JP2022154305A - 4-methyl-1-pentene-based polymer composition and use of the same - Google Patents

Abstract

To provide a 4-methyl-1-pentene-based polymer composition which can obtain a molding having good stretchability, a molding containing the 4-methyl-1-pentene-based polymer composition, and a stretched molding.SOLUTION: A 4-methyl-1-pentene-based polymer composition (X) contains (A) 100 pts.mass of a 4-methyl-1-pentene-based polymer satisfying the following requirements (a1) to (a3), and (B) 1-90 pts.mass of a hydrogenated resin obtained from a hydrogenated petroleum resin or aromatic hydrocarbon. (a1) Structural unit derived from 4-methyl-1-pentene of 90-100 mol%, and a structural unit derived from α-olefin having 2 to 20 carbon atoms of 0-10 mol%, (a2) intrinsic viscosity [η] of 0.5-5.0 dl/g, and (a3) melting point (Tm) of 180-260°C.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a stretch-moldable 4-methyl-1-pentene polymer composition, a molded article containing the composition, and a stretched molded article.

4-Methyl-1-pentene polymers are widely used in various applications because of their excellent heat resistance, releasability and chemical resistance. For example, a film containing a 4-methyl-1-pentene polymer can be used as a release film for manufacturing printed wiring boards, a release film for molding composite materials, and a release paper for manufacturing synthetic leather, taking advantage of its good releasability. and other release films (see Patent Document 1). In addition, moldings containing 4-methyl-1-pentene polymers are used for laboratory equipment and mandrels for manufacturing rubber hoses, taking advantage of their heat resistance, chemical resistance, acid resistance, and transparency. there is

Patent Document 2 teaches that a wrap film obtained from a resin composition containing polybutene or a hydrogenated petroleum hydrocarbon resin and polymethylpentene is excellent in heat resistance, self-adhesiveness, and transparency. . Further, Patent Document 3 teaches that a film or the like made of a resin composition containing a 4-methyl-1-pentene copolymer and a hydrogenated resin is excellent in transparency. However, these documents do not discuss the improvement of stretchability of 4-methyl-1-pentene copolymers.

JP 2010-027745 A JP-A-6-136149 JP 2015-7179 A WO2013/099876

As a method for producing a stretched molded article from a 4-methyl-1-pentene polymer, the applicant of the present application proposed a polymer composition obtained by mixing 4-methyl-1-pentene polymers with different properties. It is proposed to manufacture a stretch molded product using a material (see Patent Document 4). However, a 4-methyl-1-pentene polymer composition that maintains the inherent heat resistance and transparency of the 4-methyl-1-pentene polymer, has excellent stretchability and can be stretched uniformly, and a uniform There has been a demand for the emergence of a stretched molded product that is stretched to a

The present invention provides a 4-methyl-1-pentene polymer composition capable of obtaining a molded article having good stretchability, a molded article containing the 4-methyl-1-pentene polymer composition, and An object of the present invention is to provide a stretch molded product.

As a result of intensive studies by the present inventors to solve the above problems, the present inventors have found that a hydrogenated resin comprising a specific 4-methyl-1-pentene polymer and a hydrogenated petroleum resin or an aromatic hydrocarbon. The inventors have found that the composition, and the molded article and the stretched molded article obtained therefrom can solve the above-mentioned problems, leading to the present invention. That is, the present invention relates to the following [1] to [7].

[1]
(A) 100 parts by mass of a 4-methyl-1-pentene polymer that satisfies the following requirements (a1) to (a3);
(B) a 4-methyl-1-pentene polymer composition (X) containing 1 to 90 parts by mass of a hydrogenated petroleum resin or a hydrogenated resin obtained from an aromatic hydrocarbon;
(a1) 90 to 100 mol % of structural units derived from 4-methyl-1-pentene, and 0 to 10 mol % of structural units derived from α-olefin having 2 to 20 carbon atoms.
(a2) The intrinsic viscosity [η] measured in decalin at 135°C is 0.5 to 5.0 dl/g.
(a3) The melting point (Tm) measured by DSC is 180 to 260°C.

[2]
The 4-methyl-1-pentene polymer composition (X) according to [1] above, wherein the component (B) satisfies the following requirements (b1) and (b2).
(b1) The softening point is 80° C. or higher.
(b2) a number average molecular weight (Mn) of 300 to 5,000;

[3]
The 4-methyl-1-pentene polymer composition (X) according to [2] above, wherein the component (B) further satisfies the following requirements (b3) and (b4).
(b3) The hydrogenation rate is 80% or more.
(b4) The main monomer is at least one selected from C9 aromatic hydrocarbons, dicyclopentadiene and α-methylstyrene.

[4]
According to JIS K7196, using a test piece with a thickness of 1 mm, a pressure of ² kg/cm was applied to a flat indenter with a diameter of 1 mm at a heating rate of 5 ° C./min, and the needle penetration temperature (TMA, ° C. ) is 170 to 260° C., the 4-methyl-1-pentene polymer composition (X) according to any one of the above [1] to [3].
[5]
A molded article comprising the 4-methyl-1-pentene polymer composition (X) according to any one of [1] to [4].

