ｃ₃Ｈ₆－であり、Ｒ⁶は、炭素数１１～２１のアルキルである。）

(In formulas (2') and (3'), R ³ and R ⁴ are each independently CH ₃ -, C ₂ H ₅ -, HOCH ₂ -, HOC ₂ H ₄ - or HOCH ₂ CH (CH ₃ )-, R ⁵ is -C ₂ H ₄ - or -C ₃ H ₆ -, and R ⁶ is alkyl having 11 to 21 carbon atoms.)

The antistatic agent (Y) containing a boron-based compound according to the present invention is a donor-acceptor obtained by reacting the above-mentioned semipolar organic boron compound as a donor component and the above-mentioned basic nitrogen compound as an acceptor component. A type antistatic agent is preferable, and a donor-acceptor type antistatic agent represented by the following formula (2) or formula (3) is more preferable.

（式（２）中および式（３）中、Ｒ¹及びＲ²は、それぞれ独立して、Ｒ⁷ＣＯ－ＯＣＨ₂－又はＨＯＣＨ₂－で、かつ少なくとも一方がＲ⁷ＣＯ－ＯＣＨ₂－であり、Ｒ³及びＲ⁴は、それぞれ独立して、ＣＨ₃－、Ｃ₂Ｈ₅－、ＨＯＣＨ₂－、ＨＯＣ₂Ｈ₄－又はＨＯＣＨ₂ＣＨ（ＣＨ₃）－であり、Ｒ⁵は、－Ｃ₂Ｈ₄－又は－Ｃ₃Ｈ₆－であり、Ｒ⁶及びＲ⁷は、それぞれ独立して、炭素数１１～２１のアルキルである。）

(In formula (2) and formula (3), R ¹ and R ² are each independently R ⁷ CO-OCH ₂ - or HOCH ₂ -, and at least one is R ⁷ CO-OCH ₂ - , R ³ and R ⁴ are each independently CH ₃ -, C ₂ H ₅ -, HOCH ₂ -, HOC ₂ H ₄ - or HOCH ₂ CH(CH ₃ )-, and R ⁵ is - C ₂ H ₄ - or -C ₃ H ₆ -, and R ⁶ and R ⁷ are each independently alkyl having 11 to 21 carbon atoms.)

Specific examples of the antistatic agent (Y) containing a boron compound that is preferably used in the present invention, which is such a donor-acceptor type antistatic agent, are shown in the following formulas (4) to (11).

In the above formulas (4) to (11) given as examples, the semipolar organic boron compound part in the upper part is used as a donor component, the tertiary amine part in the lower part is used as an acceptor component, and the two are reacted at a molar ratio of about 1:1. It is a donor-acceptor type antistatic agent, and in the donor component, "δ+" indicates that polarity exists in the covalent bond within the molecule, and (+) indicates that the electron donating property of the oxygen atom becomes stronger. (-) indicates that the electron-attracting property of the boron atom is strengthened, "→" indicates the path where electrons are attracted, and "--" indicates that the bonding force between atoms is weakened. Indicates the condition.

The donor-acceptor type antistatic agent is prepared by mixing and melting the donor component and acceptor component in a molar ratio of about 1:1 and reacting them before mixing with the 4-methyl-1-pentene polymer (X). It is preferable to prepare it by If the donor component and acceptor component are simply mixed into the 4-methyl-1-pentene polymer (X) separately without reacting in advance, there is a very small chance that both components will react in the mixture. Almost no compounds are formed, making it difficult to obtain the effects of the present invention. In addition, the molar ratio of the donor component and acceptor component is preferably as close to 1:1 as possible, and if the molar ratio range is about 1:0.8 to 1:1.25, the molecular compound will be sufficiently formed. Therefore, the effects of the present invention can be easily obtained, which is preferable.

In the 4-methyl-1-pentene polymer composition of the present invention, the content of the antistatic agent (Y) containing a boron-based compound is preferably 0.1 to 5.0% by mass, more preferably 0. .1 to 3.0% by mass, more preferably 0.1 to 2.9% by mass, even more preferably 0.1 to 2.5% by mass, particularly preferably 0.1 to 2% by mass. .0% by mass. The lower limit of the content of the antistatic agent (Y) containing a boron-based compound is not particularly limited, but is preferably 0.2% by mass, more preferably 0.3% by mass. When the content of the antistatic agent (Y) containing a boron-based compound is 0.1% by mass or more, a sufficient antistatic effect can be obtained, and when the content is 5.0% by mass or less, a molded article obtained from the composition can be obtained. Because it is less likely to cause problems such as precipitation of the antistatic agent (Y) on the surface, embrittlement of the molded body due to the high content of the antistatic agent (Y), and breakage of the fibers obtained from the composition. preferable.

As the donor-acceptor type antistatic agent suitable as the boron-based compound-containing antistatic agent (Y) constituting the 4-methyl-1-pentene polymer composition of the present invention, a commercially available one can be used. Can be done. Specifically, Biomicelle BN-105 (mC ₄₂ H ₈₁ O ₈ B + nC ₂₃ H ₄₈ ON ₂ , see product safety data sheet) manufactured by Boron Institute Co., Ltd. and Biomicelle BN-77 (mC ₄₂ H ₈₁ O ₈ B+nC ₂₃ H ₄₇ O ₂ N, see product safety data sheet).

Other components The 4-methyl-1-pentene polymer composition of the present invention may contain the above-mentioned 4-methyl-1-pentene polymer (X) to the extent that the effects of the present invention are not impaired, depending on the intended use. In addition to the antistatic agent (Y) containing the boron-based compound, other components may also be contained. Other components include a polymer different from the 4-methyl-1-pentene polymer (X) (hereinafter also referred to as other polymer), and an antistatic agent (Y) containing the boron-based compound. ) (hereinafter also referred to as other additives) may optionally be contained.

