JP2024073145A - Resin composition, molding, and method for manufacturing porous sheet and porous bottle - Google Patents

Abstract

To provide a new resin composition which contains a biomass-derived 4-methyl-1-pentene-based polymer.SOLUTION: There are provided a resin composition which contains a polyester resin, and a biomass-derived 4-methyl-1-pentene-based polymer satisfying the following requirement; requirement: a percentage content of a constitutional unit (P) derived from 4-methyl-1-pentene containing a biomass-derived component is 30 to 100 mol%, and a percentage content of a constitutional unit (Q) derived from at least one α-olefin selected from ethylene and α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 0 to 70 mol%, wherein total molar number of the constitutional unit (P) and the constitutional unit (Q) is 100 mol%; a molding composed of the resin composition; and a method for manufacturing a porous sheet and a porous bottle.SELECTED DRAWING: None

Description

The present disclosure relates to a resin composition, a molded body, and a method for producing a porous sheet and a porous bottle.

4-Methyl-1-pentene polymers, which have 4-methyl-1-pentene as the main constituent monomer, have excellent heat resistance, releasability, and chemical resistance, and are therefore widely used in a variety of applications, including display devices, resin films for printing paper, and synthetic paper.

In display devices such as liquid crystal displays and illuminated signs, images can be made clear by shining light from behind, but as lighter and thinner display devices are required, the mainstream method has been to replace the backlight method, which has a light source directly on the back, with a method in which light from the peripheral area is reflected by a reflector or reflective sheet and irradiated from the back. In order to improve display performance while achieving even lighter and thinner displays, reflectors and reflective sheets that are thin and lightweight, have excellent mechanical strength, high reflectivity, and excellent light scattering properties are desired.

For example, Patent Document 1 discloses a white polyester film that is optimal for use as a substrate for liquid crystal display reflectors, which has a higher reflectance and produces a brighter screen. The white polyester film has an average surface reflectance of 90% or more in the wavelength range of 400 to 700 nm, and the reflectance (maximum value - minimum value) in this wavelength range is 10% or less.

For example, Patent Document 2 discloses a polyester resin composition that contains 60 to 98% by weight of polyester (A), 1 to 25% by weight of 4-methyl-1-pentene polymer (B), and 1 to 15% by weight of polar group-modified styrene elastomer (C) (where the total of (A), (B), and (C) is 100% by weight) as a polyester resin composition that can be molded into a sheet that exhibits higher light reflectance performance by more finely dispersing resin components that are incompatible with polyester.

Furthermore, as an example of a polyester sheet having superior light reflecting performance to conventional polyester sheets, Patent Document 3 discloses a polyester sheet comprising a polyester (A), a 4-methyl-1-pentene polymer (B) having a specific heat of fusion and a mesodiad fraction (m) of 98.5 to 100%, and a compatibilizer (C), in which the content ratios of (A), (B), and (C) are, when the total of (A), (B), and (C) is taken as 100 parts by mass, (A) is 60 to 98.9 parts by mass, (B) is 1 to 25 parts by mass, and (C) is 0.1 to 15 parts by mass, and further, (B) satisfies the following requirements (a) to (d):
(a) The content of structural units derived from 4-methyl-1-pentene is 100 to 90 mol %, and the total content of structural units derived from at least one α-olefin selected from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 0 to 10 mol %.
(b) The heat of fusion ΔHm (unit: J/g) and melting point Tm (unit: ° C.) measured by differential scanning calorimetry (DSC) satisfy the following requirements (1) and (2).
(1) ΔHm≧0.5×Tm−76
(2) Melting point Tm: 200 to 260 ° C.
(c) A melt flow rate (MFR) measured in accordance with ASTM D1238 at 260° C. and a load of 5 kg is 0.1 to 500 g/10 min.
(d) the meso dyad fraction (m) as measured by ¹³ C-NMR is 98.5 to 100%.