[6]
A stretched molded article comprising the 4-methyl-1-pentene polymer composition (X) according to any one of [1] to [5].
[7]
The stretched molded article according to the above [6], which is a film, sheet or blow molded article.

According to the present invention, there is provided a 4-methyl-1-pentene polymer composition capable of obtaining a molded article having good stretchability, and a molded article containing the 4-methyl-1-pentene polymer composition. , as well as stretch molded articles.

FIG. 1 shows the original film (marked) before stretching in Example 1. FIG. 2 shows the stretched film of Example 1. FIG. 3 shows the stretched film of Example 2. FIG. 4 shows the stretched film of Comparative Example 1. FIG.

The present invention will be specifically described below. In this specification, A and B mean from A to B, unless otherwise specified. Moreover, in this specification, polymerization and copolymerization may be referred to as polymerization, and polymers and copolymers may be collectively referred to as polymers.

4-methyl-1-pentene polymer composition (X)
The 4-methyl-1-pentene polymer composition (X) of the present invention is obtained from (A) a 4-methyl-1-pentene polymer and (B) a hydrogenated petroleum resin or an aromatic hydrocarbon. and a hydrogenated resin as an essential component.

<(A) 4-methyl-1-pentene polymer>
The (A) 4-methyl-1-pentene polymer according to the present invention satisfies the following requirements (a1) to (a3).
(a1) 90 to 100 mol % of structural units derived from 4-methyl-1-pentene, and 0 to 10 mol % of structural units derived from α-olefin having 2 to 20 carbon atoms.
(a2) The intrinsic viscosity [η] measured in decalin at 135°C is 0.5 to 5.0 dl/g.
(a3) The melting point (Tm) measured by DSC is 180 to 260°C.

Each of the requirements (a1) to (a3) will be described below.
・Requirement (a1)
(A) 4-methyl-1-pentene-based polymer according to the present invention has 90 to 100 mol% of structural units derived from 4-methyl-1-pentene, and an α-olefin having 2 to 20 carbon atoms It is a polymer (homopolymer or copolymer) in which the structural unit derived from is 0 to 10 mol%. (A) The content of structural units derived from 4-methyl-1-pentene in the 4-methyl-1-pentene polymer is preferably 91.0 to 99.9 mol%, more preferably 91.9 mol%. 5 to 99.5 mol%, more preferably 92.0 to 99.0 mol%, and the content of structural units derived from an α-olefin having 2 to 20 carbon atoms is preferably 0.1 ~9.0 mol%, more preferably 0.5 to 8.5 mol%, still more preferably 1.0 to 8.0 mol%.

When each structural unit is in the above range, (A) the 4-methyl-1-pentene polymer composition (X) containing a 4-methyl-1-pentene polymer has excellent heat resistance and transparency, and further stretches It is also preferable because it has good properties. In addition, the molded article and the stretched molded article containing the 4-methyl-1-pentene polymer composition (X) also have excellent heat resistance and transparency, and the stretched molded article is uniformly stretched. Therefore, it is preferable.

When the (A) 4-methyl-1-pentene-based polymer has a structural unit derived from an α-olefin having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene), the number of carbon atoms is 2 -20 α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 1-octene, 1-decene, 1 -dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-eicosene and the like are mentioned as suitable examples.

Among these, ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-hexadecene, 1-heptadecene, 1-octadecene, more preferably ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-hexadecene , 1-heptadecene and 1-octadecene, more preferably 1-octene, 1-decene, 1-hexadecene, 1-heptadecene and 1-octadecene.
These α-olefins having 2 to 20 carbon atoms can be used alone or in combination of two or more.

The (A) 4-methyl-1-pentene-based polymer according to the present invention may contain structural units derived from other polymerizable compounds as long as the object of the present invention is not impaired.
Examples of such other polymerizable compounds include vinyl compounds having a cyclic structure such as styrene, vinylcyclopentene, vinylcyclohexane, and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids such as maleic anhydride; Derivatives thereof; conjugated dienes such as butadiene, isoprene, pentadiene, and 2,3-dimethylbutadiene; 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5 -heptadiene, 7-methyl-1,6-octadiene, dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylenenorbornene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5 -isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylidene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl- non-conjugated polyenes such as 2,2-norbornadiene;

The (A) 4-methyl-1-pentene-based polymer contains units derived from such other polymerizable compounds in all polymerizations contained in the (A) 4-methyl-1-pentene-based polymer. may be contained in an amount of 10 mol % or less, preferably 5 mol % or less, more preferably 3 mol % or less, relative to 100 mol % of structural units derived from a chemical compound.

・Requirements (a2)
The (A) 4-methyl-1-pentene polymer according to the present invention has an intrinsic viscosity [η] measured in decalin at 135° C. of 0.5 to 5.0 dl/g, preferably 1.0 to 4.5 dl/g, more preferably 1.3 to 4.2 dl/g, still more preferably 1.5 to 4.0 dl/g.
The value of the intrinsic viscosity [η] can be adjusted, for example, by adjusting the amount of hydrogen added during polymerization when producing the 4-methyl-1-pentene polymer (A).

