JP2022151038A - Resin composition and molding - Google Patents

Abstract

To improve high temperature shape-retaining property of a molding which is formed of a resin composition containing a polyethylene-based resin, a 4-methyl-1-pentene-based polymer and a compatibilizer.SOLUTION: A resin composition contains 100 pts.mass of a polyethylene-based resin (A) (excluding polyethylene-based wax (C)), 0.1-10 pts.mass of a 4-methyl-1-pentene-based polymer (B), and 0.1-10 pts.mass of a polyethylene-based wax (C), wherein intrinsic viscosity [η] of the 4-methyl-1-pentene-based polymer (B) is 0.20-2.0 dl/g.SELECTED DRAWING: None

Description

The present invention relates to a resin composition and a molded article thereof.

Polyethylene-based resins are widely used as packaging materials.
A polyethylene-based resin film is sometimes processed into a bag shape by being welded by heat sealing. There is a need to improve production efficiency by shortening the heat-sealing time, but if the temperature during heat-sealing is raised too high, the film will be cut by fusion.

As a method for imparting heat resistance to a polyethylene-based resin film, for example, a method of providing a heat-resistant layer on the surface layer is known, but this method is undesirable from the viewpoint of cost because the number of manufacturing steps increases. In recent years, from the viewpoint of recycling, it is desired to use a mono-material or a material similar to polyethylene resin together, and it is not desirable to coat polyolefin film with a component that has significantly different properties, such as a polar material. .

On the other hand, 4-methyl-1-pentene-based polymers are polyolefins that are excellent in heat resistance, releasability, etc., and are used in various fields such as medical instruments, heat-resistant wires, heat-resistant tableware, and stripping materials.
Patent Document 1 describes a resin composition containing a polyethylene resin, a 4-methyl-1-pentene polymer, and a compatibilizer made of polyethylene wax or the like. It is described that it is excellent in moldability, heat resistance, etc. In addition, the compatibilizer enhances the dispersibility of the 4-methyl-1-pentene polymer, and the 4-methyl-1-pentene polymer is effectively molded. It is suggested to coat the surface of the product.

JP 2011-140594 A

A molded article formed from a conventional resin composition containing a polyethylene-based resin, a 4-methyl-1-pentene-based polymer, and a compatibilizer has good shape retention performance at high temperatures (hereinafter referred to as "high-temperature shape retention ”), there is room for further improvement.

An object of the present invention is to improve the shape retention performance at high temperatures of a molded article formed from a resin composition containing a polyethylene resin, a 4-methyl-1-pentene polymer, and a compatibilizer. do.

The present invention relates to, for example, the following [1] to [8].
[1]
100 parts by mass of polyethylene resin (A) (excluding polyethylene wax (C) described later), 0.1 to 10 parts by mass of 4-methyl-1-pentene polymer (B), and polyethylene Wax (C) 0.1 to 10 parts by mass,
A resin composition, wherein the 4-methyl-1-pentene polymer (B) has an intrinsic viscosity [η] of 0.20 to 2.0 dl/g.
[2]
The resin composition according to [1] above, wherein the content of the 4-methyl-1-pentene polymer (B) is more than 3 parts by mass and not more than 10 parts by mass.
[3]
The resin composition of [1] or [2], wherein the 4-methyl-1-pentene polymer (B) has a melting point (Tm) of 210° C. or higher as measured by DSC.
[4]
The resin composition according to any one of [1] to [3], wherein the content of the polyethylene wax (C) is 1 to 8 parts by mass.
[5]
The resin composition according to any one of [1] to [4] above, wherein the polyethylene wax (C) is a polyethylene wax comprising a copolymer of ethylene and an α-olefin having 3 to 10 carbon atoms.
[6]
A molded article formed from the resin composition according to any one of [1] to [5].
[7]
The molded article of the above [6], which is a film.
[8]
The molded article according to [7], wherein the film is a food packaging film.

According to the present invention, it is possible to improve the high-temperature shape retention of a molded article formed from a resin composition containing a polyethylene-based resin, a 4-methyl-1-pentene-based polymer, and a compatibilizer.