-Other polymers As other polymers, thermoplastic resins other than the 4-methyl-1-pentene polymer (X) of the present invention can be widely used. The content of other polymers is preferably 30% by mass or less, more preferably 20% by mass or less, based on the total mass of the 4-methyl-1-pentene polymer composition of the present invention. The content is preferably 10% by mass or less, and more preferably 10% by mass or less.

The thermoplastic resin is not particularly limited as long as it is different from the 4-methyl-1-pentene polymer (X), but examples of the thermoplastic resin include the following.
Thermoplastic polyolefin resin: For example, polyethylene such as low density, medium density, high density polyethylene, high pressure low density polyethylene, polypropylene such as isotactic polypropylene, syndiotactic polypropylene, poly 1-butene, poly 4-methyl- 1-pentene, poly3-methyl-1-pentene, poly3-methyl-1-butene, ethylene/α-olefin copolymer, propylene/α-olefin copolymer, 1-butene/α-olefin copolymer , 4-methyl-1-pentene/α-olefin copolymer, cyclic olefin copolymer, chlorinated polyolefin, and modified polyolefin resin obtained by modifying these olefin resins;

Thermoplastic polyamide resin: For example, aliphatic polyamide (nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612);
Thermoplastic polyester resin: For example, polyethylene terephthalate, polybutylene terephthalate, polyester elastomer;
Thermoplastic vinyl aromatic resin: For example, polystyrene, ABS resin, AS resin, styrene elastomer (styrene/butadiene/styrene block polymer, styrene/isoprene/styrene block polymer, styrene/isobutylene/styrene block polymer, hydrogenation of these) things);

Thermoplastic polyurethane; vinyl chloride resin; vinylidene chloride resin; acrylic resin; vinyl acetate copolymers such as ethylene/vinyl acetate copolymer; ethylene/acrylate methacrylate copolymer; ionomer; ethylene/vinyl alcohol copolymer; polyvinyl Alcohol; fluorine resin; polycarbonate; polyacetal; polyphenylene oxide; polyphenylene sulfide polyimide; polyarylate; polysulfone; polyether sulfone; rosin resin; terpene resin and petroleum resin;
Copolymer rubber: For example, ethylene/α-olefin/diene copolymer, propylene/α-olefin/diene copolymer, 1-butene/α-olefin/diene copolymer, polybutadiene rubber, polyisoprene rubber, neoprene Rubber, nitrile rubber, butyl rubber, polyisobutylene rubber, natural rubber, silicone rubber.

Among the above-mentioned thermoplastic polyolefin resins, for example, polyethylene and polypropylene can also be used as crystal nucleating agents, and in that case, the preferable content is 4-methyl-1-pentene polymer (X) and other polymers. The amount is 0.001 to 5% by mass based on 100 parts by mass of the total amount.

Among these thermoplastic resins, preferably low density, medium density, high density polyethylene, high pressure low density polyethylene, isotactic polypropylene, syndiotactic polypropylene, poly 1-butene, poly 3-methyl-1-pentene. , poly-3-methyl-1-butene, ethylene/α-olefin copolymer, propylene/α-olefin copolymer, 1-butene/α-olefin copolymer, styrene elastomer, vinyl acetate copolymer, ethylene・Methacrylic acid acrylate copolymers, ionomers, fluorine resins, rosin resins, terpene resins, and petroleum resins, and more preferably polyethylene and isotactic in terms of improved heat resistance, improved low temperature resistance, and flexibility. Polypropylene, syndiotactic polypropylene, ethylene/α-olefin copolymer, propylene/α-olefin copolymer, 1-butene/α-olefin copolymer, vinyl acetate copolymer, styrene elastomer, rosin resin, These are terpene resins and petroleum resins.

Part or all of the other polymer may be a graft-modified polymer obtained by graft-modifying the polymer with a polar monomer. The graft modification is carried out in accordance with the above-mentioned "graft modification" described for the 4-methyl-1-pentene polymer (X).
In the 4-methyl-1-pentene polymer composition of the present invention, one type of other polymer may be used alone, or two or more types may be used in combination.

・Other additives The 4-methyl-1-pentene polymer composition of the present invention may contain resin additives other than the antistatic agent (Y) containing the boron-based compound as other additives. .
Other additives include, for example, nucleating agents, anti-blocking agents, pigments, dyes, fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, ultraviolet absorbers, antibacterial agents, surfactants, Weathering stabilizer, heat stabilizer, anti-slip agent, foaming agent, crystallization aid, antifogging agent, anti-aging agent, hydrochloric acid absorber, impact modifier, crosslinking agent, co-crosslinking agent, crosslinking aid, adhesive, Examples include softeners, processing aids, and antistatic agents other than the antistatic agent (Y) containing the boron-based compound. These other additives may be used alone or in combination of two or more.

The content of other additives is not particularly limited depending on the use within a range that does not impair the purpose of the present invention, but may be It is preferably .001 to 30% by mass.

As the nucleating agent, known nucleating agents can be used to further improve the moldability of the 4-methyl-1-pentene polymer composition, that is, to increase the crystallization temperature and speed up the crystallization rate. Specifically, dibenzylidene sorbitol-based nucleating agents, phosphate ester salt-based nucleating agents, rosin-based nucleating agents, benzoic acid metal salt-based nucleating agents, fluorinated polyethylene, 2,2-methylenebis(4,6-di-t) -butylphenyl) phosphate, pimelic acid and its salts, 2,6-naphthalene dicarboxylic acid dicyclohexylamide, ethylene bisstearamide, and the like.