(A) 4-methyl-1-pentene-based polymer having a value of intrinsic viscosity [η] within the above range exhibits good fluidity during mixing for preparing a resin composition and during various molding, and the obtained molding It is believed to contribute to the toughness of the body. In addition, such (A) 4-methyl-1-pentene-based polymer, the 4-methyl-1-pentene-based polymer composition (X) of the present invention containing the same, and molding obtained from the composition (X) The body and stretch molded body are excellent in transparency.

・Requirements (a3)
The (A) 4-methyl-1-pentene polymer according to the present invention has a melting point (Tm) measured by DSC of 180 to 260°C, preferably 190 to 250°C, more preferably 195 to 240°C. More preferably, it is 200 to 235°C.

The value of the melting point (Tm) tends to depend on the stereoregularity of the polymer and the content of α-olefin constitutional units having 2 to 20 carbon atoms. can be obtained by controlling the content of α-olefin structural units having 2 to 20 carbon atoms.

The (A) 4-methyl-1-pentene polymer having a melting point (Tm) within the above range is preferable from the viewpoint of heat resistance and moldability. In addition, the 4-methyl-1-pentene polymer composition (X) of the present invention containing this and the molded articles and stretch molded articles obtained therefrom have excellent heat resistance and uniform and excellent properties. Therefore, it is preferable.

· Density Although the (A) 4-methyl-1-pentene polymer according to the present invention is not particularly limited, its density is preferably 820 to 850 kg / m ³ , more preferably 825 to 850 kg/m ³ , more preferably 825-845 kg/m ³ .

The above density value can be adjusted, for example, by selecting the type and content of other α-olefin polymerized together with 4-methyl-1-pentene.
When the density value is within the above range, the 4-methyl-1-pentene-based polymer (A), the 4-methyl-1-pentene-based polymer composition (X) of the present invention containing the same, and the composition obtained therefrom It is preferable from the viewpoint of the heat resistance of the molded article and the stretched molded article.

(A) Method for producing 4-methyl-1-pentene-based polymer (A) 4-methyl-1-pentene-based polymer according to the present invention is 4-methyl that satisfies the above requirements (a1) to (a3) The production method is not particularly limited as long as the 1-pentene polymer can be obtained. -1-pentene) or other polymerizable compounds. As the polymerization method, it can be produced by, for example, a gas phase method, a solution method, a slurry method, or the like. As catalysts, in addition to conventionally known olefin polymerization catalysts such as vanadium-based catalysts, titanium-based catalysts, and magnesium-supported titanium catalysts, for example, metallocene catalysts include WO 2001/53369 and WO 2001/27124. No. pamphlet, International Publication No. 2006/054613 pamphlet, International Publication No. 2014/050817 pamphlet, JP-A-3-193796 or JP-A-2-41303.

Further, (A) the 4-methyl-1-pentene-based polymer according to the present invention comprises 4-methyl-1-pentene and, if necessary, the α-olefin having 2 to 20 carbon atoms (4-methyl-1 - Pentene) and other polymerizable monomers can be obtained by single-stage polymerization in a single polymerization layer, and 4-methyl-1-pentene (co)polymers produced in separate steps are mixed. can also be obtained by Furthermore, the 4-methyl-1-pentene (co)polymer can also be obtained by continuously polymerizing in multiple stages through a plurality of polymer layers. In either case, the resin may be prepared so that the physical properties of the entire resin are within the above ranges.

Further, the 4-methyl-1-pentene-based polymer (A) can be a commonly available 4-methyl-1-pentene-based polymer, for example, TPX (manufactured by Mitsui Chemicals, Inc.) registered trademark), etc. can be used.

<(B) Hydrogenated Petroleum Resin or Hydrogenated Resin Obtained from Aromatic Hydrocarbon>
The 4-methyl-1-pentene polymer composition (X) of the present invention is (B) a hydrogenated petroleum resin or a hydrogenated resin obtained from an aromatic hydrocarbon (hereinafter abbreviated as hydrogenated resin (B) may be used).

(hydrogenated petroleum resin)
The hydrogenated petroleum resin, which is one of the hydrogenated resins (B), is a hydrogenated compound obtained by partially or wholly hydrogenating an aliphatic petroleum resin whose main raw material is the C5 fraction of tar naphtha. isoprene, trans-1,3-pentadiene, cis-1,3-pentadiene, cyclopentadiene, dicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene, and conjugated diolefins having 4 to 6 carbon atoms. Hydrogenated resins obtained by polymerizing polyunsaturated hydrocarbons can be mentioned, among which hydrogenated compounds of dicyclopentadiene resins are preferred.

