JP7029500B2 - Thermoplastic resin composition and molded article obtained from it - Google Patents

Description

The present invention relates to a thermoplastic resin composition having an excellent balance of tensile properties, heat resistance, and surface appearance, and a molded product made of the same. More specifically, the present invention relates to a resin composition comprising a specific polymer obtained from 4-methyl-1-pentene.

Thermoplastic resin compositions composed of propylene-based polymers and 4-methyl-1-pentene-based polymers are known, and supplement the heat resistance, which is a drawback of propylene-based polymers, to make up for the heat resistance of 4-methyl-1-pentene-based polymers. It has been attracting attention as a composition capable of compensating for the processability which is a drawback of the above. Patent Document 1 discloses a technique of using a blend of 4-methyl-1-pentene polymer and polypropylene in a specific ratio as a diaphragm for a speaker. However, in the diaphragm for a speaker manufactured by using a two-component composition composed of 4-methyl-1-pentene polymer and polypropylene, the compatibility between 4-methyl-1-pentene polymer and polypropylene is not sufficient. As a result, phase separation may occur and the appearance of the surface of the molded product may be deteriorated.

In Patent Documents 2 and 3, in order to improve the compatibility of both components in a blend composed of 4-methyl-1-pentene polymer and polypropylene, a 1-butene polymer as a compatibilizer is added to the surface. Methods for improving the appearance are disclosed. However, even with this method, the appearance is still insufficient depending on the application in which the molded product is used, and the appearance is maintained while taking advantage of the excellent inherent performance of the propylene-based polymer and the 4-methyl-1-pentene-based polymer. There is a demand from the industrial world for the development of an excellent composition and a molded product obtained from the composition.

Special Fair 2-34520 Gazette Japanese Unexamined Patent Publication No. 2004-238469 Japanese Unexamined Patent Publication No. 2015-120331

Even in the preliminary study by the present inventors, even if the heat resistance of the two-component composition composed of 4-methyl-1-pentene polymer and polypropylene may reach almost the required level, both components are sufficient. It has been confirmed that the surface smoothness tends to deteriorate due to incompatibility with, and it tends to be difficult to sufficiently develop mechanical strength such as elongation at break (see Examples of the present specification, which will be described later). ). In other words, a composition that utilizes both the excellent heat resistance inherent in 4-methyl-1-pentene polymer and the good processability and versatility of propylene-based polymers, and also has excellent mechanical properties and surface appearance. Was not known until now.

As a result of diligent studies to solve the above problems, the present inventors have combined a two-component composition composed of 4-methyl-1-pentene polymer and polypropylene with a skeleton derived from 4-methyl-1-pentene and propylene. We have found that the above-mentioned problems can be solved by adding a compatibilizer made of a specific copolymer containing the causative skeleton, and arrived at the present invention.

That is, the gist of the present invention is as follows.
[1] 10 to 90 parts by mass of the 4-methyl-1-pentene polymer (A) and 90 to 10 parts by mass of the propylene polymer (B) satisfying the following requirements (Aa) and (Ab) (however). , (A) and (B) are 100 parts by mass).
A 4-methyl-1-pentene copolymer containing 1 to 50 parts by mass of a 4-methyl-1-pentene copolymer (C) that simultaneously satisfies the following requirements (C-a) to (C-e). Composition.
(A-a) Constituent unit derived from 4-methyl-1-pentene [i] 100-90 mol% and
Constituent unit [ii] derived from α-olefin (excluding 4-methyl-1-pentene) having 2 to 20 carbon atoms consists of 0 to 10 mol% (however, constituent unit [i] and constituent unit [ii]. The total is 100 mol%).
(Ab) The melting point (Tm) measured by DSC is in the range of 200 to 250 ° C.
(C-a) Constituent unit [i] 92-60 mol% derived from 4-methyl-1-pentene,
Consists of 8-40 mol% derived from α-olefins (excluding 4-methyl-1-pentene) having 2 to 20 carbon atoms (however, constituent units [i] and constituent units [ii]. The total is 100 mol%).
(C-b) The ultimate viscosity [η] measured in decalin at 135 ° C. is in the range of 1.0 to 4.0 dl / g.
(C) The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), measured by gel permeation chromatography (GPC) is 1.0 to 3. It is in the range of 5.
(Cd) The density is in the range of 825 to 860 kg / m ³ .
(C-e) The melting point (Tm) measured by DSC is not observed or is in the range of less than 160 ° C.
[2] The structural unit [ii] derived from an olefin having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) in the 4-methyl-1-pentene copolymer (C) is derived from propylene. The 4-methyl-1-pentene copolymer composition according to [1], which is the structural unit [ii'] to be derived.
[3] The 4-methyl-1 according to [1] or [2], wherein the 4-methyl-1-pentene copolymer (C) satisfies both the following requirements (Cf) and (Cg). -Pentene copolymer composition.
The constituent unit [i] derived from (Cf) 4-methyl-1-pentene is 80 to 60 mol%, and the constituent unit [i] is 80 to 60 mol%.
The constituent unit [ii] derived from an α-olefin having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 20 to 40 mol% (however, the constituent unit [i] and the constituent unit [ii]. ] Is 100 mol%).
(Cg) Melting point (Tm) measured by DSC is not observed.
[4] A molded product containing the 4-methyl-1-pentene polymer composition according to any one of the above [1] to [3].
[5] The molded product according to the above [4], which is a film.
[6] The molded product according to the above [4], which is a fiber.

The 4-methyl-1-pentene copolymer composition of the present invention is a thermoplastic resin composition having an excellent balance of tensile properties, heat resistance, and surface appearance, and the molded product thereof is used for various purposes such as films and fibers. Is useful in.

6 is an SEM photograph of the filament surface obtained in Example 8. It is a TEM photograph of the filament cross section obtained in Example 8. 6 is an SEM photograph of the filament surface obtained in Comparative Example 5. It is a TEM photograph of the filament cross section obtained in Comparative Example 5.