The present invention will now be described in more detail.
In the present invention, a numerical range represented by "to" means a range including the numerical values before and after "to" as lower and upper limits.

[Resin composition]
The resin composition according to the present invention comprises a polyethylene resin (A), a 4-methyl-1-pentene polymer (B), and a polyethylene wax (C), and the 4-methyl-1-pentene polymer It is characterized in that the intrinsic viscosity of coalescence (B) is within a predetermined range.

<<Polyethylene resin (A)>>
The resin composition according to the present invention contains a polyethylene resin (A). However, the polyethylene wax (C) described later is excluded from the polyethylene resin (A).

Examples of the polyethylene-based resin (A) include high-density polyethylene (HDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE). Among these, linear low-density polyethylene is preferred because of its relatively excellent miscibility with the 4-methyl-1-pentene polymer (B).

The polyethylene-based resin (A) may be an ethylene homopolymer or a copolymer of ethylene and α-olefin. The ratio of α-olefin-derived structural units to all structural units in the copolymer is preferably 30 mol % or less, preferably 20 mol % or less, and more preferably 10 mol % or less. The α-olefin preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and still more preferably 3 to 6 carbon atoms. Examples of α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene, among which propylene, 1-butene, 1-hexene and 1-octene are preferred.

The density of the polyethylene resin (A) (measured according to the density gradient tube method of JIS K7112) is preferably 900 to 980 kg/m ³ , more preferably 910 to 960 kg/m ³ , still more preferably 910 to 930 kg/m is ³ .

The melt flow rate (MFR; conforming to JIS K7210, 190° C., 2.16 kg load) of the polyethylene resin (A) is preferably 0.1 to 20 g/10 min, more preferably 1 to 10 g/10 min. .

The Vicat softening point (according to JIS K7206) of the polyethylene resin (A) is preferably 100 to 120°C, more preferably 100 to 110°C.
The melting point (according to JIS K7121) of the polyethylene resin (A) is preferably 100 to 135°C, more preferably 110 to 125°C.

<<4-methyl-1-pentene polymer (B)>>
The resin composition according to the present invention contains a 4-methyl-1-pentene polymer (B). However, the polyethylene wax (C) described later is excluded from the 4-methyl-1-pentene polymer (B).

4-methyl-1-pentene-based polymer (B) is a polymer in which at least a portion of the structural units are structural units derived from 4-methyl-1-pentene, 4-methyl-1-pentene homopolymer or a copolymer of 4-methyl-1-pentene and other monomers.

The intrinsic viscosity [η] of the 4-methyl-1-pentene polymer (B) measured in decalin solvent at 135° C. is 0.20 to 2.0 dl/g, preferably 0.20 to 1.0 dl/g. 8 dl/g, more preferably 0.20 to 1.2 dl/g. When the intrinsic viscosity [η] of the 4-methyl-1-pentene-based polymer (B1) is within this range, the dispersibility in the polyethylene-based resin (A) can be enhanced, and further, the resin composition of the present invention. A molded article formed from this material has excellent shape retention at high temperatures, and is also excellent in transparency and releasability.

The ratio of structural units derived from 4-methyl-1-pentene to the total structural units of the 4-methyl-1-pentene polymer (B) is preferably 90.0 to 100 mol%, more preferably It is 95.0 to 100 mol %, more preferably 98.0 to 100 mol %. The ratio of the total structural units derived from an olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene to the total structural units of the 4-methyl-1-pentene polymer (B) is preferably It is 0 to 10.0 mol %, more preferably 0 to 5.0 mol %, still more preferably 0 to 2.0 mol %.

Examples of olefins having 2 to 20 carbon atoms other than 4-methyl-1-pentene contained as structural units in the 4-methyl-1-pentene polymer (B) include linear or branched α- Included are olefins, cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, functionalized vinyl compounds, and the like.

Specific examples of linear or branched α-olefins contained as structural units in the 4-methyl-1-pentene polymer (B) include:
Ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. having 2 to 2 carbon atoms 20, preferably 10 to 18 linear α-olefins; and 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene. , 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, etc., preferably 5 to 20, more preferably 5 to 10 Branched α-olefins are included.