As an example of a polyester film containing microvoids that is excellent in flexibility and lightweight, Patent Document 4 discloses a polyester film containing microvoids obtained by biaxially stretching and heat treating a polymer mixture in which polyester is mixed with a thermoplastic resin that is incompatible with the polyester, the polyester film containing microvoids being characterized in that the thermoplastic resins that are incompatible with polyester include at least a polystyrene resin, a polymethylpentene resin, and a polypropylene resin, and the polystyrene resin content (a weight %), the polymethylpentene resin content (b weight %), and the polypropylene resin content (c weight %) satisfy the following relationship:
0.01≦a/(b+c)≦1
c/b≦1
5≦a+b+c≦30

On the other hand, as a measure against global warming, in order to move away from dependence on petroleum and create an environment with low carbon dioxide gas emissions, a resin film that combines fossil fuel-derived polyolefin with biomass-derived polyolefin has also been proposed.
For example, Patent Document 5 describes a porous stretched film that emits little carbon dioxide gas and is easy to recover from folding, which contains at least a polyolefin resin and an inorganic filler, and
The polyolefin resin includes a polypropylene resin,
A porous stretched film is disclosed, characterized in that the polypropylene resin contains a plant-derived polypropylene resin.

Japanese Patent Application Laid-Open No. 4-239540 JP 2015-214663 A International Publication No. 2018/123592 Japanese Patent Application Laid-Open No. 10-338763 Patent No. 7076057

However, the above-mentioned Patent Documents 1 to 5 do not disclose or suggest biomass-derived 4-methyl-1-pentene polymers. There is also a demand for the development of molded articles that have excellent light reflectance performance equivalent to that of molded articles containing conventional polyesters, while reducing the increase in environmental load (e.g., carbon dioxide) in the global environment and maintaining the excellent properties inherent to polyester resins, such as mechanical strength, dimensional stability, and durability.

An object of one embodiment of the present disclosure is to provide a resin composition containing a novel biomass-derived 4-methyl-1-pentene polymer and a molded article made of the resin composition.
Another problem to be solved by another embodiment of the present disclosure is to provide a method for producing a molded article made of a resin composition containing a novel biomass-derived 4-methyl-1-pentene polymer.

Means for solving the above problems include the following aspects.
<1> A polyester resin,
A biomass-derived 4-methyl-1-pentene polymer that satisfies the following requirements:
A resin composition comprising:
Requirements: The content of structural units (P) derived from 4-methyl-1-pentene containing a biomass-derived component is 30 to 100 mol %, and the content of structural units (Q) derived from at least one α-olefin selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 0 to 70 mol % (with the proviso that the total number of moles of the structural units (P) and the structural units (Q) is 100 mol %).
<2> A molded article made of the resin composition according to <1>.
<3> The molded body according to <2>, which is porous.
<4> The molded body according to <3>, which is a porous sheet.
<5> The molded article according to <3>, which is a porous bottle.
<6> A method for producing a porous sheet made of the resin composition according to <1>,
A method for producing a porous sheet, comprising the step of stretching the resin composition.
<7> A method for producing a porous bottle made of the resin composition according to <1>,
A method for producing a porous bottle, comprising the step of blow molding the resin composition.

According to one embodiment of the present disclosure, there is provided a resin composition containing a novel biomass-derived 4-methyl-1-pentene polymer, and a molded article made of the resin composition.
According to another embodiment of the present disclosure, there is provided a method for producing a molded article made of a resin composition containing a novel biomass-derived 4-methyl-1-pentene polymer.

In this specification, the terms "polymer" and "(co)polymer" are used to include homopolymers and copolymers, unless otherwise specified.
In this specification, the use of "to" indicating a range of numerical values means that the numerical values before and after it are included as the lower limit and upper limit.
In this specification, the units written either before or after "to" indicating a numerical range refer to the same units unless otherwise specified.
As used herein, a combination of two or more preferred aspects is a more preferred aspect.
In addition, unless otherwise specified in this specification, each component in the composition or each structural unit in the polymer may be contained alone or in combination of two or more types.
In this specification, the amount of each component in a composition or each structural unit in a polymer means, when a plurality of substances or structural units corresponding to each component or each structural unit in a polymer are present in the composition, the total amount of the corresponding substance present in the composition or each of the plurality of structural units present in the polymer, unless otherwise specified.
The present disclosure will be described in detail below.

<Resin Composition>
The resin composition according to the present disclosure contains a polyester resin and a biomass-derived 4-methyl-1-pentene polymer that satisfies the following requirements.
The resin composition according to the present disclosure contains a novel biomass-derived 4-methyl-1-pentene polymer and a polyester resin, and therefore is excellent in suppressing an increase in the environmental load (e.g., greenhouse gases such as carbon dioxide) in the global environment, and further, while maintaining excellent properties inherent to polyester resins, such as mechanical strength, dimensional stability, and durability, the resin composition has excellent light reflecting performance equivalent to that of molded articles containing conventional polyesters.
Hereinafter, each component contained in the resin composition according to the present disclosure will be described in detail.