(Hydrogenated resin obtained from natural resin)
A hydrogenated resin obtained from a natural resin, which is one of the hydrogenated resins (B), is a resin obtained by partially or completely hydrogenating a natural resin. Examples include hydrogenated terpene-based resins obtained by hydrogenating terpene-based resins having terpene as a constituent unit, and hydrogenated rosin-based resins obtained by hydrogenating rosin-based resins obtained from pine trees. . Examples thereof include terpene resins such as α-pinene resin, β-pinene resin, aromatic modified terpene resin, terpene phenol resin, and hydrogenated terpene resin.

(Hydrogenated resin obtained from aromatic hydrocarbon)
The hydrogenated resin obtained from an aromatic hydrocarbon, which is one of the hydrogenated resins (B), is partially or completely composed of an aromatic petroleum resin and a copolymer petroleum resin thereof whose main raw material is a C9 fraction. Hydrogenated compounds, specifically, those obtained by hydrogenating C9 aromatic petroleum resins obtained by polymerizing styrene, isopropenyltoluene, vinyltoluene, α-methylstyrene, and indenes, for example. Among them, those obtained from styrene and α-methylstyrene are preferred, and those obtained from α-methylstyrene are more preferred. The aromatic petroleum resin includes C5/C9 copolymerized petroleum resin (resin obtained by copolymerizing C5 fraction and C9 fraction of cracked naphtha oil), styrenes of tar naphtha fraction, indene, coumarone, and other distillates. A coumarone-indene resin containing cyclopentadiene, etc., an alkylphenol resin represented by a condensate of p-tert-butylphenol and acetylene, o-xylene, p-xylene or m-xylene is reacted with formalin. Also included are xylene-based resins such as Among these, hydrogenated compounds of C9 aromatic petroleum resins and hydrogenated compounds of C5/C9 aromatic petroleum resins are preferred, and hydrogenated compounds of C9 aromatic petroleum resins are particularly preferred.

Among the hydrogenated resins (B), hydrogenated resins obtained from aromatic hydrocarbons are preferred.
The hydrogenated resin (B) preferably satisfies requirements (b1) and (b2) below, and more preferably satisfies requirements (b3) and (b4) below.

・Requirement (b1)
The softening point of the hydrogenated resin (B) is preferably 80°C or higher, more preferably 100°C or higher, and still more preferably 100 to 250°C. When the softening point is within the above range, the obtained 4-methyl-1-pentene polymer composition (X) has excellent heat resistance, which is preferable.
The softening point is measured by the ring and ball method according to JIS K-2207. That is, a specified ring was filled with a sample, supported horizontally in a water bath or a glycerin bath, a specified sphere was placed in the center of the sample, the bath temperature was increased at a rate of 5°C/min, and the sample wrapped around the sphere was , The softening point is the temperature when the bottom plate of the ring base is touched.

・Requirement (b2)
The hydrogenated resin (B) preferably has a number average molecular weight (Mn) of 300 to 5,000, more preferably 400 to 3,000, and even more preferably 500 to 2,000 as measured by GPC.

・Requirement (b3)
The hydrogenated resin (B) preferably has a hydrogenation rate of 80% or more, more preferably 80 to 100%. When the hydrogenation rate of the hydrogenated resin (B) is within the above range, the 4-methyl-1-pentene polymer composition (X) has excellent transparency. The hydrogenation rate can be measured by ¹ H-NMR.

・Requirement (b4)
The main monomer constituting the hydrogenated resin (B) is preferably at least one selected from C9 aromatic hydrocarbons, dicyclopentadiene and α-methylstyrene, more preferably α-methylstyrene.
The content of the main monomer constituting the hydrogenated resin (B) is preferably 50 to 100 mol%, more preferably 75 to 100 mol%, relative to the total amount of the hydrogenated resin (B). .

The hydrogenated resin (B) may contain a monomer other than the main monomer. Other monomers include the hydrogenated petroleum resin and the monomer constituting the hydrogenated resin obtained from the aromatic hydrocarbon. Monomers similar to those exemplified can be mentioned.
The hydrogenated resin (B) may be used alone or in combination of two or more.

The hydrogenated resin (B) may be appropriately produced by a conventional method, or a commercially available product may be used. Commercially available products include, for example, α-methylstyrene hydrogenated resin, trade name "Regalrez" manufactured by Eastman Chemical Co., Ltd., and terpene-based hydrogenated resin, "YS Resin" manufactured by Yasuhara Chemical Co., Ltd. "Clearon" and the like, and the C9 aromatic hydrocarbon-based hydrogenated resins include the product name "FTR" manufactured by Mitsui Chemicals, Inc., the product name "Arcon" manufactured by Arakawa Chemical Industries, Ltd., and the product manufactured by Idemitsu Kosan Co., Ltd. , trade name "Imarve" manufactured by Exxon Mobil Corporation, trade name "Opera" and "Escoretz" manufactured by Exxon Mobil Co., Ltd., trade name "Plastolyn" manufactured by Eastman Chemical Co., Ltd., and the like. Eastman Chemical Co., Ltd. trade name "Eastotac" and the like.