Hereinafter, the 4-methyl-1-pentene copolymer composition of the present invention will be described in detail.
The 4-methyl-1-pentene copolymer composition of the present invention comprises 10 to 90 parts by mass of the 4-methyl-1-pentene polymer (A) and 90 to 10 parts by mass of the propylene polymer (B) satisfying specific requirements. 1 to 50 parts by mass of the 4-methyl-1-pentene-based copolymer (C) satisfying a specific requirement is contained in a portion (provided that the total of (A) and (B) is 100 parts by mass). It is a composition consisting of. Hereinafter, each component (A), (B) and (C) constituting the composition will be described.

≪4-Methyl-1-pentene polymer (A) ≫
The polymer (A) satisfies the following requirements (Aa) and (Ab).
Requirement (AA): The content of the structural unit [i] derived from 4-methyl-1-pentene in the polymer (A) is 90 mol% or more and 100 mol% or less, preferably 95 mol% or more and 100 mol%. The content of the structural unit [ii] derived from α-olefin having 2 to 20 carbon atoms other than 4-methyl-1-pentene is 0 mol% or more and 10 mol% or less, preferably 0 mol% or more. It is 5 mol% or less (however, the total content of the constituent unit [i] and the constituent unit [ii] is 100 mol%).

Since the content of the structural unit [i] in the polymer (A) is 90 mol% or more, it has an advantage of excellent heat resistance as a composition, and it has good handleability and elasticity in a molded product for film applications. It has the advantage of excellent rate.

Examples of α-olefins having 2 or more and 20 or less carbon atoms other than 4-methyl-1-pentene forming the structural unit [ii] include ethylene, propylene, 1-butene, 1-hexene, 1-heptene, and 1 -Octene, 1-decene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-eikosen and the like can be mentioned. As the α-olefin forming the structural unit [ii], an olefin having 8 or more carbon atoms and 18 or less carbon atoms (for example, 1-octene, 1) is used from the viewpoint of imparting an appropriate elastic modulus, flexibility, and flexibility to the composition. -Decenes, 1-tetradecene, 1-hexadecene, 1-heptadecene and 1-octadecene) are preferred.

The polymer (A) is a structural unit derived from 4-methyl-1-pentene [i] and a structural unit derived from an α-olefin other than 4-methyl-1-pentene, as long as the effects of the present invention are not impaired. Other structural units [iii] other than [ii] may be included. The content of the other constituent units is, for example, 0 to 10 mol% (provided that the total content of the constituent units [i], [ii] and [iii] is 100 mol%).

Specific examples of the monomer forming the other structural unit [iii] are the same as those of the specific example of the monomer forming the other structural unit that can be contained in the copolymer (C) described later.

The value of the content (mol%) of each structural unit in the polymer (A) was obtained by a measurement method using ¹³ C-NMR, similarly to the copolymer (C) described later. ..

Requirement (Ab): Melting point (Tm) measured by DSC of the polymer (A) (may be simply referred to as DSC melting point in the following description) is 200 to 250 ° C., preferably 200 ° C. to It is in the range of 245 ° C, more preferably 200 ° C to 240 ° C. Since the DSC melting point (Tm) of the polymer (A) is in the above range, the composition has an appropriate elastic modulus as compared with the case where it is higher than the above range, and has a heat resistance as compared with the case where it is lower than the above range. Good sex.

The DSC melting point (Tm) of the polymer (A) is a value measured by the following method using a differential scanning calorimeter (DSC) in accordance with JIS K7121.

Approximately 5 mg of the polymer (A) is sealed in an aluminum pan for measurement of a differential scanning calorimeter (DSC220C type) manufactured by Seiko Instruments Co., Ltd. at room temperature, and the temperature is increased from room temperature to 200 ° C. at a rate of 10 ° C./min. Heat. To completely melt the polymer (A), hold at 200 ° C. for 5 minutes and then cool to −50 ° C. at a rate of 10 ° C./min. The temperature at which the peak is observed in this cooling process is defined as the crystallization temperature (Tc). After holding at -50 ° C for 5 minutes, the polymer (A) is heated to 200 ° C for the second time at a rate of 10 ° C / min, and the temperature at which the peak is observed by this second heating is the DSC melting point (Tm) of the polymer (A). ). When a plurality of peaks are detected, the peak detected on the highest temperature side is adopted.

The polymer (A) according to the present invention satisfies either of the following requirements (Ac) or (Ad) in addition to the above requirements (Aa) and (Ab), and preferably both. Meet the requirements.

Requirement (A-c): The crystallization temperature (Tc) of the polymer (A) is in the range of 150 to 220 ° C., preferably 180 ° C. to 220 ° C., and more preferably 190 ° C. to 220 ° C. When the crystallization temperature (Tc) of the polymer (A) is in the above range, the composition has appropriate flexibility as compared with the case where it is higher than the above range, so that cracks are less likely to occur, and it is lower than the above range. Rigidity and crystallinity can be increased as compared with the above.

Requirement (Ad): The ultimate viscosity [η] of the polymer (A) measured at 135 ° C. in a decalin solvent is 1.0 to 4.0 dl / g, preferably 1.0 dl / g. It is ~ 3.5 dl / g, and more preferably 1.0 dl / g to 3.0 dl / g. When the ultimate viscosity [η] of the polymer (A) is within the above range, the number of low molecular weight substances is small, so that the composition is less sticky when it is film-molded, and the laminated film or the like is molded by the extrusion laminating method. Is possible.

The ultimate viscosity [η] of the polymer (A) is a value measured by the following method using a Ubbelohde viscometer.

After dissolving 20 mg of the polymer (A) in 25 ml of decalin, the specific viscosity ηsp is measured in an oil bath at 135 ° C. using a Ubbelohde viscometer. This decalin solution is diluted by adding 5 ml of decalin, and then the specific viscosity ηsp is measured in the same manner as above. This dilution operation is repeated twice more, and the value of ηsp / C when the concentration (C) is extrapolated to 0 is set to the ultimate viscosity [η] (unit: dl / g) (see the formula below).