<<Biomass-derived 4-methyl-1-pentene polymer>>
The resin composition according to the present disclosure contains a biomass-derived 4-methyl-1-pentene polymer that satisfies the following requirements.
Requirements: The content of structural units (P) derived from 4-methyl-1-pentene containing a biomass-derived component is 30 to 100 mol %, and the content of structural units (Q) derived from at least one α-olefin selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 0 to 70 mol % (with the proviso that the total number of moles of the structural units (P) and the structural units (Q) is 100 mol %).
The biomass-derived 4-methyl-1-pentene polymer is a novel biomass-derived polymer. Furthermore, a resin composition containing the biomass-derived 4-methyl-1-pentene polymer is excellent in suppressing an increase in the environmental load (e.g., greenhouse gases such as carbon dioxide) in the global environment, and has performance comparable to that of a conventional resin composition containing a 4-methyl-1-pentene polymer derived from fossil fuels.

The biomass-derived 4-methyl-1-pentene polymer contains a biomass-derived component, and may contain only a biomass-derived component, or may contain both a biomass-derived component and a fossil fuel-derived (hereinafter also referred to as "non-biomass-derived") component.
As used herein, "biomass-derived components" refers to components derived from any renewable natural source and its residues, such as from plants or animals, including fungi, yeasts, algae and bacteria.

[Biomass ratio]
Whether or not a biomass-derived 4-methyl-1-pentene polymer contains a biomass-derived component can be confirmed by measuring the biomass degree of the biomass-derived 4-methyl-1-pentene polymer.
The term "biomass degree" refers to the value of the ¹⁴ C content obtained by a radiocarbon ( ¹⁴ C) measurement method in accordance with ASTM D6866, that is, the concentration of carbon derived from biomass.
Carbon dioxide in the atmosphere contains a certain amount of ^14C , so plants that grow by absorbing carbon dioxide from the atmosphere contain ^14C in the same ratio as the ratio of ^14C in the atmosphere at the time of growth, and this ratio is maintained even after the plant is fixed. Furthermore, biomass-derived components made from these plants contain ^14C in the same ratio as the ^14C contained in the plant. On the other hand, it is known that fossil fuels contain almost no ^14C .
Since ¹⁴ C is a radioactive isotope with a half-life of 5,730 years, it decays and decreases at a constant rate. By using this to measure the proportion of ¹⁴ C, it is possible to confirm whether the raw material is a biomass-derived component or a non-biomass-derived component.

The biomass degree is determined by calculating the percentage of carbon derived from biomass by measuring the percentage of ^14C (pMC) of all carbon atoms contained in a biomass-derived 4-methyl-1-pentene polymer or a resin composition containing said polymer in accordance with ASTM D6866. Note that pMC is an abbreviation for Percent Modern Carbon.

The biomass-derived 4-methyl-1-pentene polymer preferably has a biomass degree of 1% or more according to ASTM D 6866. There is no particular upper limit, and it may be 100%. It is more preferably 1 to 100%, even more preferably 10 to 100%, and particularly preferably 50 to 100%.

The biomass content of the biomass-derived 4-methyl-1-pentene polymer can be appropriately set by adjusting the content of the biomass-derived component in the polymer.

The biomass-derived 4-methyl-1-pentene polymer is preferably a polymer containing 4-methyl-1-pentene as a main component, and may be a homopolymer of 4-methyl-1-pentene or a copolymer of 4-methyl-1-pentene and a monomer other than 4-methyl-1-pentene (i.e., ethylene and an α-olefin having 3 to 20 carbon atoms).
The main component referred to here means the component that is the most abundant among the components that constitute the polymer, and the content of the structural unit (P) derived from 4-methyl-1-pentene described below is preferably more than 50 mol%, more preferably 52 mol% or more, and even more preferably 55 mol% or more (however, the total number of moles of the structural unit (P) and the structural unit (Q) is 100 mol%). There is no particular restriction on the upper limit, and it may be 100 mol%.
In this specification, the content (mol %) of each structural unit in the above polymer is measured by a ¹³ C-NMR measurement method, and specifically, is determined by the method described in the examples below.
The requirements that the biomass-derived 4-methyl-1-pentene polymer must satisfy will be further described below.