<4-methyl-1-pentene polymer composition (X)>
In the 4-methyl-1-pentene polymer composition (X) of the present invention, the hydrogenated resin (B) is added to 100 parts by mass of the 4-methyl-1-pentene polymer (A), The composition contains 1 to 90 parts by mass, preferably 2 to 70 parts by mass, more preferably 5 to 50 parts by mass, and even more preferably 10 to 30 parts by mass. The 4-methyl-1-pentene-based polymer composition (X) of the present invention contains the hydrogenated resin (B) in the 4-methyl-1-pentene-based polymer (A) in the above range, so that heat resistance , excellent in transparency and stretchability.

The 4-methyl-1-pentene-based polymer composition (X) of the present invention includes (A) the 4-methyl-1-pentene-based polymer, and the hydrogenated resin (B), in addition to other components Alternatively, it may be a composition containing other polymers and various additives within a range that does not impair the object of the present invention.
Other polymers include, for example, thermoplastic resins and rubbers, especially olefin polymers, styrene polymers, thermoplastic polyamide resins, thermoplastic polyester resins, thermoplastic vinyl aromatic resins, thermoplastic polyurethanes, and rubbers. etc. These polymers may be used singly or in combination of two or more.

Examples of olefin polymers include low-density polyethylene, medium-density polyethylene, high-density polyethylene, high-pressure low-density polyethylene, polypropylene, poly-1-butene, poly-3-methyl-1-butene, and ethylene/α-olefin copolymers. Copolymers, propylene/α-olefin copolymers, 1-butene/α-olefin copolymers, cyclic olefin copolymers, chlorinated polyolefins, olefinic thermoplastic elastomers, and the like.

Examples of the styrenic polymer include polystyrene, ABS resin, AS resin, styrene/butadiene/styrene block polymer, styrene/ethylene/butene/styrene block polymer, styrene/isobutylene/styrene block polymer, and the above hydrogenated products. be done.

Various additives used as other components include various weather stabilizers, heat stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, nucleating agents, lubricants, Pigments, dyes, anti-aging agents, hydrochloric acid absorbents, inorganic or organic fillers, organic or inorganic foaming agents, cross-linking agents, co-cross-linking agents, cross-linking aids, adhesives, softeners, flame retardants, etc. .

The 4-methyl-1-pentene polymer composition (X) of the present invention preferably satisfies either of the following requirements (X1) and requirements (X2), more preferably the following requirements (X1) and requirements (X2 ).

・Requirement (X1)
The 4-methyl-1-pentene copolymer composition (X) conforms to JIS K7196, using a test piece with a thickness of 1 mm, at a heating rate of 5 ° C./min, and with a 1 mmφ flat indenter of 2 kg / cm. A pressure of ² is applied, and the needle penetration temperature (TMA, °C) obtained from the TMA curve is preferably 170 to 260°C, more preferably 180 to 230°C. When the needle penetration temperature (TMA, °C) is within the above range, the 4-methyl-1-pentene polymer composition (X) and the molded article obtained therefrom and the stretched molded article are excellent in heat resistance, which is preferable.

・Requirements (X2)
The 4-methyl-1-pentene copolymer composition (X) generally has an internal haze value of 0.1 to 80, preferably 0.1 to 70, more preferably 0.1 to 65 range. It is preferable that the haze value is in the above range because the obtained molded article has excellent transparency.

- Method for producing 4-methyl-1-pentene-based polymer composition (X) The 4-methyl-1-pentene-based polymer composition (X) of the present invention is prepared by combining each component described above by various known methods. It can be manufactured by mixing. For example, a method of mechanically mixing the (A) 4-methyl-1-pentene polymer and the hydrogenated resin (B) in a predetermined range by various known mixing methods, or after mixing, extruder It can be produced by a method of melt-kneading using

Here, (A) the 4-methyl-1-pentene-based polymer is the hydrogenated resin (B) at any time during the production of the 4-methyl-1-pentene-based polymer composition (X) of the present invention. may be mixed into For example, after obtaining the hydrogenated resin (B), the 4-methyl-1-pentene polymer (A) and the hydrogenated resin (B) may be mixed.

Molded Articles and Uses Thereof The 4-methyl-1-pentene polymer composition (X) of the present invention can be molded by various known molding methods such as extrusion molding, press molding, injection molding, calender molding and blow molding. A molded body containing the 4-methyl-1-pentene copolymer composition (X) can be obtained by the molding method of , and the primary molded body obtained by the molding method is continuously or separately processed. It can be subjected to a molding method involving stretching, such as uniaxial stretching, biaxial stretching, multiaxial stretching, blow molding, and vacuum molding, to obtain a molded body that is a stretched molded body (secondary molded body). Biaxial stretching may be simultaneous stretching or sequential stretching. The 4-methyl-1-pentene polymer composition (X) of the present invention can also be stretched at the same time as molding, for example, it can be stretched at the same time as molding by inflation molding or blow molding.

The 4-methyl-1-pentene-based polymer composition (X) of the present invention has excellent stretchability even when the 4-methyl-1-pentene-based polymer is used as a main component. It can be preferably used for the production of bodies and can produce homogeneously stretched molded bodies. Further, the molded body can be subjected to secondary processing such as thermoforming, or laminated with other materials to form a molded body.