Specific examples of the cyclic olefin contained as a structural unit in the 4-methyl-1-pentene polymer (B) include cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, vinylcyclohexane, and the like. , cyclic olefins having 3 to 20 carbon atoms, preferably 5 to 15 carbon atoms.

Specific examples of the aromatic vinyl compound contained as a structural unit in the 4-methyl-1-pentene polymer (B) include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, Included are mono- or polyalkylstyrenes such as styrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene.

Examples of conjugated dienes contained as structural units in the 4-methyl-1-pentene polymer (B) include 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 4 -methyl-1,3-pentadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, and other conjugated dienes having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms.

Specific examples of the non-conjugated polyene contained as a structural unit in the 4-methyl-1-pentene polymer (B) include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4- octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1,4,8-decatriene (DMDT), dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylenenorbornene, 5-vinylnorbornene , 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropene-2-norbornene, 2,3-diisopropylidene-5-norbornene , 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, and the like, having from 5 to 20 carbon atoms, preferably from 5 to 10 carbon atoms.

Examples of functionalized vinyl compounds contained as structural units in the 4-methyl-1-pentene polymer (B) include hydroxyl group-containing olefins, halogenated olefins, unsaturated carboxylic acids, unsaturated amines, unsaturated acid anhydrides substances, unsaturated carboxylic acid halides, unsaturated epoxy compounds, specific examples thereof include those exemplified in paragraphs [0045] to [0047] of JP-A-2011-140594. .

The melting point (Tm) of the 4-methyl-1-pentene polymer (B) measured under the following conditions by a differential scanning calorimeter (DSC) is preferably 210° C. or higher, more preferably 215 to 250. °C, more preferably 220 to 245°C, particularly preferably 225 to 240°C.

(Measuring conditions for melting point)
About 5 mg of the sample is packed in an aluminum pan, heated to 280 ° C. at a heating rate of 10 ° C./min, held at 280 ° C. for 5 minutes, then cooled to 20 ° C. at a cooling rate of 10 ° C./min. After holding for 5 minutes, the temperature at which the melting peak is obtained when the temperature is again increased to 280°C at a heating rate of 10°C/min is defined as the melting point. When multiple peaks are detected, the highest temperature among the temperatures giving melting peaks is taken as the melting point.

When the melting point (Tm) is within this range, the molding processability of the resin composition of the present invention and the blocking resistance during storage of molded products (such as film molded products) of the resin composition of the present invention are well balanced.

The density of the 4-methyl-1-pentene polymer (B) (measured according to the density gradient tube method of JIS K7112) is usually in the range of 820-840 kg/m ³ .

The content of the 4-methyl-1-pentene polymer (B) in the resin composition of the present invention is 0.1 to 10 parts by mass, preferably 3 parts per 100 parts by mass of the polyethylene resin (A). It is more than 10 parts by mass, more preferably 5 to 10 parts by mass, still more preferably 5.2 to 8.0 parts by mass.

4-methyl-1-pentene polymer (B) is a conventionally known method, for example, JP 2011-140594 (especially paragraphs [0083] - [0109], Examples) to be produced by the method described. can be done.

<<Polyethylene wax (C)>>
The resin composition according to the present invention contains a polyethylene wax (C) (hereinafter also simply referred to as "wax (C)").

When the 4-methyl-1-pentene polymer (B) is mixed with the polyethylene resin (A), the 4-methyl-1-pentene polymer (B) may not be compatible with the polyethylene resin (A). be.

The polyethylene wax (C) functions as a compatibilizer for improving compatibility between the polyethylene resin (A) and the 4-methyl-1-pentene polymer (B).
The content of the polyethylene wax (C) in the resin composition of the present invention is 0.1 to 10 parts by mass, preferably 1 to 8 parts by mass, based on 100 parts by mass of the polyethylene resin (A). More preferably, it is 2.0 to 5 parts by mass.

The density of the polyethylene wax (C) is preferably between the density of the polyethylene resin (A) and the density of the 4-methyl-1-pentene polymer (B). Substances with similar densities are considered to tend to mix with each other more easily, and are considered to be more effective as a compatibilizer.