[Η] = lim (ηsp / C) (C → 0)
Requirement (A-e): The density of the polymer (A) measured in accordance with JIS K7112 (density gradient tube method) is 820 to 850 kg / m ³ , preferably 825 to 845 kg / m ³ . , More preferably 830 to 840 kg / m ³ . When the density is in the above range, the mechanical strength of the composition tends to be higher than when it is smaller than the above range, and the impact strength of the composition tends to be higher than when it is larger than the above range.

The polymer (A) satisfies any of the following requirements (Af) or (Ag) in addition to the above requirements (Aa) to (Ae), and preferably satisfies both requirements.

Requirement (AF): The melt flow rate (MFR) of the polymer (A) measured at 260 ° C. and a 5.0 kg load according to ASTM D1238 is extruded with the copolymer (B) described later. It is not particularly specified as long as it is easily mixed in the machine and can be coextruded, but it is usually 0.5 g / 10 min to 200 g / 10 min, more preferably 1 g / 10 min to 150 g / 10 min, and further preferably 1 g / 10 min to 100 g. / 10 min. When the MFR is in the above range, the composition can be easily extruded to a relatively uniform film thickness.

Requirement (Ag): The molecular weight distribution (Mw / Mn) of the polymer (A) is usually 1.0 to 7.0, preferably 2.0 to 6.0. The molecular weight distribution (Mw / Mn) of the polymer (A) is a value calculated by the method described in Examples.
The polymer (A) may be either a polymer having an isotactic structure or a polymer having a syndiotactic structure, but a polymer having an isotactic structure is particularly preferable and easily available. be. Further, the polymer (A) is not particularly limited in stereoregularity as long as the composition exhibits desired performance.

The polymer (A) may be produced by polymerizing olefins, or may be produced by thermally decomposing a high molecular weight 4-methyl-1-pentene polymer. Further, the polymer (A) may be purified by a method such as solvent separation in which the polymer (A) is separated by the difference in solubility in the solvent, or molecular distillation in which the polymer (A) is separated by the difference in boiling point.

≪Propene polymer (B) ≫
The polypropylene (B) in the present invention is a known polymer mainly composed of propylene, and examples thereof include a propylene homopolymer and a propylene / α-olefin copolymer of propylene and an α-olefin other than propylene. (Random copolymer, block copolymer, propylene / ethylene copolymer, propylene / 1-butene copolymer, propylene / ethylene / 1-butene copolymer, or a mixture thereof) and the like can be mentioned. As the propylene polymer (B), an isotactic propylene polymer and a syndiotactic propylene polymer are preferably used, and the isotactic mesopendad fraction (mm mm) showing the stereoregularity of the former or the stereoregulation of the latter is used. The syndiotactic mesopendad fraction (rrrr) exhibiting the sex is preferably 90% or more, more preferably 92% or more, still more preferably 93% or more. When the stereoregularity is high, the crystallinity of the resin is improved, and high thermal stability and mechanical properties can be imparted.

When a propylene / α-olefin copolymer is used as the propylene polymer (B), the α-olefin-derived skeleton content in the polymer is preferably 5% by mass or less. Further, the propylene / α-olefin copolymer may be a random copolymer or a block copolymer, and may contain a nucleating agent (crystallization nucleating agent). The nucleating agent is not particularly limited, and various inorganic compounds, various carboxylic acids or metal salts thereof, dibenzylidene sorbitol-based compounds, aryl phosphate-based compounds, cyclic polyvalent metal aryl phosphate-based compounds and aliphatic monocarboxylic acid alkalis. Examples thereof include metal salts, mixtures with basic aluminum, lithium, hydroxy, carbonate and hydrate, and α-crystal nucleating agents such as various polymer compounds. These crystallization nucleating agents can be used alone or in combination of two or more materials.

The MFR of polypropylene (B) can be measured according to JIS K7210. Specifically, it is preferably 0.5 to 50 g / 10 minutes, more preferably 1 to 15 g / 10 minutes, and 2 to 10 g / 10 minutes under the measurement conditions of a temperature of 230 ° C. and a load of 2.16 kg. It is more preferably 10 minutes. When the MFR of the propylene-based polymer is in the above range, it is suitable for extrusion molding.

The ash content caused by the polymerization catalyst residue and the like contained in polypropylene (B) is preferably as small as possible from the viewpoint of reducing the amount of minute foreign substances (fish eyes) when the composition of the present invention is used for film applications. , Usually 50 ppm or less. More preferably, it is 40 ppm or less. By setting the content to 50 ppm or less, minute foreign substances and defects are remarkably reduced, and contamination when the molded film is used for electronic component applications can be reduced.

≪4-Methyl-1-pentene copolymer (C) ≫
The copolymer (C) simultaneously satisfies the following requirements (C-a) to (C-e).
Requirement (C-a): The copolymer (C) contains a structural unit [i] derived from 4-methyl-1-pentene in a proportion of 60 to 92 mol%, and other than 4-methyl-1-pentene. It has a structural unit [ii] derived from α-olefin having 2 or more carbon atoms and 20 or less carbon atoms in a proportion of 8 to 40 mol%. (However, the total of the content of the constituent unit [i] and the content of the constituent unit [ii] is 100 mol%.)
The content of the structural unit [i] is preferably 60 to 90 mol%, more preferably 62 to 85 mol%, and particularly preferably 65 to 85 mol%.
When the content of the structural unit [i] is 60 mol% or more, the stress relaxation property of the composition is improved.

The content of the constituent unit [ii] (when the constituent unit [ii] is two or more, the total content of the two or more) is preferably 10 to 40 mol%, more preferably 15 to 38. It is mol%, particularly preferably 15 to 35 mol%.