The amount of the nucleating agent is not particularly limited, but is preferably 0.001 to 5 parts by weight based on 100 parts by weight of the total amount of the 4-methyl-1-pentene polymer (X) and other polymers. . The nucleating agent can be added as appropriate during polymerization, after polymerization, or during molding.

As the anti-blocking agent, known anti-blocking agents can be used. Specifically, finely powdered silica, finely powdered aluminum oxide, finely powdered clay, powdered or liquid silicone resin, tetrafluoroethylene resin, finely powdered crosslinked resin, such as crosslinked acrylic, methacrylic resin powder, amide lubricant, etc. can be mentioned. Among these, fine powder silica and crosslinked acrylic and methacrylic resin powders are preferred.

Examples of pigments include inorganic pigments (titanium oxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and organic pigments (azo lake type, thioindigo type, phthalocyanine type, anthraquinone type). Examples of dyes include azo dyes, anthraquinone dyes, and triphenylmethane dyes. The amount of these pigments and dyes added is not particularly limited, but the total amount is usually 5% by mass or less, preferably 0.1 to 3% by mass based on the total mass of the 4-methyl-1-pentene polymer composition. %.

Examples of fillers include glass fibers, carbon fibers, silica fibers, metal (stainless steel, aluminum, titanium, copper, etc.) fibers, carbon black, silica, glass beads, silicates (calcium silicate, talc, clay, etc.), and metals. Examples include oxides (iron oxide, titanium oxide, alumina, etc.), metal carbonates (calcium sulfate, barium sulfate), powders of various metals (magnesium, silicon, aluminum, titanium, copper, etc.), mica, and glass flakes.

Examples of the lubricant include waxes (such as carnauba wax), higher fatty acids (such as stearic acid), higher alcohols (such as stearyl alcohol), and higher fatty acid amides (such as stearic acid amide).

Examples of plasticizers include aromatic carboxylic acid esters (dibutyl phthalate, etc.), aliphatic carboxylic acid esters (methyl acetyl ricinoleate, etc.), aliphatic dialboxylic acid esters (adipic acid-propylene glycol polyester, etc.), and aliphatic carboxylic acid esters (dibutyl phthalate, etc.). Examples include tricarboxylic acid esters (triethyl citrate, etc.), phosphoric acid triesters (triphenyl phosphate, etc.), epoxy fatty acid esters (epoxybutyl stearate, etc.), and petroleum resins.

Examples of mold release agents include lower (C1-4) alcohol esters of higher fatty acids (butyl stearate, etc.), polyhydric alcohol esters (C4-30) of fatty acids (hydrogenated castor oil, etc.), glycol esters of fatty acids, and fluids. Examples include paraffin.

As the antioxidant, known antioxidants can be used. Specifically, phenolics (2,6-di-t-butyl-4-methylphenol, etc.), polycyclic phenols (2,2'-methylenebis(4-methyl-6-t-butylphenol, etc.), phosphorus (tri(2,4-di-t-butylphenyl) phosphate, tetrakis(2,4-di-t-butylphenyl)-4,4-biphenylene diphosphonate, etc.), sulfur (thiodipropion) dilauryl acid, etc.), amine-based antioxidants (N,N-diisopropyl-p-phenylenediamine, etc.), lactone-based antioxidants, and the like.

Examples of flame retardants include organic flame retardants (nitrogen-containing, sulfur-containing, silicon-containing, phosphorus-containing, etc.), inorganic flame retardants (antimony trioxide, magnesium hydroxide, zinc borate, red phosphorus, etc.) ).

Examples of the ultraviolet absorber include benzotriazole-based, benzophenone-based, salicylic acid-based, and acrylate-based ultraviolet absorbers.
Examples of antibacterial agents include quaternary ammonium salts, pyridine compounds, organic acids, organic acid esters, halogenated phenols, and organic iodine.

Surfactants include nonionic, anionic, cationic or amphoteric surfactants. Examples of nonionic surfactants include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polypropylene glycol ethylene oxide adducts, polyethylene oxide, and glycerin. Examples include polyhydric alcohol type nonionic surfactants such as fatty acid esters, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol or sorbitan, alkyl ethers of polyhydric alcohols, and aliphatic amides of alkanolamines. Examples of anionic surfactants include sulfate ester salts such as alkali metal salts of higher fatty acids, sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates, and higher alcohol phosphate ester salts. Examples include phosphate ester salts. Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts. Examples of the amphoteric surfactant include amino acid-type double-sided surfactants such as higher alkylaminopropionates, and betaine-type amphoteric surfactants such as higher alkyl dimethyl betaine and higher alkyl dihydroxyethyl betaine.

Examples of the heat stabilizer include conventionally known stabilizers such as amine stabilizers, phenol stabilizers, and sulfur stabilizers. Specifically, aromatic secondary amine stabilizers such as phenylbutylamine and N,N'-di-2-naphthyl-p-phenylenediamine; dibutylhydroxytoluene and tetrakis[methylene(3,5-di-t- butyl-4-hydroxy)hydrocinnamate]methane, phenolic stabilizers such as octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate; bis[2-methyl-4-(3- thioether stabilizers such as n-alkylthiopropionyloxy)-5-t-butylphenyl] sulfide; dithiocarbamate stabilizers such as nickel dibutyldithiocarbamate; 2-mercaptobenzoylimidazole and zinc salts of 2-mercaptobenzimidazole; Examples include sulfur-based stabilizers such as dilaurylthiodipropionate and distearylthiodipropionate. These stabilizers may be used alone or in combination of two or more.