Furthermore, the difference between the density of polyethylene resin (A) and the density of polyethylene wax (C) is preferably less than 50 kg/m ³ , more preferably less than 20 kg/m ³ . When the difference in density is within the above range, the effect as a compatibilizing agent is further enhanced, and both the releasability and transparency of the resin composition can be achieved.

The polyethylene wax (C) may be obtained by direct polymerization of ethylene alone or by direct polymerization of ethylene and α-olefin, or may be obtained by thermal decomposition of high molecular weight polyethylene. It may be obtained by direct polymerization of ethylene alone or by direct polymerization of ethylene and α-olefin. The polyethylene-based wax may also be purified by a method such as solvent fractionation for fractionation based on the difference in solubility in a solvent, or molecular distillation for fractionation based on the difference in boiling point. Examples of preferred polyethylene-based waxes are described, for example, in JP-A-2009-144146.

The polyethylene wax (C) comprises, for example, a homopolymer of ethylene or a copolymer of ethylene and an α-olefin, preferably a copolymer of ethylene and an α-olefin having 3 to 10 carbon atoms. Specific examples of α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene, preferably propylene, 1-butene and 1-hexene. , 4-methyl-1-pentene.

The density of the polyethylene wax (C) (measured according to the density gradient tube method of JIS K7112) is preferably 890-980 kg/m ³ , more preferably 900-980 kg/m ³ . When the density of the polyethylene wax (C) is within the above range, the dispersibility of the polyethylene wax (C) in the polyethylene resin (A) is improved.

The intrinsic viscosity [η] of the polyethylene wax (C) measured at 135° C. in a decalin solvent is preferably 0.05 to 0.60 dl/g, more preferably 0.06 to 0.40 dl/g. Yes, more preferably 0.10 to 0.20 dl/g.

The polyethylene-based wax (C) having an intrinsic viscosity [η] within the above range can be appropriately dispersed in the polyethylene-based resin (A) when molding the resin composition of the present invention. Extrusion load can be reduced. As a result, the productivity of molded articles can be improved.

The melt viscosity of the polyethylene wax (C) at 140° C. is preferably 10 to 10000 mPa·s, more preferably 200 to 9000 mPa·s.
The melting point of the polyethylene-based wax (C), measured by the method employed in Examples described later, is preferably 70 to 130°C, more preferably 90 to 130°C.

《Optional component》
The resin composition of the present invention can be any resin other than the polyethylene resin (A), the 4-methyl-1-pentene polymer (B) and the wax (C) as long as the objects and effects of the present invention are not impaired. may contain ingredients. Examples of optional ingredients include flame retardants such as brominated bisphenols, brominated epoxy resins, brominated polystyrene, brominated polycarbonate, triphenyl phosphate, phosphonic acid amides and red phosphorus; flame retardants such as antimony trioxide and sodium antimonate. Auxiliaries; heat stabilizers such as phosphates and phosphites; antioxidants such as hindered phenols; Additives such as antistatic agents, crystal nucleating agents, plasticizers, foaming agents, anti-slip agents, anti-blocking agents, anti-fogging agents, dyes, anti-aging agents, hydrochloric acid absorbers, and copper damage inhibitors are included.

(Method for producing resin composition)
The resin composition of the present invention, for example, polyethylene resin (A), 4-methyl-1-pentene polymer (B), and wax (C), and optional components are mixed simultaneously or in any order. It can be manufactured by Mixing can be carried out using a tumbler, V-blender, Nauta mixer, Banbury mixer, kneading rolls, single-screw or twin-screw extruder, and the like.

Each component may be mixed in one step. On the other hand, first, a resin composition (also referred to as a masterbatch) having a high ratio of 4-methyl-1-pentene polymer (B) and wax (C) to polyethylene resin (A) is prepared, and then obtained. The resin composition of the present invention may be obtained by mixing the obtained masterbatch with an additional polyethylene-based resin (A).

[Use]
The resin composition of the present invention can be molded into various molded articles depending on the purpose.
The resin composition of the present invention is formed into, for example, sheets, films, pipes, tubes, bottles, fibers, or tapes, preferably sheets, films, pipes, or tubes, and particularly preferably sheets or films (hereinafter referred to as , sheets and films are collectively referred to as “films” without distinction.).