When the content of the structural unit [ii] in the copolymer (C) is 8 mol% or more, the compatibility between the 4-methyl-1-pentene copolymer and the polypropylene copolymer in the obtained composition and the compatibility and Excellent workability and flexibility.

When the content of the structural unit [ii] is less than 40 mol%, the compatibility between the 4-methyl-1-pentene copolymer and the polypropylene copolymer of the composition is improved.

As an α-olefin having 2 or more and 20 or less carbon atoms other than 4-methyl-1-pentene, which forms a structural unit [ii], ethylene is used from the viewpoint of mechanical properties and heat resistance of the composition and availability. , Propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-hexadecene, 1-octadecene are preferred, and α-olefins having 2 to 4 carbon atoms, that is, ethylene, propylene, 1-butene are further used. Preferably, propylene is particularly preferred. That is, it is preferable that the copolymer (C) is composed of a skeleton [i] derived from 4-methyl-1-pentene and a skeleton [ii'] derived from propylene.
Further, when the α-olefin is in the above preferable range, the impact resistance of the obtained laminate is also improved.

As the α-olefin forming the structural unit [ii], only one kind may be used, or two or more kinds may be used in combination. When used in combination, it is desirable to use at least one type of propylene.

The copolymer (C) has 2 or more and 20 or less carbon atoms other than the structural unit [i] derived from 4-methyl-1-pentene and 4-methyl-1-pentene as long as the effect of the present invention is not impaired. It may contain other structural units [iii] other than the structural unit [ii] derived from α-olefin. The content of the other constituent units [iii] is, for example, 0 to 10 mol% (however, the total content of the constituent units [i], [ii] and [iii] is 100 mol%).

Examples of the monomer forming the other structural unit include cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, functional vinyl compounds, hydroxyl group-containing olefins, halogenated olefins and the like.

The content (mol%) of each structural unit in the copolymer (C) was obtained by the measurement method by ¹³ C-NMR under the following conditions.

~ Conditions ~
Measuring device: Nuclear magnetic resonance device (ECP500 type, manufactured by JEOL Ltd.)
Observation nucleus: 13C (125MHz)
Sequence: Single pulse Proton decoupling Pulse width: 4.7 μsec (45 ° pulse)
Repeat time: 5.5 seconds Number of integrations: 10,000 times or more Solvent: Ortodichlorobenzene / Deuterated benzene (volume ratio: 80/20) Mixed solvent Sample concentration: 55 mg / 0.6 mL
Measurement temperature: 120 ° C
Reference value for chemical shift: 27.50 ppm
Requirement (C-b): The ultimate viscosity [η] of the copolymer (C) measured at 135 ° C. in a decalin solvent is 1.0 to 4.0 dl / g, preferably 1.1 to 4.0 dl / g. It is 3.5 dl / g, more preferably 1.2 to 3.5 dl / g. When the ultimate viscosity [η] of the copolymer (C) is within the above range, the number of low molecular weight substances is small, so that the composition is less sticky and the moldability is improved.

The ultimate viscosity [η] of the copolymer (C) is a value measured by the same method as the ultimate viscosity [η] of the polymer (A).

Requirement (C-c): The molecular weight distribution (Mw / Mn) of the copolymer (C) is 1.0 to 3.5, preferably 1.1, from the viewpoint of preventing stickiness of the composition and appearance. It is ~ 3.0.

The weight average molecular weight (Mw) of the copolymer (C) is preferably 1 × 10 ⁴ to 2 × 10 ⁶ and more preferably 1 × 10 ⁴ to 1 × 10 ⁶ from the viewpoint of moldability of the composition. Is.

The weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) of the copolymer (C) are values calculated by the method described in Examples.

Requirement (Cd): The density measured according to JIS K7112 (density gradient tube method) of the copolymer (C) is 830 to 860 kg / m ³ from the viewpoint of handleability, preferably 830. It is ~ 850 kg / m ³ .

Requirement (C—e): The melting point (Tm) of the copolymer (C) is not observed or is less than 160 ° C, preferably not observed, or is in the range of 110-155 ° C, more preferably not observed. Alternatively, it is in the range of 115 to 150 ° C., and particularly preferably no melting point (Tm) is observed.

The melting point (Tm) of the copolymer (C) is a value measured by the same method as the melting point (Tm) of the polymer (A).
The copolymer (C) preferably satisfies the following requirement (Cf) in addition to the above requirements (C-a) to (C-e).

Requirement (Cf): The melt flow rate (MFR) of the copolymer (C), measured at 230 ° C. with a load of 2.16 kg according to ASTM D1238, is the fluidity of the composition during molding. From the viewpoint of the above, it is preferably 0.1 to 100 g / 10 min, more preferably 0.5 to 50 g / 10 min, and further preferably 0.5 to 30 g / 10 min.

The copolymer (C) is prepared by a conventionally known metallocene catalyst system, for example, the method itself described in International Publication No. 2005/121192, International Publication No. 2011/055803, International Publication No. 2014/050817, and the like. Alternatively, it can be easily prepared by changing the production conditions within the range normally performed by those skilled in the art in order to change the specific items of the polymer properties.

≪4-Methyl-1-pentene copolymer composition≫
The 4-methyl-1-pentene copolymer composition of the present invention can be produced by blending and kneading each of the above-mentioned components in the above-mentioned concentration range using a known method. As a known production method, for example, a method of mixing with a multi-stage polymerization method, a plast mill, a Henshell mixer, a V-blender, a ribbon blender, a tumbler blender, a kneader luder, or the like, or after mixing, a single-screw extruder, a twin-screw extruder, a kneader, etc. Examples thereof include a method of granulating or crushing after melt-kneading with a Banbury mixer or the like.

≪Molded body≫
The molded product containing the 4-methyl-1-pentene copolymer composition of the present invention is, for example, extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, stamping molding, vacuum molding. It is obtained by a known heat molding method such as molding, calendar molding, filament molding, foam molding, powder slush molding and the like. Further, the molded product of the present invention can also be produced by appropriately combining the copolymer, the copolymer composition and the modified product according to the present invention.