<<Structural Unit (P)>>
The biomass-derived 4-methyl-1-pentene polymer contains a structural unit (P) derived from 4-methyl-1-pentene (hereinafter also simply referred to as "structural unit (P)").
The content of the structural unit (P) derived from biomass-derived 4-methyl-1-pentene is 30 to 100 mol%, preferably 50 to 100 mol%, more preferably 80 to 100 mol%, even more preferably 90 to 100 mol%, and particularly preferably 95 to 100% (however, the total number of moles of the structural unit (P) and the structural unit (Q) is 100 mol%).

The structural unit (P) preferably contains a biomass-derived component.
The structural unit (P) can be formed, for example, by using a biomass-derived raw material as a raw material monomer (e.g., 4-methyl-1-pentene, etc.) that forms the structural unit (P), thereby introducing a biomass-derived component into the structural unit (P).
Examples of the biomass-derived raw material that forms the structural unit (P) include biomass-derived propylene and biomass-derived 4-methyl-1-pentene.
The raw material containing a biomass-derived component only needs to contain a raw material derived from biomass in at least a portion thereof, and all of the raw material does not have to be a raw material derived from biomass.

The biomass-derived raw material may be a commercially available product or may be obtained synthetically.
An example of a method for producing biomass-derived 4-methyl-1-pentene is a method for obtaining the propylene by dimerization of biomass-derived propylene. The method for dimerizing propylene is not particularly limited, and known synthesis methods can be used, and suitable examples include the dimerization methods described in JP-A-61-083135 and WO 2006/085531.

The biomass degree of the biomass-derived raw material forming the structural unit (P) is preferably 10% or more. There is no particular upper limit to the biomass degree, but it may be 100%. The biomass degree is more preferably 10 to 100%, even more preferably 30 to 100%, even more preferably 50 to 100%, and particularly preferably 85 to 100%.

The method for adjusting the biomass degree of the biomass-derived raw material is not particularly limited, and can be adjusted by, for example, the following methods: (1) a method of mixing 4-methyl-1-pentene with a biomass degree of 100% and 4-methyl-1-pentene containing 100% non-biomass-derived components (fossil fuel-derived components) in a ratio that results in a desired biomass degree, and (2) a method of mixing multiple 4-methyl-1-pentenes with specific biomass degrees to adjust to 4-methyl-1-pentene with a desired biomass degree.
Also, 4-methyl-1-pentene having a desired biomass content may be obtained and used as it is as a biomass-derived raw material.

The structural unit (P) derived from 4-methyl-1-pentene may consist only of biomass-derived components, or may consist of biomass-derived components and non-biomass-derived components (fossil fuel-derived components).
The non-biomass-derived component means a component having a biomass degree of 0%. For example, by using propylene having a biomass degree of 0% or 4-methyl-1-pentene having a biomass degree of 0%, a non-biomass-derived component can be introduced into the structural unit (P).

<<Structural Unit (Q)>>
The biomass-derived 4-methyl-1-pentene polymer may contain a structural unit (Q) (hereinafter also simply referred to as "structural unit (Q)") derived from at least one α-olefin selected from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene).

Examples of the α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) include 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, and 1-eicosene.
From the viewpoint of copolymerizability and physical properties of the resulting copolymer, the ethylene and the α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) are preferably ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-hexadecene, 1-heptadecene, and 1-octadecene, more preferably ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-hexadecene, 1-heptadecene, and 1-octadecene, and even more preferably 1-octene, 1-decene, 1-hexadecene, 1-heptadecene, and 1-octadecene.
The ethylene and the α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) may be used alone or in combination of two or more kinds.

The structural unit (Q) may contain only a biomass-derived component, or may contain both a biomass-derived component and a fossil fuel-derived component.
In the biomass-derived 4-methyl-1-pentene polymer, at least one of the structural unit (P) and the structural unit (Q) preferably contains a biomass-derived component. When the structural unit (P) contains a biomass-derived component, the structural unit (Q) may contain only a fossil fuel-derived component.
When the structural unit (Q) contains a biomass-derived component, it is sufficient that at least a portion of the raw material monomers forming the structural unit (Q) contains a biomass-derived raw material, and all of the raw materials do not have to be biomass-derived raw materials. The biomass-derived raw materials forming the structural unit (Q) may be commercially available products or may be obtained by synthesis.

The biomass ratio of the raw material forming the structural unit (Q) is preferably 0 to 50%, more preferably 0 to 30%, even more preferably 0 to 20%, and particularly preferably 0 to 10%.