The film according to the present invention is characterized by being formed from the resin composition according to the present invention described above. 1 to 300 μm, more preferably 10 to 100 μm.

A molded article formed from the resin composition of the present invention is excellent in shape retention at high temperature, and is also excellent in transparency and releasability.
Molded articles of the resin composition of the present invention can be used as substrates in various fields such as semiconductor processes, medical instruments, heat-resistant electric wires, heat-resistant tableware, and peeling materials. Examples of more specific uses of molded articles of the resin composition of the present invention include, but are not limited to, cap liners, gaskets, glass interlayers, doors, door frames, window frames, rims, baseboards, and opening frames. Floor materials, ceiling materials, wallpaper, etc., stationery, office supplies, non-slip sheets, building surface materials, pipes, electric wires, sheaths, wire harnesses, protective film adhesive layers, hot-melt adhesive materials, sanitary supplies, medical bags and tubes , non-woven fabrics, elastic materials, fibers, shoe soles, shoe midsoles, inner soles, soles, sandals, packaging films, food packaging films (outer layer, inner layer, sealant, single layer), stretch films, wrap films, tableware, Includes retort containers, stretched films, and breathable films.

Among these, the film of the present invention is preferably used as a food packaging film.
It is also preferable that the film molded article of the resin composition of the present invention is used for applications that make use of these releasability. Specifically, the molded film of the resin composition of the present invention can be used as an adhesive film by forming an adhesive layer. The adhesive layer is an acrylic adhesive layer, an ester adhesive layer, an olefin adhesive layer, a urethane adhesive layer, or the like, and a material having adhesive strength suitable for the substrate to be adhered may be used.

Conventionally known molding methods such as extrusion molding, injection molding, solution casting, and inflation molding can be used for molding the resin composition of the present invention.
Further, the molding process of the resin composition of the present invention is obtained by obtaining a primary molded body by primary molding such as extrusion molding, injection molding, solution casting, etc., and further molding the primary molded body by blow molding, stretching, etc. You may For example, when obtaining a film-like molded body, the primary molded body obtained by molding the resin composition of the present invention into a sheet by a T-die extrusion method or the like is uniaxially or biaxially stretched to obtain it. good too.

The film of the present invention may be used as a surface protective film having a surface layer and an adhesive layer comprising the film of the present invention. This surface protective film may have a substrate layer between the surface layer and the adhesive layer, and may further have a layer different from these three layers.

The adhesive layer can be composed of conventionally known adhesives such as olefin elastomers, styrene elastomers, acrylic adhesives, etc. described in paragraphs [0163] to [0170] of JP-A-2011-140594. can.

EXAMPLES The present invention will be described in more detail based on examples below, but the present invention is not limited to these examples.
<Measurement or evaluation method>
The physical properties of the raw materials and films were measured and evaluated as follows.

[Constituent unit content in 4-methyl-1-pentene polymer]
The amount of structural units derived from 4-methyl-1-pentene (hereinafter referred to as "4-methyl-1-pentene content") and the amount of structural units derived from α-olefins other than 4-methyl-1-pentene The amount (hereinafter referred to as "α-olefin content") was calculated from the ¹³ C-NMR spectrum using the following equipment and conditions.
Measuring device: ECP500 type nuclear magnetic resonance device manufactured by JEOL Ltd. Solvent: o-dichlorobenzene/heavy benzene (80/20% by volume) mixed solvent Sample concentration: 55 mg/0.6 mL
Measurement temperature: 120°C
Observation nuclei: ¹³ C (125 MHz)
Sequence: Single pulse proton decoupling Pulse width: 4.7 μs (45° pulse)
Repeat time: 5.5 seconds Accumulation times: 10,000 times or more Standard value for chemical shift: 27.50 ppm
The ¹³ C-NMR spectrum obtained was used to quantify the composition of 4-methyl-1-pentene and α-olefin.