The molded body will be specifically described below.
It is also preferable that the molded product is a molded product obtained by primary molding such as extrusion molding, injection molding, or solution casting, and further processed by a method such as blow molding or stretching. For example, when the molded product is in the form of a film or a sheet, the molded product obtained by molding into a sheet by a T-die extrusion molding method or the like is further uniaxially stretched or biaxially stretched. Is also preferable. As the above-mentioned applications, film applications that take advantage of the high melting point are preferable.

In extrusion molding, conventionally known extruders and molding conditions can be adopted, for example, a melted copolymer using a single-screw screw extruder, a kneading extruder, a ram extruder, a gear extruder and the like. Alternatively, the composition can be formed into a desired shape by extruding the composition from a specific die or the like.

The stretched film is obtained by stretching an extruded sheet or an extruded film (unstretched) as described above by a known stretching method such as a tenter method (longitudinal horizontal stretching, horizontal vertical stretching), a simultaneous biaxial stretching method, or a uniaxial stretching method. Obtainable.

The draw ratio when stretching a sheet or an unstretched film is usually about 20 to 70 times in the case of biaxial stretching, and usually about 2 to 10 times in the case of uniaxial stretching. It is desirable to obtain a stretched film having a thickness of about 5 to 200 μm by stretching.

Inflation film can also be manufactured as a film-shaped molded product. Drawdown is unlikely to occur during inflation molding.

The blow-molded article can be manufactured by using a conventionally known blow-molding apparatus and adopting known conditions. In this case, the obtained blow-molded product may be a multi-layer molded product, and contains at least one layer of the copolymer, the copolymer composition or the modified product according to the present invention.

For example, in extrusion blow molding, a tubular parison is formed by extruding from a die in a molten state with a resin temperature of 100 ° C. to 300 ° C., and then air is blown after holding the parison in a mold having a desired shape, and the resin temperature is 130 ° C. A hollow molded body can be manufactured by mounting it on a mold at about 300 ° C. The stretch (blow) magnification is preferably about 1.5 to 5 times in the lateral direction.

In injection blow molding, the parison is molded by injecting it into a parison mold at a resin temperature of 100 ° C to 300 ° C, and then air is blown after holding the parison in a mold having a desired shape, and the resin temperature is 120 ° C to 300. A hollow molded product can be manufactured by mounting it on a mold at ° C. The stretch (blow) magnification is preferably 1.1 to 1.8 times in the vertical direction and 1.3 to 2.5 times in the horizontal direction.

The obtained blow molded article is excellent in transparency, rigidity or flexibility, heat resistance and impact resistance, and also excellent in moisture resistance.

Examples of the press-molded body include a mold stamping molded body, which can be obtained by, for example, simultaneously press-molding a base material and a skin material and performing composite integral molding (mold stamping molding) of both. The substrate can be formed of the copolymer, copolymer composition or modified product according to the present invention. The press-molded product is not easily charged and has excellent rigidity or flexibility, heat resistance, transparency, impact resistance, aging resistance, surface gloss, chemical resistance, and abrasion resistance.

The foam molded product using the copolymer, copolymer composition or modified product according to the present invention can be obtained at a high foaming magnification, has good injection moldability, and has high rigidity and material strength. ..

The filament molded product can be produced, for example, by extruding a molten copolymer, a copolymer composition or a modified product through a spinneret. Specifically, the spunbond method and the meltbron method are preferably used. The filament thus obtained may be further stretched. This stretching may be performed so that at least one axial direction of the filament is molecularly oriented, and it is usually desirable to perform this stretching at a magnification of about 5 to 10 times. The filament molded product according to the present invention is not easily charged, and is excellent in transparency, flexibility, heat resistance, impact resistance, and elasticity.

From the molded product of the present invention, powder slash molded products such as automobile parts, home appliance parts, toys, and miscellaneous goods can be manufactured. The molded product is not easily charged and is excellent in flexibility, heat resistance, impact resistance, aging resistance, surface gloss, chemical resistance, abrasion resistance and the like.

In addition, examples of the molded product according to the present invention include a laminate having at least one layer composed of the copolymer, the copolymer composition, or the modified product according to the present invention. The laminated body is excellent in vibration damping and shock absorbing properties such as shock reduction and shock mitigation.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. Numerical values for components in the table below indicate parts by mass unless otherwise specified.

[Measurement conditions, etc.]
The measurement conditions and the like of the physical properties in the examples are as follows.

[Polymer composition]
The 4-methyl-1-pentene and propylene contents of the 4-methyl-1-pentene polymer (A) and the 4-methyl-1-pentene copolymer (C) are determined by the following apparatus and conditions by ¹³ C-NMR. Measured by. Using ECP500 type nuclear magnetic resonance device manufactured by Nippon Denshi Co., Ltd., orthodichlorobenzene / heavy benzene (80/20% by volume) mixed solvent, sample concentration 55 mg / 0.6 mL, measurement temperature 120 ° C., observation nucleus ¹³ C (125 MHz), sequence is single pulse proton decoupling, pulse width is 4.7 μsec (45 ° pulse), repetition time is 5.5 seconds, integration frequency is 10,000 times or more, 27.50 ppm is the standard for chemical shift. Measured as a value. The composition of polymers other than the polymers (A) and (B) was also analyzed by the ¹³ C-NMR method basically according to this method.

〔density〕
The polymer density was calculated from the weight of each sample measured in water and air using an ALFA MIRAGE electronic hydrometer MD-300S according to ASTM D1505 (underwater substitution method).

[DSC melting point (Tm)]
The DSC melting point (Tm) of the polymer was measured by a differential scanning calorimeter (DSC) with a DSC220C device manufactured by Seiko Instruments. Samples 7-12 mg were sealed in an aluminum pan and heated from room temperature to 200 ° C. at 10 ° C./min. The sample was held at 200 ° C. for 5 minutes for complete melting and then cooled to −50 ° C. at 10 ° C./min. After standing at −50 ° C. for 5 minutes, the sample was reheated to 200 ° C. at 10 ° C./min. The peak temperature of this second (second) heating was adopted as the DSC melting point (Tm).