The content of the structural unit (Q) is 0 to 70 mol%, preferably 0 to 50 mol%, more preferably 0 to 20 mol%, even more preferably 0 to 10 mol%, and particularly preferably 0 to 5 mol% (with the proviso that the total number of moles of the structural unit (P) and the structural unit (Q) is 100 mol%).
The structural unit (Q) may contain one type alone, or may contain two or more types.

<<Other structural units>>
The biomass-derived 4-methyl-1-pentene polymer may contain structural units other than the structural unit (P) and the structural unit (Q) (hereinafter, also referred to as “other structural units”) as long as the effects of the present invention are not impaired.

Specific examples of monomers that form the other structural units include cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, functional vinyl compounds, hydroxyl group-containing olefins, halogenated olefins, etc.

Examples of cyclic olefins, aromatic vinyl compounds, conjugated dienes, non-conjugated polyenes, functional vinyl compounds, hydroxyl-containing olefins, and halogenated olefins include the compounds described in paragraphs 0034 to 0041 of JP 2013-169685 A.

Among these, the monomers that form the other structural units are preferably cyclic olefins and aromatic vinyl compounds, and particularly preferably vinylcyclohexane and styrene.

The content of other structural units is preferably 0 to 10 mol %, more preferably 0 to 5 mol %, and even more preferably 0 to 3 mol %, based on the total structural units of the biomass-derived 4-methyl-1-pentene polymer.
The other structural units may be contained in one type only, or in two or more types.

The biomass-derived 4-methyl-1-pentene polymer preferably satisfies the following requirements (I) to (III).
[Requirement (I)]
The biomass-derived 4-methyl-1-pentene polymer has an intrinsic viscosity [η] of 0.5 to 6.0 dl/g measured in decalin at 135° C. The intrinsic viscosity [η] is preferably 0.5 to 5.0 dl/g, more preferably 1.0 to 4.5 dl/g, still more preferably 1.3 to 4.0 dl/g, and particularly preferably 1.5 to 3.0 dl/g.
The value of the intrinsic viscosity [η] can be adjusted, for example, by the amount of hydrogen added during polymerization when the 4-methyl-1-pentene polymer is produced.

[Requirement (II)]
The 4-methyl-1-pentene polymer has a melting point (Tm) measured by differential scanning calorimetry (DSC) of 180 to 250° C. The melting point (Tm) is preferably 190 to 250° C., more preferably 195 to 240° C., and even more preferably 200 to 235° C.

The above melting point (Tm) value tends to depend on the stereoregularity of the polymer and the content of structural unit (Q) derived from at least one α-olefin selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene), and can be obtained by using a stereospecific catalyst for olefin polymerization and further controlling the content of structural unit (Q) derived from at least one α-olefin selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene).

[Requirement (III)]
The 4-methyl-1-pentene polymer has a density of 800 to 850 kg/m ^3. The density is preferably 820 to 850 kg/m ³ , more preferably 825 to 850 kg/m ³ , and further preferably 825 to 845 kg/m ³ .
The density value can be appropriately adjusted, for example, by selecting the type and content of other α-olefin to be polymerized together with 4-methyl-1-pentene.
The density can be determined by the method described in the Examples below.

The melt flow rate (MFR) of the 4-methyl-1-pentene polymer measured in accordance with ASTM D1238 at 260°C under a load of 5 kg is preferably in the range of 0.5 to 200 g/10 min, more preferably 1 to 100 g/10 min, and even more preferably 5 to 50 g/10 min. An MFR in the above range is preferable in terms of fluidity during molding.

The molecular weight distribution (Mw/Mn) of the 4-methyl-1-pentene polymer is usually 1.0 to 30.0, preferably 2.0 to 10.0, and more preferably 2.0 to 8.0. The molecular weight distribution (Mw/Mn) of the 4-methyl-1-pentene polymer is a value calculated by the method described in the Examples.

The meso diad fraction (m) of the 4-methyl-1-pentene polymer measured by ¹³ C-NMR is preferably 90.0 to 100%, more preferably 93.0 to 100%, further preferably 95.0 to 100%, and particularly preferably 97.0 to 100%.
When the mesodiad fraction (m) is within the above range, fish eyes and poor appearance due to eye plugs are unlikely to occur during molding of a resin composition containing the polymer. This is presumably because the uniformity of the composition distribution is improved by narrowing the melting point distribution.
The meso dyad fraction (m) can be determined by the method described in the Examples below.