The shape of the molded body is not particularly limited, and can be in various known shapes such as film or sheet, hollow, tube, and container. It can be preferably used for parts, food containers, electric parts and the like.

Tube-shaped moldings include medical tubes, cooling water pipes, hot water pipes, cosmetic tubes, wire coating materials, millimeter wave signal cable coatings, high frequency signal cable coatings, eco-friendly wire coatings, chemical liquid tubes, cosmetic tubes, and food products. It can be preferably used in industrial materials, industrial members, building materials, medical parts, food containers, electric parts, such as tubes, vehicle-mounted cable covering materials, signal cable covering materials, and the like.

In addition to the properties of 4-methyl-1-pentene copolymer such as releasability and transparency, the film-like molded product has excellent gas barrier properties, flexibility, uniform stretchability, etc. while maintaining transparency. Due to its characteristics, it is widely used in packaging films and sheets, automotive parts films and sheets, industrial films and sheets, agricultural and civil engineering films and sheets, medical and cell culture films and sheets, electrical and electronic It is suitably used for films and sheets for equipment members, films and sheets for household goods, and the like.

Specifically, for example, it is suitably used for the following applications.
Packaging films; for example, food packaging films, stretch films, wrap films, breathable films, shrink films,
Release films; for example, release films for flexible printed circuit boards, release films for ACM substrates, release films for rigid flexible substrates, release films for advanced composite materials, release films for curing carbon fiber composite materials, glass fiber composites release film for curing materials, release film for curing aramid fiber composite material, release film for curing nanocomposite material, release film for curing filler filler material, release film for semiconductor sealing, release film for polarizing plate, Release films for diffusion sheets, release films for prism sheets, release films for reflection sheets, cushion films for release films, release films for fuel cells, release films for various rubber sheets, release films for urethane curing, Release films such as release films for epoxy curing,
Separators; for example, battery separators, lithium ion battery separators, fuel cell electrolyte membranes, adhesive/adhesive material separators,
Stretched films; for example, insulating films, films for film capacitors, capacitor films, capacitor films for fuel cells,
Semiconductor process films; for example, dicing tapes, back grinding tapes, die bonding films, films for polarizing plates,
Surface protective films; for example, protective films for polarizing plates, protective films for liquid crystal panels, protective films for optical parts, protective films for lenses, protective films for electric parts and electrical appliances, protective films for mobile phones, protective films for personal computers, masking Film Electronic member film; e.g. diffusion film, reflective film, radiation resistant film,
Construction material film; for example, construction material window film, laminated glass film, bulletproof material, bulletproof glass film, heat shield sheet, heat shield film.

These films or sheets include a film or sheet obtained by molding the 4-methyl-1-pentene polymer composition (X) by an extrusion method or the like, and a uniaxially stretched film or sheet obtained by a known method. A stretched film or sheet obtained by stretching by a method such as biaxial stretching or multiaxial stretching is preferable, and a stretched film or stretched sheet is particularly preferable.

As the hollow molded article and blow molded article, a molded article having the 4-methyl-1-pentene polymer composition (X) as a single layer, or the 4-methyl-1-pentene polymer composition ( Any molded article having a multilayer structure containing at least one layer of X) may be used.

In the present invention, the blow-molded article can be produced by a generally known blow-molding method. As the molding method, for example, a parison (preform) is molded from the melted 4-methyl-1-pentene polymer composition (X), the parison is sandwiched between molds, and then the inside of the parison is filled. There are a direct blow molding method in which a container is molded by blowing pressurized gas, and an injection blow molding method in which a preform is once molded by injection molding or extrusion molding and then the preform is blow molded. In addition, the injection blow molding method includes the hot parison method, which is a one-stage injection molding machine and blow molding machine, and the cold parison method, in which the injection molded preform is completely cooled and then reheated to perform blow molding. etc.

Specifically, the 4-methyl-1-pentene polymer composition (X) is melted and the resin is injection-molded into a mold to form a preform. in a molten or softened state, or in a cooled and solidified state, is reheated to a predetermined temperature using an infrared heater or the like, and after heating, a gas is injected into a specific mold and biaxially stretched to obtain the desired shape. It can be suitably manufactured by molding into. Molding conditions are not particularly limited. .0 times is usually done.

In the present invention, the blow molded article containing the 4-methyl-1-pentene polymer composition (X) has at least one layer containing the 4-methyl-1-pentene polymer composition (X). It's fine if you have it.

Applications of the hollow molded article or blow molded article include hollow containers, bottles, cups and the like. Containers, toner containers, powder containers, gasoline tank containers, kerosene containers, flasks and other laboratory equipment, etc. Bottles such as cosmetic bottles, hair styling products, drinking water bottles, carbonated drink bottles, alcohol bottles, detergent bottles , softener bottle, bleach bottle, shampoo bottle, conditioner bottle, drug bottle, adhesive bottle, pesticide bottle, medical bottle, infusion bottle, baby bottle, medical bag, infusion bag, blood storage bag The cups include food cups, packaging cups, medical product cups, and the like.