[Ultimate viscosity]
The ultimate viscosity [η] of the polymer was measured at 135 ° C. using a decalin solvent.

[Molecular weight (Mw, Mn) / Molecular weight distribution (Mw / Mn)]
For the molecular weight of the polymer, a liquid chromatograph: ALC / GPC 150-C plus type manufactured by Waters (integrated type with a differential refractometer detector) was used, and GMH6-HT x 2 and GMH6-HTL x 2 manufactured by Tosoh Corporation were used as columns. Was connected in series, o-dichlorobenzene was used as a mobile phase medium, and the measurement was carried out at a flow rate of 1.0 ml / min and 140 ° C.

The obtained chromatogram was analyzed by a known method using a calibration curve using a standard polystyrene sample to calculate Mw / Mn value and Mz / Mw value. The measurement time per sample was 60 minutes.

[Tensile test, tear strength and surface roughness measurement]
(How to make a test piece)
The compositions of Examples and Comparative Examples were put into a hopper of a 20 mmφ single-screw extruder (single-screw sheet forming machine, manufactured by Tanaka Iron Works Co., Ltd.) equipped with a T-die having a lip width of 240 mm. Then, the cylinder temperature was set to 270 ° C. and the die temperature was set to 270 ° C., and the melt-kneaded product was extruded from the T-die with a thickness of 50 μm and cast-molded to obtain a cast film.

(Measurement of tensile properties)
Next, a tensile tester (universal tensile tester 3380, manufactured by Instron) was used for a test piece obtained by cutting a film having a thickness of 50 μm into a strip having a width of 15 mm and a length of 100 mm in accordance with JIS K7127 (1999). The tensile elastic modulus (YM) (unit: MPa) and the tensile elongation at break (EL) of the test piece in the MD direction and the TD direction under the conditions of a chuck distance of 50 mm, a tensile speed of 200 mm / min, and a temperature of 23 ° C. (Unit:%) was measured.

(Measurement of Elmendrev tear strength)
The film adjusted to a thickness of 50 μm was lightly manufactured by Toyo Seiki Co., Ltd. in accordance with JIS K 7128-991 with the tear load of the Elemendorff method in both the MD direction and the TD direction under the conditions of 23 ° C and 55% RH. The Elmendrev tear strength was measured with a load tearing device.

(Measurement of surface roughness)
A film adjusted to a thickness of 50 μm was cured under the conditions of a temperature of 23 ° C ± 2 ° C and a humidity of 50% ± 10% for 24 hours, and a surface roughness measuring instrument (model: SE-30KS-manufactured by Kosaka Laboratory) and analysis. The measurement was performed according to JISB0601-1994 using an apparatus (model: TDA-22-Kosaka Laboratory), and the average surface roughness (Ra) and the ten-point average roughness (Rz) were determined.

[Measurement of TMA 1.6 mm displacement temperature]
Using a film adjusted to a thickness of 50 μm, a test piece with a width of 4 mm and a length of 10 mm was prepared. It was measured at 23 ° C. to 250 ° C. with a load of 49 mN). The temperature at the time of displacement of 1.6 mm from the TMA curve was read and used as the TMA 1.6 mm displacement temperature (° C.).

(Gloss measurement)
The film was adjusted to a thickness of 50 μm and measured according to JIS Z8741.

[Compounding material]
The compounding materials used in Examples and Comparative Examples are as follows.
(A) 4-Methyl-1-pentene Polymer According to the methods described in Examples and Comparative Examples of International Publication No. 2006/054613 and International Publication No. 2014/050187, 4-methyl-1-pentene, 1- By changing the charging ratio of decene and hydrogen, three kinds of copolymers (A-1), (A-2) and (A-3) were obtained.
Table 1 shows the measurement results of various physical properties of the obtained polymer (A).
The content of 4-methyl-1-pentene in the copolymer (A-1) was 98.0 mol%, and the content of 1-decene was 2.0 mol%. The density was 833 kg / m ³ , the ultimate viscosity [η] was 2.4 dl / g, and the MFR (260 ° C., 5 kg load) was 25 g / 10 min. The DSC melting point (Tm) was 232 ° C, and the TMA 1.6 mm displacement temperature was 225 ° C.
The content of 4-methyl-1-pentene in the copolymer (A-2) was 98.7 mol%, and the content of 1-decene was 1.3 mol%. The density was 832 kg / m ³ , the ultimate viscosity [η] was 2.4 dl / g, and the MFR (260 ° C., 5 kg load) was 25 g / 10 min. The DSC melting point (Tm) was 232 ° C, and the TMA 1.6 mm displacement temperature was 225 ° C.
The content of 4-methyl-1-pentene in the copolymer (A-3) was 97.2 mol%, and the content of 1-decene was 2.8 mol%. The density was 832 kg / m ³ , the ultimate viscosity [η] was 1.2 dl / g, and the MFR (260 ° C., 5 kg load) was 180 g / 10 min. The DSC melting point (Tm) was 232 ° C, and the TMA 1.6 mm displacement temperature was 225 ° C.

(B) Propylene Polymer Prime Polypro (registered trademark) F113G manufactured by Prime Polymer Co., Ltd. was used. The density of this propylene homopolymer was 910 kg / m ³ , MFR (230 ° C., 2.16 kg load): 3 g / 10 minutes, and the TMA 1.6 mm displacement temperature was 155 ° C.

(C) 4-Methyl-1-pentene-based copolymer [Synthesis Example 1] Synthesis of copolymer (C-1) 300 ml in a SUS autoclave with a stirring blade having a capacity of 1.5 L sufficiently substituted with nitrogen. N-hexane (dried on activated alumina in a dry nitrogen atmosphere) and 450 ml of 4-methyl-1-pentene were charged at 23 ° C. 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL) was charged into this autoclave, and the stirrer was rotated.

Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure (gauge pressure) was 0.40 MPa.

Subsequently, 1 mmol of methylaluminoxane and 0.01 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-) prepared in advance in terms of Al were used. 0.34 ml of a toluene solution containing butyl-fluorenyl dichloride was pressed into an autoclave with nitrogen to initiate a polymerization reaction. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C.

60 minutes after the start of the polymerization, 5 ml of methanol was press-fitted into the autoclave with nitrogen to stop the polymerization reaction, and then the inside of the autoclave was depressurized to atmospheric pressure. After decompression, acetone was added to the reaction solution while stirring the reaction solution to obtain a polymerization reaction product containing a solvent.

Then, the obtained polymerization reaction product containing the solvent was dried under reduced pressure at 100 ° C. for 12 hours to obtain 36.9 g of a powdery copolymer (C-1).
Table 1 shows the measurement results of various physical properties of the obtained copolymer (C-1).

The content of 4-methyl-1-pentene in the copolymer (C-1) was 72.5 mol%, and the content of propylene was 27.5 mol%. The density of the copolymer (C-1) was 839 kg / m ³ . The limit viscosity [η] of the copolymer (C-1) is 1.5 dl / g, the weight average molecular weight (Mw) is 337,000, and the molecular weight distribution (Mw / Mn) is 2.1. The melt flow rate (MFR) was 11 g / 10 min. The DSC melting point (Tm) of the copolymer (C-1) was not observed.

[Synthesis Example 2] Synthesis of Copolymer (C-2) 300 ml of n-hexane (dried on activated alumina in a dry nitrogen atmosphere) was placed in a SUS autoclave with a stirring blade having a capacity of 1.5 L and sufficiently nitrogen-substituted. And 450 ml of 4-methyl-1-pentene were charged at 23 ° C. 0.75 ml of a 1.0 mmol / ml toluene solution of triisobutylaluminum (TIBAL) was charged into this autoclave, and the stirrer was rotated.

Next, the autoclave was heated to an internal temperature of 60 ° C. and pressurized with propylene so that the total pressure (gauge pressure) was 0.19 MPa.

Subsequently, 1 mmol of methylaluminoxane and 0.01 mmol of diphenylmethylene (1-ethyl-3-t-butyl-cyclopentadienyl) (2,7-di-t-) prepared in advance in terms of Al were used. 0.34 ml of a toluene solution containing butyl-fluorenyl dichloride was pressed into an autoclave with nitrogen to initiate a polymerization reaction. During the polymerization reaction, the temperature was adjusted so that the internal temperature of the autoclave was 60 ° C.

60 minutes after the start of the polymerization, 5 ml of methanol was press-fitted into the autoclave with nitrogen to stop the polymerization reaction, and then the inside of the autoclave was depressurized to atmospheric pressure. After decompression, acetone was added to the reaction solution while stirring the reaction solution to obtain a polymerization reaction product containing a solvent.

Then, the obtained polymerization reaction product containing the solvent was dried under reduced pressure at 100 ° C. for 12 hours to obtain 44.0 g of a powdery copolymer (C-2).

Table 1 shows the measurement results of various physical properties of the obtained copolymer (C-2).
The content of 4-methyl-1-pentene in the copolymer (C-2) was 84.1 mol%, and the content of propylene was 15.9 mol%. The density of the copolymer A-1 was 838 kg / m ³ . The limit viscosity [η] of the copolymer (C-2) is 1.5 dl / g, the weight average molecular weight (Mw) is 340,000, and the molecular weight distribution (Mw / Mn) is 2.1. The melt flow rate (MFR) was 11 g / 10 min. The DSC melting point (Tm) of the copolymer (C-2) was 132 ° C.

(D) Butene-based copolymer As the butene-based copolymer (D) used in the comparative example, a 1-butene-propylene copolymer manufactured by Mitsui Kagaku Co., Ltd. was used. MFR (230 ° C, 2.16 kg load); 12 g / 10 min, butene-induced skeletal content; 75 mol%, propylene-induced skeletal content; 25 mol%, density; 890 kg / cm ³ , extreme viscosity; 1.5 g / dl, Molecular weight distribution (Mw / Mn); 4.8, DSC melting point (Tm); 75 ° C.

[Example 1]
50 parts by mass of 4-methyl-1-pentene / α-olefin copolymer (A-1), 50 parts by mass of polypropylene (B) manufactured by Prime Polymer Co., Ltd., and 4-methyl obtained in Synthesis Example 1. 5 parts by mass of the -1-pentene / α-olefin copolymer (C-1) was blended. Further, for 100 parts by mass of the composition, 1000 ppm of the hindered phenol-based antioxidant Irganox 1010 manufactured by Ciba Japan Co., Ltd., 1000 ppm of the phosphorus-based processing heat stabilizer Irgafos 168, and calcium steer manufactured by NOF CORPORATION. The rate was blended at 500 ppm. After that, it was put into a hopper of a 20 mmφ single-screw extruder (single-screw sheet forming machine, manufactured by Tanaka Iron Works Co., Ltd.) equipped with a T-die having a lip width of 240 mm. Then, the cylinder temperature was set to 270 ° C. and the die temperature was set to 270 ° C., and the melt-kneaded product was extruded from the T-die to a thickness of 50 μm and cast-molded to prepare a sample for measurement. Table 2 shows the results of measuring the physical characteristics of this film.

[Example 2] to [Example 6]
In Example 1, the types of (A) 4-methyl-1-pentene polymer, (B) propylene polymer, and (C) 4-methyl-1-pentene copolymer are shown in Table 2 or Table 3. A measurement sample was prepared in the same manner as in Example 1 except that the compounding amount was used, and the physical properties were measured. The results of various measurements are shown in Tables 2 and 3.