The 4-methyl-1-pentene polymer preferably has a heat of fusion (ΔHm) at the melting peak (Tm) measured by differential scanning calorimetry (DSC) in the range of 180°C to 250°C of 3 to 60 J/g, more preferably 10 to 60 J/g.

The content of the 4-methyl-1-pentene polymer is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, and further preferably 10 to 25% by mass. In another preferred embodiment, the content of the 4-methyl-1-pentene polymer is preferably 60 to 98.9% by mass, more preferably 60 to 94% by mass. In any case, the total mass of the 4-methyl-1-pentene polymer and the polyester resin described below is 100% by mass.
The 4-methyl-1-pentene polymer may be one type alone or may contain two or more types.

[Method for producing 4-methyl-1-pentene polymer]
The biomass-derived 4-methyl-1-pentene polymer can be obtained by polymerizing 4-methyl-1-pentene and, as necessary, ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene), and a monomer forming the other structural unit. (However, at least one of the 4-methyl-1-pentene, ethylene, and the α-olefin having 3 to 20 carbon atoms contains a biomass-derived component.)

The polymerization method can be, for example, a gas phase method, a solution method, a slurry method, or the like. As for the catalyst, in addition to conventionally known olefin polymerization catalysts such as vanadium catalysts, titanium catalysts, and magnesium-supported titanium catalysts, for example, metallocene catalysts can be used, such as those described in WO 2001/53369, WO 2001/27124, WO 2006/054613, WO 2014/050817, JP-A-3-193796, or JP-A-2-41303.

The 4-methyl-1-pentene polymer can be obtained by single-stage polymerization of 4-methyl-1-pentene and, if necessary, the above-mentioned ethylene and α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) or monomers forming other structural units in a single polymerization step, or by mixing 4-methyl-1-pentene (co)polymers produced in separate steps. Furthermore, the 4-methyl-1-pentene (co)polymer can be obtained by continuously polymerizing the 4-methyl-1-pentene (co)polymer in multiple stages through multiple polymerization steps. The 4-methyl-1-pentene polymer can also be obtained by heat-treating a 4-methyl-1-pentene polymer once produced using the above-mentioned catalyst or the like in an extruder, mixer, or the like.
As the 4-methyl-1-pentene polymer, a commercially available 4-methyl-1-pentene polymer derived from biomass may be used.

<<Polyester Resin>>
The resin composition according to the present disclosure includes a polyester resin. The polyester resin is not particularly limited as long as it is a polyester resin that can be used in combination with the 4-methyl-1-pentene polymer. Examples of such polyester resins include polyester resins obtained by polymerizing a monomer containing a dicarboxylic acid and a diol in the presence of a known polyester polymerization catalyst such as an antimony catalyst, a germanium catalyst, or a titanium catalyst.

The dicarboxylic acid component is not particularly limited, and examples thereof include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids.
Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, phthalic acid, diphenic acid and their ester derivatives.
Examples of the aliphatic dicarboxylic acid include adipic acid, sebacic acid, dodecadioic acid, eicosanoic acid, dimer acid and ester derivatives thereof.
Examples of alicyclic dicarboxylic acids include 1,4-cyclohexanedicarboxylic acid and its ester derivatives.
The dicarboxylic acid component may contain a polyvalent carboxylic acid. Examples of the polyvalent carboxylic acid include trimellitic acid, pyromellitic acid and ester derivatives thereof.

Typical examples of diol components include ethylene glycol, propanediol, butanediol, neopentyl glycol, pentanediol, hexanediol, octanediol, decanediol, cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyethylene glycol, tetramethylene glycol, and polyethers such as polyethylene glycol and polytetramethylene glycol.

From the standpoint of mechanical strength, heat resistance, production costs, etc., the polyester resin preferably contains polyethylene terephthalate (PET), and is more preferably polyethylene terephthalate (PET).

It is preferable that the polyester resin has a small density difference with the 4-methyl-1-pentene polymer. If the density difference between the polyester resin and the 4-methyl-1-pentene polymer is small, the dispersibility of the 4-methyl-1-pentene polymer in the polyester resin is excellent, and a resin composition with excellent transparency and releasability can be obtained.

The density difference between the polyester resin and the 4-methyl-1-pentene polymer is preferably 0 to 1,500 kg/m ³ , more preferably 1 to 600 kg/m ³ , even more preferably 5 to 400 kg/m ³ , still more preferably 10 to 150 kg/m ³ , and particularly preferably 10 to 100 kg/m ³ .