[Intrinsic viscosity [η]]
The intrinsic viscosity [η] was measured at 135°C using decalin solvent. Specifically, 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 decalin solvent was added to this decalin solution to dilute it, and then the specific viscosity ηsp was measured in the same manner. This dilution operation was further repeated twice, and the value of ηsp/C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity (see the formula below).
[η]=lim(ηsp/C) (C→0)

[Melting point (Tm)]
The melting point (Tm) was determined by exothermic and endothermic curves using a DSC measuring device (DSC220C) manufactured by Seiko Instruments Inc., and the temperature at the maximum melting peak position during heating was defined as the melting point (Tm). The measurement was carried out according to ASTM D3418 as follows.

・For measurement of 4-methyl-1-pentene polymers (B-1) to (B-5) About 5 mg of the sample was placed in an aluminum pan for measurement and heated from 20°C to 280°C at a heating rate of 10°C/min. and held at 280°C for 5 minutes, then lowered to 20°C at a cooling rate of 10°C/min, held at 20°C for 5 minutes, and then heated again from 20°C to 280°C at a heating rate of 10°C/min. °C. The melting peak that appeared during the second heating was taken as the melting point (Tm). When multiple peaks were detected, the maximum temperature was taken as the melting point (Tm).

・In the case of measurement of wax (C-1) About 5 mg of the sample is placed in an aluminum pan for measurement, heated from -10°C to 200°C at a heating rate of 10°C/min, held at 200°C for 5 minutes, The temperature was lowered to -10°C at a cooling rate of 10°C/min, held at -10°C for 5 minutes, and then heated again from -10°C to 200°C at a heating rate of 10°C/min. The melting peak that appeared during the second heating was taken as the melting point (Tm). When multiple peaks were detected, the maximum temperature was taken as the melting point (Tm).

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

[All Haze]
The total haze of the film was measured according to JIS K7105.
From the measured values, the haze was evaluated according to the following criteria.
○: 45% or less ×: greater than 45%

[Things in the film]
The amount of gelled material present in the film was assessed visually. The meanings of the symbols in Table 2 are as follows.
○: no gelled product △: gelled product slightly present ×: gelled product present in large amount

[Thermo-mechanical analysis (TMA)]
Using a TMA7100C manufactured by Hitachi High-Tech Co., Ltd., the distance over which the film stretched was measured while the temperature was raised from 23°C to 110°C under the following conditions.
Test mode: Film stretch mode Test temperature range: 23°C to 200°C
Test load: 5gf (49mN)
Heating rate: 5 ° C./min Test piece shape: 5 mm width x 10 mm length between chucks
Pre-annealing treatment: None Measurement atmosphere: Nitrogen (100 ml/min)
The measured distance was evaluated for high-temperature shape retention according to the following criteria. (The larger the value, the poorer the shape retention at high temperature.)
○: The distance extended is less than 9% ×: The distance extended is 9% or more

[Water contact angle and releasability evaluation]
A DropMaster 500 image processing type solid-liquid interface analysis system was used to measure the contact angle value when a water droplet was dropped on the obtained film. Based on the measured values, the releasability was evaluated according to the following criteria. (The larger the contact angle value, the higher the releasability for highly hydrophobic and highly polar materials.)
○: 103 ° or more ×: less than 103 °

<raw materials>
Polyethylene resin:
EVOLUE (registered trademark) SP2540 (trade name, manufactured by Prime Polymer Co., Ltd., LLDPE, density: 924 kg/m ³ , melting point: 120°C, Vicat softening point: 106°C) was used as the polyethylene resin (A-1). Got ready.

4-methyl-1-pentene polymer:
A 4-methyl-1-pentene polymer was produced by the following method.
[Synthesis Example 1]
(Synthesis of transition metal compound)
(8-octamethylfluorene-12′-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a] Indene)) Zirconium dichloride was synthesized according to the method described in Preliminary Experiment 5 of WO2014/123212.