In the present invention, since the 4-methyl-1-pentene polymer composition (X) has good stretching properties, particularly preferred molded articles are stretch-molded such as stretched films, stretched sheets, and blow-molded articles. bodies, and their precursors such as films, sheets and hollow bodies. Examples of applications of such molded bodies include pharmaceutical containers, food containers, beverage containers, food containers, seasoning containers, industrial materials, industrial members, building materials, medical parts, electrical parts, and the like.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.
In the following examples, etc., each physical property was measured or evaluated as follows.

[Constituent unit content in polymer]
The content of structural units in the polymer of the 4-methyl-1-pentene-based polymer, that is, the 4-methyl-1-pentene content and the α-olefin content, was measured by ¹³ C-NMR using the following equipment and conditions. gone. In addition, in this measurement result, the content of 4-methyl-1-pentene is not included in the α-olefin content.

Using an ECP500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd., a mixed solvent of ortho-dichlorobenzene/heavy benzene (80/20% by volume) was used as the solvent, the sample concentration was 55 mg/0.6 mL, the measurement temperature was 120°C, and the number of observation nuclei was ¹³ . C (125 MHz), sequence is single pulse proton decoupling, pulse width is 4.7 μs (45° pulse), repetition time is 5.5 seconds, integration count is 10,000 or more, chemical shift standard is 27.50 ppm measured as a value. The ¹³ C-NMR spectrum obtained was used to quantify the composition of 4-methyl-1-pentene and α-olefin.

[Intrinsic viscosity [η]]
It is a value measured at 135° C. using decalin solvent. That is, about 20 mg of polymerized powder, pellets or resin mass was dissolved in 15 ml of decalin, and the specific viscosity ηsp was measured in an oil bath at 135°C. 5 ml of the decalin solvent was added to the decalin solution to dilute it, and then the specific viscosity ηsp was measured in the same manner. This dilution operation was repeated twice, and the value of ηsp/C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity (see the following formula).
[η]=lim(ηsp/C) (C→0)

[Melting point (Tm), crystallization temperature (Tc)]
Using a DSC measurement device (DSC7000X) manufactured by Seiko Instruments Inc., about 5 mg of a sample is packed in an aluminum pan for measurement, heated to 300 ° C. at 100 ° C./min, held at 300 ° C. for 5 minutes, and then heated at 10 ° C./ The crystallization temperature (Tc) was calculated from the apex of the exothermic peak of crystallization when the temperature was lowered to −60° C. per minute, and the melting point (Tm) was calculated from the apex of the endothermic peak during crystal melting.

[density]
Density was measured according to JIS K7112 (density gradient tube method).

[Melt flow rate (MFR)]
The MFR of the 4-methyl-1-pentene polymer was measured under conditions of 260° C. and a load of 5 kg according to ASTM D1238.

[Number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw/Mn)]
The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw/Mn) were measured as follows using a gel permeation chromatograph, Alliance GPC-2000, manufactured by Waters. The separation columns were two TSKgel GNH6-HT and two TSKgel GNH6-HTL, each with a diameter of 7.5 mm and a length of 300 mm. - Using dichlorobenzene (Wako Pure Chemical Industries) and BHT (Takeda Pharmaceutical) 0.025% by weight as antioxidant, moving at 1.0 ml/min, sample concentration was 15 mg/10 mL, sample injection volume was 500 micro liters and a differential refractometer was used as a detector.

<raw materials>
[Production Example 1] (Production of 4-methyl-1-pentene polymer (A-1))
synthesis
Physical properties shown in Table 1 by changing the proportions of 4-methyl-1-pentene, 1-hexadecene, 1-octadecene, and hydrogen according to the methods of Comparative Example 7 and Comparative Example 9 of WO 2006/054613 pamphlet. A 4-methyl-1-pentene polymer (A-1) having Pellets (A-1) prepared as follows were used for the measurement of physical properties.

Pelletization For 100 parts by mass of the 4-methyl-1-pentene polymer (A-1) obtained above, tri(2,4-di-t-butylphenyl) phosphate is added as a secondary antioxidant. 0.1 part by mass, 0.1 part by mass of n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl) propionate as a heat stabilizer, and calcium stearate as a hydrochloric acid absorbent. 0.1 part by mass was blended. After that, using a twin-screw extruder BT-30 (screw system 30 mmφ, L/D = 46) manufactured by Plastic Engineering Laboratory Co., Ltd., under the conditions of a set temperature of 270 ° C. and a resin extrusion rate of 60 g / min and 200 rpm. Granulation was performed to obtain pellets (A-1).