As the crosslinking agent, for example, organic peroxide is used.
Examples of the organic peroxide include dicumyl organic peroxide, di-tert-butyl organic peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, and 2,5-dimethyl-2,5-dimethyl -(tert-butylperoxy)hexyne-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl- 4,4-bis(tert-butylperoxy)valerate, benzoyl organic peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl organic peroxide, tert-butyl peroxybenzoate, tert-butyl perbenzoate, tert-butyl peroxyisopropyl carbonate , diacetyl organic peroxide, lauroyl organic peroxide, and tert-butylcumyl organic peroxide.

The organic peroxide is based on 100 parts by mass of the total amount of 4-methyl-1-pentene (co)polymer (A), 4-methyl-1-pentene copolymer (B), and other polymers (D), It is preferably used in a proportion of 0.05 to 10 parts by mass.

During the crosslinking treatment with organic peroxide, sulfur, p-quinonedioxime, p,p'-dibenzoylquinonedioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, and Peroxy crosslinking coagents such as methylolpropane-N,N'-m-phenylene dimaleimide, or divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, Polyfunctional methacrylate monomers such as allyl methacrylate, polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be blended.

By using the above compound, a uniform and mild crosslinking reaction can be expected. In particular, divinylbenzene is preferably used in the present invention. Divinylbenzene is easy to handle, has good compatibility with polymers, has the effect of solubilizing organic peroxides, and acts as a dispersant for organic peroxides. Therefore, a homogeneous crosslinking effect can be obtained, and a dynamically heat-treated product with well-balanced fluidity and physical properties can be obtained.

The amount of the crosslinking aid is not particularly limited, but is preferably 0.05 to 10 parts by weight based on 100 parts by weight of the 4-methyl-1-pentene polymer and other polymers. used.

Examples of the softener include process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, mineral oil softeners such as petrolatum, coal tar softeners such as coal tar and coal tar pitch, castor oil, rapeseed oil, Fatty oil-based softeners such as soybean oil and coconut oil; waxes such as tall oil, beeswax, carnauba wax, and lanolin; fatty acids or metal salts thereof such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, and calcium stearate; Naphthenic acid or its metal soap, pine oil, rosin or its derivatives, terpene resin, petroleum resin, coumaron indene resin, synthetic polymer substances such as atactic polypropylene, ester plastics such as dioctyl phthalate, dioctyl adipate, dioctyl sebacate, etc. agent, carbonate ester plasticizer such as diisododecyl carbonate, microcrystalline wax, sub (factice), liquid polybutadiene, modified liquid polybutadiene, liquid thiocol, hydrocarbon-based synthetic lubricating oil, and the like. Among these, petroleum softeners and hydrocarbon synthetic lubricating oils are preferred.

The blending amount of the softener is not particularly limited, but it is preferably 1 to 200 parts by weight based on 100 parts by weight of the total amount of the 4-methyl-1-pentene polymer and other polymers. The softener improves the mixability and moldability of the composition when preparing the 4-methyl-1-pentene polymer composition, making it easier to process, and also suppressing fillers (such as carbon black). Helps with dispersion.

Examples of antistatic agents other than the antistatic agent (Y) containing the boron-based compound include the above-mentioned surfactants, fatty acid esters, and polymer type antistatic agents. Examples of fatty acid esters include stearic acid and oleic acid esters, and examples of polymer antistatic agents include polyether ester amide. It is also preferable that the 4-methyl-1-pentene polymer composition of the present invention does not contain any antistatic agent other than the antistatic agent (Y) containing a boron compound.

The 4-methyl-1-pentene polymer composition of the present invention has excellent antistatic properties and excellent moldability. The 4-methyl-1-pentene polymer composition of the present invention can achieve sufficient antistatic properties by only containing a small amount of the antistatic agent (Y) containing a boron compound, so it can be molded with excellent transparency. It is also suitable for body manufacturing. The 4-methyl-1-pentene polymer composition of the present invention preferably has a haze when measured according to JIS K 7136 using a 2 mm thick molded article obtained by injection molding as a test piece. It is 2.0 to 8.0%, more preferably 2.0 to 7.0%, and the molded article obtained from the composition exhibits excellent transparency. In addition, the 4-methyl-1-pentene polymer composition of the present invention has a surface resistivity (Ω /sq) is preferably in the range of 5.0×10 ¹⁶ or less, more preferably in the range of 1.0×10 ¹³ to 2.5×10 ¹⁶ , even more preferably in the range of 1.0×10 ¹³ to 1.0×10 ¹⁶ The molded article obtained from the composition exhibits excellent antistatic properties. The 4-methyl-1-pentene polymer composition of the present invention has excellent moldability, and when a molded article is produced by injection molding, for example, molding defects such as voids and streaks are less likely to occur.

Method for producing 4-methyl-1-pentene copolymer composition The method for producing the 4-methyl-1-pentene copolymer composition according to the present invention is not particularly limited, but for example, 4-methyl-1-pentene copolymer composition It can be produced by mixing the polymer (X), the antistatic agent (Y) containing a boron-based compound, and other arbitrary components as necessary in the above-mentioned addition ratio, and then melt-kneading the mixture.