[Synthesis Example 2]
(Manufacture of olefin polymerization catalyst)
At 30° C., 30 mL of purified decane and a solid having a D50 of 28 μm and an aluminum atom content of 43% by mass were placed in a three-necked flask equipped with a 200-mL stirrer and sufficiently nitrogen-substituted under a nitrogen stream. Polymethylaluminoxane (synthesized using the method described in International Publication No. 2014/123212, hereinafter also referred to as "solid MAO") was charged 14.65 mmol in terms of aluminum atoms to form a suspension. To the suspension, the transition metal compound synthesized in Synthesis Example 1 (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5 ,6,7,7a,8-octahydrocyclopenta[a]indene)) 50.0 mg (0.0586 mmol) of zirconium dichloride was added as a 4.58 mmol/L toluene solution with stirring. Stirring was stopped after 1 hour, and the obtained mixture was washed with 100 mL of decane by a decantation method, and then decane was added to make 50 mL of slurry liquid (Zr loading rate: 98%).

[Synthesis Example 3]
(Preparation of prepolymerization catalyst component)
To the slurry prepared in Synthesis Example 2, 1.0 mL of a decane solution of triisobutylaluminum (0.5 mmol/mL in terms of aluminum atoms) was added at 25° C. under a nitrogen stream. After cooling to 15° C., 10 mL of 4-methyl-1-pentene was charged into the reactor over 60 minutes. The start of charging was defined as the start of prepolymerization. After 2.0 hours from the initiation of polymerization, the stirring was stopped, and the resulting mixture was washed with 100 mL of decane three times by decantation. A decane slurry (9.5 g/L, 0.56 mmol-Zr/L) was used as a prepolymerization catalyst component.

[Polymerization Example B1]
(Production of polymer)
At room temperature under a nitrogen stream, 425 mL of purified decane was placed in a SUS polymerization vessel equipped with a stirrer and having an internal volume of 1 L, and the temperature was raised to 40°C. After reaching 40° C., 0.8 mL (0.4 mmol in terms of aluminum atoms) of a decane solution of triisobutylaluminum (0.5 mmol/mL in terms of aluminum atoms) was charged, and then the preliminary preparation of Synthesis Example 3 prepared above was charged. A decane slurry of a polymerization catalyst component was charged in an amount of 0.00040 mmol in terms of zirconium atom. 235 NmL of hydrogen was charged, and then 196 mL of 4-methyl-1-pentene was continuously charged into the polymerization vessel at a constant rate over 2 hours. The polymerization was started at the time when the charging was started, and the temperature was kept at 45° C. for 4.5 hours. 235 NmL of hydrogen was charged 1 hour and 2 hours after the initiation of polymerization. After 4.5 hours from the start of the polymerization, the temperature was lowered to room temperature, the pressure was released, and the polymerization solution 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, and the polymer (hereinafter referred to as “4-methyl-1-pentene polymer (B-1)” or “polymer (B-1)” ). Yield was 104 g. Polymer (B-1) had a melting point (Tm) of 231° C., an intrinsic viscosity [η] of 0.28 dl/g, and a density of 832 kg/m ³ .

[Polymerization Examples B2 and B3]
Polymers (B-2) and (B-3) shown in Table 1 were obtained in the same manner as in Polymerization Example 1 except that the amount of hydrogen was adjusted.

[Polymerization Example B4]
1 μmol of isopropyl(3-t-butyl-5-methylcyclopentadienyl)(3,6-di-t-butylfluorenyl)zirconium dichloride was added to a sufficiently nitrogen-purged glass flask, and a promoter was added thereto. A catalyst solution was obtained by adding a hexane solution of modified methylaluminoxane (product name: MMAO-3A, manufactured by Tosoh Finechem) in an amount of 0.5 mmol in terms of Al atoms.

A 1-liter glass autoclave equipped with a stirrer and sufficiently purged with nitrogen was charged with 561 ml of decane, 200 ml of 4-methyl-1-pentene, and Diarene D168, a mixture of high-purity hexadecene and octadecene (product (Mitsubishi Chemical Co., Ltd.) was charged in 9 ml. Hydrogen (6 liters/hour) was passed through this and left at 30° C. for 10 minutes. After that, 0.375 mmol of triisobutylaluminum was added, followed by the catalyst solution prepared above to initiate polymerization. Hydrogen (6 liters/hour) was continuously supplied and polymerization was carried out at 30° C. under normal pressure for 1 hour, and then a small amount of methanol was added to terminate the polymerization. The polymer solution was poured into 4 liters of methanol/acetone mixed solution (volume ratio 4/1), and the polymer was collected by filtration. The recovered polymer was dried at 80° C. for 10 hours under reduced pressure to obtain 40 g of polymer (B-4). Table 1 shows the physical properties of the polymer (B-4).