In the resin composition, the dispersibility of the 4-methyl-1-pentene polymer, which has a relatively high melting point among polyolefins, can be improved, and from the viewpoint of excellent transparency of the resulting molded article, the polyester resin preferably has a melting point (Tm) of 200°C or higher, more preferably 205°C or higher, and even more preferably 210°C or higher. The upper limit of the melting point (Tm) is preferably 500°C or lower, more preferably 400°C or lower, and even more preferably 350°C or lower.

The content of the polyester resin is preferably 60 to 99% by mass, more preferably 70 to 95% by mass, and further preferably 75 to 90% by mass. In another preferred embodiment, the content of the polyester resin is preferably 1.1 to 40% by mass, and more preferably 6 to 40% by mass. In any case, however, the total mass of the 4-methyl-1-pentene polymer and the polyester resin is 100% by mass.
The polyester resin may contain one type alone or two or more types.

The mass ratio of the 4-methyl-1-pentene polymer to the polyester resin (4-methyl-1-pentene polymer:polyester resin) is preferably 1:99 to 99:1, more preferably 7:93 to 93:7, and even more preferably 15:85 to 85:15.

[Compatibilizer]
From the viewpoint of adjusting the degree of dispersion of the 4-methyl-1-pentene polymer in the polyester resin and adjusting the interfacial peeling and pore opening between the polyester resin and the 4-methyl-1-pentene polymer, the resin composition may contain a compatibilizer.
The compatibilizer is not particularly limited, and examples thereof include polystyrene, styrene-based elastomers, and polar group-modified styrene-based elastomers.

Styrene-based elastomers contain monovinyl-substituted aromatic hydrocarbons (styrene-based aromatic hydrocarbons) as copolymerization components. Specific examples include styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-butylene-butadiene-styrene block copolymer (SBBS), styrene-butadiene rubber (SBR), styrene-isoprene rubber (SIR), styrene-ethylene copolymer, styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), poly(α-methylstyrene)-polybutadiene-poly(α-methylstyrene) (α-MeSBα-MeS), poly(α-methylstyrene)-polyisoprene-poly(α-methylstyrene) (α-MeSIα-MeS), and further examples include hydrogenated forms of the conjugated diene compounds that make up the above-mentioned copolymers, specifically butadiene and isoprene. Of these, styrene-butadiene rubber, styrene-isoprene rubber, styrene-hydrogenated butadiene rubber, and styrene-hydrogenated isoprene rubber are preferably used.

Polar group-modified styrene-based elastomers include styrene-based elastomers in which a portion of the elastomer is modified with a polar monomer. The modification can be carried out by a conventional method.

Polar monomers used for modification include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids or derivatives thereof, vinyl ester compounds, vinyl chloride, vinyl group-containing organosilicon compounds, carbodiimide compounds, etc. Among these, unsaturated carboxylic acids or derivatives thereof are particularly preferred.

Examples of unsaturated carboxylic acids or derivatives thereof include unsaturated compounds having one or more carboxylic acid groups, esters of compounds having a carboxylic acid group and alkyl alcohols, and unsaturated compounds having one or more carboxylic anhydride groups. Examples of unsaturated groups include vinyl groups, vinylene groups, and unsaturated cyclic hydrocarbon groups. These compounds can be conventionally known and are not particularly limited. Specific examples of such compounds include unsaturated carboxylic acids such as acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and nadic acid (endo-cis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid); or derivatives thereof, such as acid halides, amides, imides, anhydrides, and esters. Specific examples of such derivatives include malenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate. These unsaturated carboxylic acids and/or derivatives thereof can be used alone or in combination of two or more. Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred, with maleic anhydride being particularly preferred. They can be obtained by graft polymerizing a polar monomer in an amount of usually 1 to 100 parts by mass, preferably 5 to 80 parts by mass, per 100 parts by mass of the above-mentioned styrene-based elastomer.

Commercially available polar group-modified styrene-based elastomers can also be used. Specific examples include Dynaron (registered trademark, manufactured by JSR Corporation) 8630P and Tuftec (registered trademark, manufactured by Asahi Kasei Corporation) M1913. The polar group-modified styrene-based elastomers can be used alone or in combination of two or more types.

The polar group-modified styrene-based elastomer preferably satisfies the following requirements (i) and (ii).

(i) The melt flow rate (MFR; JIS K7210, 230°C, 2.12 kgf) is usually 1 to 100 g/10 min, preferably 10 to 50 g/10 min. When the MFR is in the above range, the melt viscosity and/or fluidity of the polyester resin and the 4-methyl-1-pentene polymer become close, and good dispersibility is achieved as a compatibilizer.