The melt-kneading method is not particularly limited, and can be performed using a commonly available melt-kneading device such as an extruder.
For example, the cylinder temperature of the part where kneading is performed in a kneader is usually 220 to 320°C, preferably 250 to 300°C. If the temperature is lower than 220°C, kneading will be insufficient due to insufficient melting, and it will be difficult to improve the physical properties of the copolymer composition. On the other hand, if the temperature is higher than 320°C, thermal decomposition of components such as the 4-methyl-1-pentene polymer (X) may occur. The kneading time is usually 0.1 to 30 minutes, particularly preferably 0.5 to 5 minutes. If the kneading time is less than 0.1 minute, sufficient melt-kneading will not be performed, and if the kneading time exceeds 30 minutes, thermal decomposition of components such as 4-methyl-1-pentene polymer (X) will occur. There are cases.

<Molded object>
The molded article according to the present invention is obtained by molding the 4-methyl-1-pentene polymer composition of the present invention described above.

(1) Molding method Various known molding methods can be applied to the 4-methyl-1-pentene copolymer composition, such as injection molding, extrusion molding, injection stretch blow molding, blow molding, Various molding methods can be mentioned, such as cast molding, calender molding, press molding, stamping molding, inflation molding, and roll molding. By these molding methods, it is possible to process the desired molded product, such as fiber, film, sheet, blow molded product, injection molded product, etc. The molding conditions are similar to those for conventionally known 4-methyl-1-pentene polymers. There are no particular restrictions on the shape of the molded body. For example, they are in the form of fibers, nonwoven fabrics, tubes, films, sheets, membranes, tapes, plates, rods, powders, particles, and the like.

(2) Applications The molded article of the present invention can be used without restriction in applications where conventional 4-methyl-1-pentene polymers can be used, but it is more suitable for applications that require antistatic properties. There is. More specific applications include clothing, sanitary products, packaging materials, electronic components, parts for electrical equipment, insulation materials, medical instruments, medical packaging materials, laboratory equipment, food containers, cushioning materials, and release films. , protective films, automobile parts, camera parts, etc.

The 4-methyl-1-pentene polymer composition of the present invention contains 4-methyl-1-pentene without adding a large amount of antistatic agent by containing a specific antistatic agent (Y) containing a boron-based compound. - The charging of the pentene polymer can be effectively suppressed, and problems such as deterioration of moldability and deterioration of hue due to the inclusion of a large amount of antistatic agent do not occur. The molded article of the present invention obtained using the 4-methyl-1-pentene polymer composition of the present invention has effectively suppressed charging, low surface resistivity, and Since the half-life of the electric charge is short, even if it is charged during the manufacturing process, the charging property quickly decreases, and an antistatic effect is obtained.

EXAMPLES Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited to these Examples.
[Measuring method]
In the following Examples and Comparative Examples, various characteristics were measured as follows.

<Comonomer content in 4-methyl-1-pentene copolymer>
The content of structural units derived from the comonomer (comonomer content) was calculated from the ¹³ C-NMR spectrum using the following equipment and conditions.
Using a Bruker Biospin AVANCE III cryo-500 nuclear magnetic resonance apparatus, the solvent was an o-dichlorobenzene/benzene-d ₆ (4/1 v/v) mixed solvent, the sample concentration was 55 mg/0.6 mL, and the measurement temperature was The temperature was 120℃, the observation core was ^13C (125MHz), the sequence was single-pulse floton broadband decoupling, the pulse width was 5.0 μs (45° pulse), the repetition time was 5.5 seconds, and the number of integrations was 64 times. , 128 ppm of benzene-d ₆ was measured as a reference value of chemical shift. The comonomer content was calculated using the following formula using the integral value of the main chain methine signal.
Comonomer content (%) = [P/(P+M)] x 100
Here, P indicates the total peak area of the comonomer main chain methine signal,
M indicates the total peak area of the 4-methyl-1-pentene main chain methine signal.

In addition, when the 4-methyl-1-pentene polymer is obtained in the two-stage polymerization process of polymerization process 1 and polymerization process 2, the comonomer content in the polymer produced in polymerization process 1 is the same as that of polymerization process 1. The comonomer content in the polymer produced in polymerization step 2 is determined by using the polymer obtained from the polymer slurry extracted at the end of polymerization, and the comonomer content in the polymer obtained in polymerization step 1, the final polymer ( It was determined using the comonomer content in polymerization step 1 + polymerization step 2) and the proportion of the polymer produced in each step. Specifically, the comonomer contents in the polymer produced in polymerization step 1 and polymerization step 2 and the final polymer are respectively m ₁ , m ₂ and m _f , and the comonomer content of the polymer produced in polymerization step 1 and polymerization step 2 is Let w ₁ and w ₂ be the proportions, respectively, then m ₂ =(m _f −w ₁ ·m ₁ )/w ₂ .

<Intrinsic viscosity [η]>
The intrinsic viscosity [η] was measured at 135°C using a decalin solvent. Specifically, about 20 mg of each copolymer was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135°C. After diluting the decalin solution by adding 5 ml of decalin solvent, the specific viscosity ηsp was measured in the same manner. This dilution operation was repeated two more times, and the value of ηsp/C (dl/g) when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity (see the formula below).
[η]=lim(ηsp/C) (C→0)
In addition, when the 4-methyl-1-pentene polymer is obtained through a two-step polymerization process of polymerization process 1 and polymerization process 2, the intrinsic viscosity [η] of the polymer (component 1) produced in polymerization process 1 is is determined using the polymer obtained from the polymer slurry extracted at the end of polymerization step 1, and the intrinsic viscosity [η] of the polymer (component 2) produced in polymerization step 2 is determined using the polymer obtained in polymerization step 1. It was determined using the intrinsic viscosity [η] of the polymer obtained, the intrinsic viscosity [η] of the final polymer (polymerization step 1 + polymerization step 2), and the proportion of the polymer produced in each step. Specifically, [η] of the polymer produced in polymerization step 1 and polymerization step 2 and the final polymer are respectively [η] ₁ , [η] ₂ and [η] _f , and polymerization step 1 and polymerization step 2 are Let w ₁ and w ₂ be the proportions of the polymers produced in , respectively, then [η] ₂ = ([η] _f −w ₁ ·[η] ₁ )/w ₂ .