[Polymerization Example B5]
In the polymerization method of Comparative Example 9 of WO 2006/054613, by changing the ratio of 4-methyl-1-pentene, other α-olefin (Diarene D168), and hydrogen, the polymer (B-5) got

wax:
[Wax (C-1)]
As the wax (C-1), Excelex 30050BT (trade name) (manufactured by Mitsui Chemicals, Inc., ethylene/1-butene copolymer, density: 905 kg/m ³ , intrinsic viscosity [η]: 0.17 dl/g , melting point: 91°C).

[Example 1]
(Manufacture of resin composition)
Per 100 parts by mass of the polyethylene resin (A-1), 5.4 parts by mass of the 4-methyl-1-pentene polymer (B-1) produced in Polymerization Example 1, and wax (C-1 ) was added in an amount of 2.7 parts by mass. The resulting compound was placed in a single-screw extruder (screw diameter: 20 mmφ, L/D = 28, manufactured by Thermo Plastics Co., Ltd.) with a coat hanger type T-type die (lip shape: 270 x 0.8 mm). Then, molding was performed under conditions of a die temperature of 270° C., a roll temperature of 80° C. and a winding speed of 2.0 m/min to obtain a film having a thickness of 50 μm. Table 2 shows the evaluation results of the film.

[Example 2]
The same operation as in Example 1 was performed except that the 4-methyl-1-pentene polymer (B-1) was changed to 5.4 parts by mass of the 4-methyl-1-pentene polymer (B-2). to obtain a film with a thickness of 50 μm. Table 2 shows the evaluation results of the film.

[Example 3]
The same operation as in Example 1 was performed except that the 4-methyl-1-pentene polymer (B-1) was changed to 5.4 parts by mass of the 4-methyl-1-pentene polymer (B-3). to obtain a film with a thickness of 50 μm. Table 2 shows the evaluation results of the film.

[Comparative Example 1]
The same operation as in Example 1 was performed except that the 4-methyl-1-pentene polymer (B-1) was changed to 5.4 parts by mass of the 4-methyl-1-pentene polymer (B-4). to obtain a film with a thickness of 50 μm. Table 2 shows the evaluation results of the film.

[Comparative Example 2]
The same operation as in Example 1 was performed except that the 4-methyl-1-pentene polymer (B-1) was changed to 5.4 parts by mass of the 4-methyl-1-pentene polymer (B-5). to obtain a film with a thickness of 50 μm. Table 2 shows the evaluation results of the film.

[Reference example 1]
A film having a thickness of 50 μm was obtained in the same manner as in Example 1, except that the formulation was changed to polyethylene resin (A-1). Table 2 shows the evaluation results of the film.

Claims (8)

100 parts by mass of polyethylene resin (A) (excluding polyethylene wax (C) described later), 0.1 to 10 parts by mass of 4-methyl-1-pentene polymer (B), and polyethylene Wax (C) 0.1 to 10 parts by mass,
A resin composition, wherein the 4-methyl-1-pentene polymer (B) has an intrinsic viscosity [η] of 0.20 to 2.0 dl/g. 2. The resin composition according to claim 1, wherein the content of said 4-methyl-1-pentene polymer (B) is more than 3 parts by mass and not more than 10 parts by mass. 3. The resin composition according to claim 1, wherein the 4-methyl-1-pentene polymer (B) has a melting point (Tm) of 210° C. or higher as measured by DSC. The resin composition according to any one of claims 1 to 3, wherein the content of the polyethylene wax (C) is 1 to 8 parts by mass. The resin composition according to any one of claims 1 to 4, wherein the polyethylene wax (C) is a polyethylene wax comprising a copolymer of ethylene and an α-olefin having 3 to 10 carbon atoms. A molded article formed from the resin composition according to any one of claims 1 to 5. The molded article according to claim 6, which is a film. The molded article according to claim 7, wherein the film is a food packaging film.