[Comparative Example 1] to [Comparative Example 4]
In Example 1, either (C) 4-methyl-1-pentene-based copolymer was not used as a compounding component, or (D) butene-based copolymer was used instead of the component (C) in Example 1. A sample for measurement was prepared in the same manner as in the above, and the physical properties were measured. The results of various measurements are shown in Table 2 or Table 3.

As can be seen from Tables 2 and 3, it can be seen that the surface roughness of the sheet made of the composition using the (C) 4-methyl-1-pentene copolymer is small. Furthermore, it can be seen that the tensile elongation at break (EL) tends to extend uniformly in both the MD and TD directions, and that the TMA displacement temperature is also maintained higher than when the (D) butene-based copolymer is used. .. In particular, it is for the inventor that the TMA displacement temperature is kept high even though the melting point of the (C) 4-methyl-1-pentene copolymer is lower than that of the (D) butene copolymer. It was a surprising effect.
This factor is due to the fact that (C) 4-methyl-1-pentene-based copolymer plays a role as a compatibilizer for (A) 4-methyl-1-pentene polymer and (B) polypropylene, and is contained in the film. It is presumed that it had the effect of evenly and finely dispersing each component.

[Example 7]
50 parts by mass of 4-methyl-1-pentene / α-olefin copolymer (A-3), 50 parts by mass of polypropylene (B) manufactured by Prime Polymer Co., Ltd., and 4-methyl obtained in Synthesis Example 2. 5 parts by mass of the -1-pentene / α-olefin copolymer (C-2) was blended. Further, for 100 parts by mass of the composition, 1000 ppm of the hindered phenol-based antioxidant Irganox 1010 manufactured by Ciba Japan Co., Ltd., 1000 ppm of the phosphorus-based processing heat stabilizer Irgafos 168, and calcium steer manufactured by NOF CORPORATION. The rate was blended at 500 ppm. Then, using a capillograph manufactured by Toyo Seiki Co., Ltd. with a nozzle diameter of 1 mm, the filament sample obtained by extruding at a barrel temperature of 260 ° C. and a head speed of 5 mm / min and winding at a winding speed of 100 m was used as a measurement sample. .. Table 4 shows the results of measuring the physical characteristics of this filament.

[Example 8] and [Comparative Example 5]
In Example 7, the measurement was carried out in the same manner as in Example 7 except that the component (C) 4-methyl-1-pentene copolymer was 10 parts by mass or the component (C) was not blended. A sample was prepared and the physical properties were measured. Table 4 shows the results of various measurements.

As can be seen from Table 4, the filament composed of the composition using the (C) 4-methyl-1-pentene copolymer has a small surface roughness.
Further, the results of observing the filament surfaces of Examples 8 and 5 with a scanning electron microscope (SEM) and the results of observing the filament cross section with a transmission electron microscope (TEM) are shown in FIGS. 1 to 4.
In Comparative Example 5 in which (C) 4-methyl-1-pentene copolymer is not blended, the filament surface is rough, and the cross-sectional morphology is also (B). The particle size of the island phase derived from the polypropylene polymer is from 1 μm to several. It is widely dispersed up to 10 μm. On the other hand, in Example 8 in which the (C) 4-methyl-1-pentene copolymer was blended, the filament surface was smooth and the cross-sectional morphology was also the island phase particles derived from the (B) polypropylene polymer. It can be seen that the diameters are uniform to about several μm and are evenly dispersed.

Claims (5)

10 to 50 parts by mass of 4-methyl-1-pentene polymer (A) and propylene polymer (B) 90 to 5 satisfying the following requirements (Aa), (Ab) and (Af). For 0 parts by mass (however, the total of (A) and (B) is 100 parts by mass).
A 4-methyl-1-pentene copolymer containing 1 to 50 parts by mass of a 4-methyl-1-pentene copolymer (C) that simultaneously satisfies the following requirements (C-a) to (C-e). Composition.
(A-a) Derived from a constituent unit [i] 100 to 90 mol% derived from 4-methyl-1-pentene and an α-olefin having 2 to 20 carbon atoms (excluding 4-methyl-1-pentene). The constituent unit [ii] is composed of 0 to 10 mol% (however, the total of the constituent unit [i] and the constituent unit [ii] is 100 mol%).
(Ab) The melting point (Tm) measured by DSC is in the range of 200 to 250 ° C.
(A-f): The melt flow rate (MFR) measured at 260 ° C. and a 5.0 kg load according to ASTM D1238 is 180 g / 10 min to 200 g / 10 min.
(C-a) Consists of a constituent unit [i] 92-60 mol% derived from 4-methyl-1-pentene and a constituent unit [ii] 8-40 mol% derived from propylene (however, the constituent unit [i]. ] And the constituent unit [ii] total 100 mol%).
(C-b) The ultimate viscosity [η] measured in decalin at 135 ° C. is in the range of 1.0 to 4.0 dl / g.
(C) The molecular weight distribution (Mw / Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), measured by gel permeation chromatography (GPC) is 1.0 to 3. It is in the range of 5.
(Cd) The density is in the range of 825 to 860 kg / m ³ .
(C-e) The melting point (Tm) measured by DSC is not observed or is in the range of less than 160 ° C. The 4-methyl-1-pentene according to claim 1, wherein the 4-methyl-1-pentene copolymer (C) satisfies both the following requirements (Cf) and (Cg). Copolymer composition.
(C-f) The constituent unit [i] derived from 4-methyl-1-pentene is 80 to 60 mol%, and the constituent unit [ii] derived from propylene is 20 to 40 mol% (provided that the constituent is 20 to 40 mol%). The sum of the unit [i] and the constituent unit [ii] is 100 mol%).
(Cg) Melting point (Tm) measured by DSC is not observed. A molded product containing the 4-methyl-1-pentene polymer composition according to claim 1 or 2. The molded product according to claim 3, wherein the molded product is a film. The molded product according to claim 3, wherein the molded product is a fiber.

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