<Melting point (Tm)>
An exothermic/endothermic curve was determined using a DSC measuring device (DSC220C) manufactured by Seiko Instruments Inc., and the temperature at the maximum melting peak position during temperature rise was defined as the melting point (Tm). The measurements were performed as follows.
Approximately 5 mg of a sample was cut out from a 0.5 mm thick injection test piece, packed in an aluminum pan for measurement, heated from 20 to 280 °C at a heating rate of 10 °C/min, held at 280 °C for 5 minutes, and heated for 10 minutes. The temperature was lowered to 20 °C at a cooling rate of °C/min, held at 20 °C for 5 minutes, and then raised again from 20 °C to 280 °C at a heating rate of 10 °C/min, and then at a cooling rate of 50 °C/min. The temperature was lowered to 50°C. The melting peak that appeared during the second temperature rise was defined as the melting point (Tm). When multiple peaks were detected, the one with the highest temperature was taken as the melting point (Tm). When a 4-methyl-1-pentene polymer is obtained in a two-step polymerization process of polymerization process 1 and polymerization process 2, the melting point (Tm) of the polymer (component 2) produced in polymerization process 2 is: It was determined by analyzing the polymer produced in polymerization step 1 and the final polymer.

<Surface resistivity>
The surface resistivity was measured according to JIS C2139 using ADC Digital Ultra High Resistance/Micro Ammeter 8340A. The sample was prepared for 24 hours at 23° C. and 50% RH, and the surface efficiency (Ω/sq) was measured at an applied voltage of 500 V and an application time of 60 seconds.

<Charge half-life time (electrostatic voltage decay test)>
The charge voltage decay was measured in accordance with JIS L1094 using a static honest meter H-0110 manufactured by Shishido Electrostatics, and the charge half-life time (seconds) was determined. The sample was prepared for 24 hours at 23° C. and 50% RH, the applied voltage was -10 kV, and the measurement period was 180 seconds. A level where the half-life time is 180 seconds or more is described as 180 seconds or more.

<Haze (total light transmittance)>
Using a 2 mm thick injection test piece, haze was measured in accordance with JIS K 7136 using a haze/transmittance meter HM-150 (D65 light source) manufactured by Murakami Color Research Institute Co., Ltd. However, no measurements were made for Comparative Example 5, which became opaque.

<Moldability confirmation>
Under the injection conditions described below, molding defects such as voids and silver stripes due to decomposed gas etc. were visually confirmed, and the following evaluations were made. Here, voids refer to air bubbles formed inside the molded product. Silver streaks are silver-white streaks that are formed in the direction of flow of the material due to gas mixed in during molding, and appear as a defective appearance.
A: No voids or silver streaks were observed, and molding was possible without any problems.
B: Voids and silver stripes were observed, and there were problems with molding.

[Production Examples 1 to 6] (Production of 4-methyl-1-pentene polymers 1 to 6)
According to the polymerization method described in Comparative Example 9 of International Publication No. 2006/054613, 4-methyl-1-pentene, other α-olefins (1-decene or a mixture of 1-hexadecene and 1-octadecene), By changing the proportion of hydrogen, 4-methyl-1-pentene polymers 1 to 6 were obtained. That is, a solid titanium catalyst was prepared and polymerized as follows.

・Preparation of solid titanium catalyst (A-1) After heating and reacting 75 g of anhydrous magnesium chloride, 280.3 g of decane, and 308.3 g of 2-ethylhexyl alcohol at 130°C for 3 hours to form a homogeneous solution, in this solution 19.9 g of 2-isobutyl-2-isopropyl-1,3-dimethoxypropane (BPMP) was added to the mixture, and the mixture was stirred and mixed at 100° C. for 1 hour.

After cooling the homogeneous solution thus obtained to 23°C, 30ml of this homogeneous solution was added dropwise to 80ml of titanium tetrachloride maintained at -20°C over 45 minutes with stirring. After the charging was completed, the temperature of this liquid mixture was raised to 110° C. over 5.8 hours, and maintained at the same temperature for 2 hours while stirring. After the 2-hour reaction was completed, the solid portion was collected by hot filtration, and after resuspending this solid portion in 100 ml of titanium tetrachloride, the heating reaction was performed again at 110° C. for 2 hours. After the reaction was completed, the solid portion was again collected by hot filtration and thoroughly washed with decane and hexane at 90° C. until no free titanium compound was detected in the washing liquid. The solid titanium catalyst component (A-1) prepared by the above procedure was stored as a decane slurry, and a portion of this was dried for the purpose of investigating the catalyst composition. The composition of the solid titanium catalyst component (A-1) thus obtained was as follows: 4.1% by mass of titanium element, 17.0% by mass of magnesium element, 57% by mass of chlorine element, 2-isobutyl-2-isopropyl -1,3-dimethoxypropane was 15.9% by mass and 2-ethylhexyl alcohol residue was 2.1% by mass.