Hydrogenated resin (B-1): Regalrez1126 manufactured by Eastman Chemical Co. (main monomer: α-methylstyrene, degree of hydrogenation: 100%, number average molecular weight (Mn): 700, softening temperature: 125°C)

[Example 1, Example 2, Comparative Example 1]
Manufacture and characterization of pressed sheets
The pellets (A-1) obtained in Production Example 1 above and the above hydrogenated resin (B-1) were blended in the amounts shown in Table 2. Next, using Labo Plastomill (twin-screw batch type melt-kneading device) manufactured by Toyo Seiki Co., Ltd., at a set temperature of 270°C, 48 g of resin charge (apparatus batch volume = 60 cm ³ ) was melt-kneaded at 50 rpm for 5 minutes, A press sheet with a thickness of 1 mm was obtained using a cooling press set at 20°C.

[Needle entry temperature (TMA)]
The needle entry temperature (TMA, ° C.) was measured using a TMA measuring device (Q400 TMA) manufactured by TA Instruments Co., Ltd., using the 1 mm thick press sheet obtained above as a test piece, in accordance with JIS K7196, at a heating rate of 5 ° C. A pressure of 2 kg/cm ² was applied to a plane indenter with a diameter of 1 mm at a pressure of 2 kg/min, and a TMA curve was obtained. Table 2 shows the results.

Production of Raw Stretched Film and Evaluation of Stretchability The pellets (A-1) obtained in Production Example 1 above and the above hydrogenated resin (B-1) were blended in the amounts shown in Table 2. Next, a hydraulic heat press machine manufactured by Shindo Metal Industry Co., Ltd. (NS-50) set at 270 to 280 ° C. was pressurized at a gauge pressure of 10 MPa for 1 to 3 minutes, and another hydraulic heat press machine manufactured by Shindo Metal Industry Co., Ltd. was set at 20 ° C. was compressed at a gauge pressure of 10 MPa and cooled for about 5 minutes to obtain a raw film having a length of 100 mm, a width of 100 mm and a thickness of 200 μm. A brass plate with a thickness of 5 mm was used as the hot plate.

[Film stretchability evaluation]
After performing grid-like marking with a marker on the 200 μm-thick film raw fabric obtained above (see FIG. 1), using a batch-type biaxial stretching machine manufactured by Bruckner-Maschinanbau, the film was stretched at 160 or 190 ° C. After preheating for 1 minute, the film was simultaneously biaxially stretched at a stretching rate of 104%/sec to obtain a biaxially stretched film. The stretching ratio was 3 times in the machine direction (MD) and 4 times in the vertical direction (Transverse Direction: TD) to obtain a stretched film. The states (photographs) of the obtained stretched films are shown in FIGS. 2 to 4, respectively. From the state of the obtained stretched film, stretchability was evaluated according to the following criteria. Table 2 shows the results.
AA: Uniformly stretchable BB: Stretchable (clearly uneven)
CC: fracture

From the evaluation results shown in Table 2, it can be seen that Examples 1 and 2 are superior to Comparative Example 1 in uniform stretchability.

INDUSTRIAL APPLICABILITY The 4-methyl-1-pentene polymer according to the present invention and the molded article containing the same are excellent in transparency and heat resistance, and also excellent in uniform stretchability. In addition, the stretched molded article according to the present invention is excellent in transparency and heat resistance, is stretched uniformly, and has less distortion and unevenness in strength. Therefore, it can be preferably used for various applications such as industrial materials, industrial members, building materials, medical parts, food containers, and electric parts.

Claims (7)

(A) 100 parts by mass of a 4-methyl-1-pentene polymer that satisfies the following requirements (a1) to (a3);
(B) a 4-methyl-1-pentene polymer composition (X) containing 1 to 90 parts by mass of a hydrogenated petroleum resin or a hydrogenated resin obtained from an aromatic hydrocarbon;
(a1) 90 to 100 mol % of structural units derived from 4-methyl-1-pentene, and 0 to 10 mol % of structural units derived from α-olefin having 2 to 20 carbon atoms.
(a2) The intrinsic viscosity [η] measured in decalin at 135°C is 0.5 to 5.0 dl/g.
(a3) The melting point (Tm) measured by DSC is 180 to 260°C. The 4-methyl-1-pentene polymer composition (X) according to claim 1, wherein the component (B) satisfies the following requirements (b1) and (b2).
(b1) The softening point is 80° C. or higher.
(b2) a number average molecular weight (Mn) of 300 to 5,000; 3. The 4-methyl-1-pentene polymer composition (X) according to claim 2, wherein the component (B) further satisfies the following requirements (b3) and (b4).
(b3) The hydrogenation rate is 80% or more.
(b4) The main monomer is at least one selected from C9 aromatic hydrocarbons, dicyclopentadiene and α-methylstyrene. According to JIS K7196, using a test piece with a thickness of 1 mm, a pressure of ² kg/cm was applied to a flat indenter with a diameter of 1 mm at a heating rate of 5 ° C./min, and the needle penetration temperature (TMA, ° C. ) is 170 to 260° C., the 4-methyl-1-pentene polymer composition (X) according to any one of claims 1 to 3. A molded article comprising the 4-methyl-1-pentene polymer composition (X) according to any one of claims 1 to 4. A stretched molded article comprising the 4-methyl-1-pentene polymer composition (X) according to any one of claims 1 to 5. 7. The stretched article according to claim 6, which is a film, sheet or blow molded article.

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