・Polymerization 4-methyl-1-pentene, which is a monomer component, and other α-olefins (1-decene, or a mixture of 1-hexadecene and 1-octadecene ( Linearene 168 (manufactured by Idemitsu Kosan Co., Ltd.) with a mixing molar ratio of 1-hexadecene/1-octadecene of 60/40) and hydrogen were introduced at 23°C with the amounts introduced appropriately adjusted. 0.5 mmol and 0.0016 mmol in terms of titanium atoms of the solid titanium catalyst component (A-1) obtained above were added, and the polymerization reaction was carried out for 1 hour while keeping the inside of the polymerization vessel at 60°C. -Methyl-1-pentene polymers 1 to 6 were obtained, respectively.
Table 1 shows the physical properties of each polymer obtained.

[Manufacture example 7]
・Preparation of catalyst component [Synthesis of transition metal complex (metallocene compound (a1))]
According to Synthesis Example 4 of International Publication No. 2014/050817, (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6, 7,7a,8-octahydrocyclopenta[a]indene)) Zirconium dichloride (metallocene compound (a1)) was synthesized.

[Preparation of solid catalyst component (metallocene catalyst)]
As a carrier, solid polymethylaluminoxane (manufactured by Tosoh Finechem Co., Ltd.), which is particulate and has a D50 of 8 μm and an aluminum atom content of 42% by mass, was used. At 30°C, in a 100 mL three-necked flask equipped with a stirrer and sufficiently purged with nitrogen, 29.9 mL of purified decane and 7.26 mL of the hexane/decane solution of the solid polymethylaluminoxane (aluminum atoms) were added under a nitrogen stream. 14.3 mmol) was added to form a suspension. To the suspension, 50 mg (0.0586 mmol in terms of zirconium atoms) of the previously synthesized metallocene compound (a1) was added as a 4.59 mmol/L toluene solution in 12.8 mL with stirring. After 1.5 hours, stirring was stopped, and decantation cleaning was performed with decane (cleaning efficiency 98%) to obtain 50 mL of slurry liquid (Zr loading rate 96%). The obtained solid catalyst component (metallocene catalyst) was in the form of particles, and its D50 was 8 μm.

[Preparation of prepolymerization catalyst component]
To the slurry liquid prepared as above, 4.0 mL of a decane solution of diisobutylaluminum hydride (1 mol/L in terms of aluminum atoms) and 15 mL (10.0 g) of 3-methyl-1-pentene were charged under a nitrogen stream. did. After 1.5 hours, stirring was stopped and decantation washing was performed with decane (washing efficiency 95%) to obtain 100 mL of decane slurry of the prepolymerized catalyst component (Zr recovery rate 93%, 0.548 mmol/L in terms of zirconium atoms). .

・Polymerization At 23°C under a nitrogen stream, 425 mL of purified decane and 0.4 mL of triethylaluminum solution (1.0 mmol/mL in terms of aluminum atoms) were added to a SUS polymerization vessel with an internal volume of 1 L and equipped with a stirrer. 0.4 mmol). Next, 0.0014 mmol in terms of zirconium atoms of the previously prepared decane slurry of the prepolymerized catalyst component was added, and the temperature was raised to 40°C. After reaching 40° C., 15 NmL of hydrogen was charged, and then 106 mL of 4-methyl-1-pentene was continuously charged into the polymerization vessel at a constant rate over 30 minutes. The polymerization was started at this time of charging, and the temperature was maintained at 45° C. for 3 hours. After 3 hours from the start of polymerization, the temperature was lowered to 23° C., the pressure was removed, and the polymerization liquid (slurry) containing a white solid was immediately filtered to obtain a solid substance. This solid substance was dried at 80° C. for 8 hours under reduced pressure to obtain 4-methyl-1-pentene polymer 7, which was a particulate 4-methyl-1-pentene homopolymer. Table 1 shows the physical properties of the obtained polymer 7.

[Manufacture example 8]
・Polymerization At 23°C under a nitrogen stream, 425 mL of purified decane and 0.4 mL of triethylaluminum solution (1.0 mmol/mL in terms of aluminum atoms) were added to a SUS polymerization vessel with an internal volume of 1 L and equipped with a stirrer. 0.4 mmol). Next, 0.0014 mmol of the prepolymerized catalyst component prepared in Production Example 7 was added in an amount of 0.0014 mmol in terms of zirconium atoms, and the temperature was raised to 40°C. After reaching 40°C, 40NmL of hydrogen was charged, and then 106mL of 4-methyl-1-pentene and 3.4mL of Linearene 168 (a mixture of 1-hexadecene and 1-octadecene, manufactured by Idemitsu Kosan Co., Ltd.) were added over 30 minutes. The polymer was continuously charged into the polymerization vessel at a constant speed. Polymerization was started at this point in time when charging started, and the temperature was maintained at 45° C. for 3 hours (polymerization step 1). After 3 hours, the system was depressurized at 45° C., and in order to discharge residual hydrogen from the system, pressurization and depressurization with nitrogen (0.6 MPa) were performed three times. Thereafter, 120 NmL of hydrogen was charged at 45°C under a nitrogen stream, and then 79.4 mL of 4-methyl-1-pentene and Linearene 168 (mixture of 1-hexadecene and 1-octadecene, manufactured by Idemitsu Kosan Co., Ltd.) A mixed solution of 10.9 mL was continuously charged into the polymerization vessel at a constant speed over 30 minutes. Polymerization was started at this point in time when charging started, and the temperature was maintained at 45° C. for 3 hours (polymerization step 2). After 3 hours had passed from the start of polymerization, the temperature was lowered to 23° C., the pressure was removed, and the polymerization liquid (slurry) containing a white solid was immediately filtered to obtain a solid substance. This solid substance was dried at 80° C. for 8 hours under reduced pressure to obtain particulate 4-methyl-1-pentene polymer 8.
The 4-methyl-1-pentene polymer 8 thus obtained is a two-stage polymerization product of polymerization step 1 and polymerization step 2, and consists of component 1 produced in polymerization step 1 and component 1 produced in polymerization step 2. It contains component 2. The mass ratio of component 1 and component 2 (component 1/component 2) was 55/45. The properties of component 1 and component 2 are shown in Table 1.

The antistatic agents used in the following Examples and Comparative Examples are as follows.
・Y-1: Biomicelle BN-105 (Boron Institute Co., Ltd.)
・Y-2: ADEKA STAB AS301-E (ADEKA Co., Ltd.)
・Y-3: Irgastat P 18 FCA (BASF Japan Ltd.)
・Y-4: Electro Stripper PC (Kao Corporation)
・Y-5: Electro Stripper PC3 (Kao Corporation)
Here, Y-1 (Biomicelle BN-105) is an antistatic agent represented by the following structural formula, and is a boron-based compound that satisfies the aforementioned formulas (1) and (2).

[Examples 1 to 10, Comparative Examples 1 to 7]
Each of the 4-methyl-1-pentene polymers obtained in the above production examples and an antistatic agent were added in the amount shown in Table 2 or Table 3 (by mass) in the composition after blending. %) in a Henschel mixer (manufactured by Mitsui Miike Seisakusho Co., Ltd., 150 L) and mixed for 2 minutes at 1460 rpm. Subsequently, a polymer composition was obtained by melt-kneading using a twin-screw extruder (PCM43, manufactured by Ikegai Co., Ltd., screw diameter: 43 mm, temperature: 280° C., rotation speed: 200 rpm).
Each of the obtained polymer compositions was molded into a 2 mm square plate using a 70 ton injection molding machine (M70B) manufactured by Meiki Seisakusho Co., Ltd. under the conditions of cylinder temperature: 280°C and mold temperature: 60°C. An injection test piece was prepared by injecting the sample into a sample.
Using this injection test piece, surface resistivity, charge half-life time, and haze were determined. The results are also shown in Table 2 or Table 3.

The 4-methyl-1-pentene polymer composition of the present invention can be used without restrictions in applications where conventional 4-methyl-1-pentene polymers can be used, but it requires antistatic properties. It is more suitable for the purpose. The molded article of the present invention using the 4-methyl-1-pentene polymer composition of the present invention can be used, for example, in clothing, sanitary products, packaging materials, electronic parts, electrical equipment parts, insulating materials, and medical instruments. It can be suitably used for applications such as medical packaging materials, laboratory equipment, food containers, cushioning materials, release films, protective films, automobile parts, and camera parts.

Claims (6)

A 4-methyl-1-pentene polymer (X) that satisfies the following requirements (X-1),
An antistatic agent (Y) containing a boron-based compound having a structure represented by the following formula (1);
Consisting only of
A 4-methyl-1-pentene polymer composition containing 0.1 to 2.0% by mass of the antistatic agent (Y) containing the boron compound .
(X-1) The content of structural units derived from 4-methyl-1-pentene is 30.0 to 100.0 mol%, and ethylene and α-olefins having 3 to 20 carbon atoms (with the exception of 4-methyl- The total content of structural units derived from (excluding 1-pentene) is 0.0 to 70.0 mol%.
The 4-methyl-1-pentene polymer composition according to claim 1, wherein the 4-methyl-1-pentene polymer (X) satisfies the following requirements (X-2) and (X-3).
(X-2) The intrinsic viscosity [η] measured in decalin at 135°C is in the range of 0.5 to 10.0 dl/g.
(X-3) At least one of the melting points (Tm) measured by DSC is 200°C or higher. The antistatic agent (Y) containing the boron-based compound is obtained by the following formula (2) or formula (3), which is obtained by reacting a semipolar organic boron compound as a donor component and a basic nitrogen compound as an acceptor component. ) The 4-methyl-1-pentene polymer composition according to claim 1 or 2, which is a donor-acceptor antistatic agent represented by:
(In formula (2), R ¹ and R ² are each independently R ⁷ CO-OCH ₂ - or HOCH ₂ -, and at least one is R ⁷ CO-OCH ₂ -, and R ³ and R ⁴ is each independently CH ₃ -, C ₂ H ₅ -, HOCH ₂ -, HOC ₂ H ₄ - or HOCH ₂ CH(CH ₃ )-, and R ⁵ is -C ₂ H ₄ - or -C ₃ H ₆ -, and R ⁶ and R ⁷ are each independently alkyl having 11 to 21 carbon atoms.)
(In formula (3), R ¹ and R ² are each independently R ⁷ CO-OCH ₂ - or HOCH ₂ -, and at least one is R ⁷ CO-OCH ₂ -, and R ³ and R ⁴ is each independently CH ₃ -, C ₂ H ₅ -, HOCH ₂ -, HOC ₂ H ₄ - or HOCH ₂ CH(CH ₃ )-, and R ⁵ is -C ₂ H ₄ - or -C ₃ H ₆ -, and R ⁶ and R ⁷ are each independently alkyl having 11 to 21 carbon atoms.) According to any one of claims 1 to 3 , the haze measured in accordance with JIS K 7136 is 2.0 to 8.0% using a 2 mm thick molded body obtained by injection molding as a test piece. The 4-methyl-1-pentene polymer composition described above. A molded article comprising the 4-methyl-1-pentene polymer composition according to any one of claims 1 to 4 . A fiber comprising the 4-methyl-1-pentene polymer composition according to any one of claims 1 to 4 .