(ii) The styrene content is usually 1 to 35% by mass, and preferably 5 to 20% by mass. If the styrene content is less than 1% by mass, compatibility with polyester resins decreases, and if it exceeds 35% by mass, compatibility with 4-methyl-1-pentene polymers decreases significantly.

The content of the compatibilizer is preferably 0.1 to 15 parts by mass, and more preferably 1 to 15 parts by mass, when the total of the polyester resin, the 4-methyl-1-pentene polymer, and the compatibilizer is 100 parts by mass.
The compatibilizer may be used alone or in combination of two or more kinds.

[Other ingredients]
The resin composition according to the present disclosure may further contain components other than the biomass-derived 4-methyl-1-pentene polymer, polyester resin, and compatibilizer (hereinafter also referred to as "other components"), within a range that does not impair the object of the present invention.
Examples of other components include various additives such as weathering stabilizers, heat stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, antislip agents, antiblocking agents, antifogging agents, nucleating agents, lubricants, pigments, dyes, antioxidants, hydrochloric acid absorbers, inorganic or organic fillers, organic or inorganic foaming agents, crosslinking agents, crosslinking assistants, adhesives, softeners, and flame retardants, as well as polymers other than the biomass-derived 4-methyl-1-pentene polymer and polyester resin (hereinafter also referred to as "other polymers").
The content of the other polymer is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 1 part by mass or less, based on 100 parts by mass of the biomass-derived 4-methyl-1-pentene polymer.

There are no particular limitations on the method for producing the resin composition according to the present disclosure, and various known methods can be used. Examples of methods for producing the resin composition include a method of dry blending the biomass-derived 4-methyl-1-pentene polymer and other components as necessary using a Henschel mixer, tumbler blender, V-blender, or the like, a method of dry blending and then melt-kneading using a single-screw extruder, multi-screw extruder, Banbury mixer, or the like, and a method of stirring and mixing in the presence of a solvent.

<Molded body>
The molded article according to the present disclosure is made of the above-mentioned resin composition. The molded article is not particularly limited, and examples thereof include molded articles obtained by known thermoforming methods such as extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, stamping molding, vacuum molding, calendar molding, filament molding, foam molding, powder slush molding, 3D modeling, and microwave heating molding.

The shape of the molded product is not particularly limited and may be any desired shape depending on the purpose, such as a flat plate, a film, a tube (cylinder), a fiber, a bottle, or the like.
The molded article according to the present disclosure may be a porous molded article. The porous molded article may be a porous sheet or a porous bottle.

<Method of manufacturing porous bottle>
The method for producing a porous bottle preferably includes a step of blow molding the above-mentioned resin composition (blow molding step).
In the blow molding process, the blow molding may be extrusion blow molding or injection blow molding.
The molding apparatus used for blow molding is not particularly limited, and any conventionally known blow molding apparatus can be used.

When a porous bottle is molded by extrusion blow molding, for example, a tubular parison is formed by extruding the resin in a molten state at a resin temperature of 100° C. to 300° C. through a die, and the parison is then held in a metal mold of a desired shape, after which air is blown into it, and the parison is fitted into the metal mold at a resin temperature of 130° C. to 300° C., whereby a hollow molded body (porous bottle) can be produced.
The stretch (blow) ratio in the extrusion blow molding is preferably about 1.5 to 5 times in the transverse direction.

When a porous bottle is molded by injection blow molding, for example, a resin is injected into a parison mold at a resin temperature of 100° C. to 300° C. to mold a parison, and then the parison is held in a mold of a desired shape, and air is blown into it, and the parison is attached to the mold at a resin temperature of 120° C. to 300° C., whereby a hollow molded body (porous bottle) can be produced.
The stretch (blow) ratio is preferably 1.1 to 1.8 times in the longitudinal direction and 1.3 to 2.5 times in the transverse direction.

<<Porous sheet>>
The porous sheet is obtained using a resin composition in which the pore opening and peelability around the finely divided dispersed phase are significantly improved compared to conventional methods, and therefore fine pores can be uniformly dispersed, resulting in excellent light reflectivity and scattering properties, and is expected to exhibit uniform characteristics across the entire surface without the occurrence of parts with reduced strength or holes.
The thickness of the porous sheet is not particularly limited, but is preferably in the range of 0.001 mm to 10 mm for practical use. The brightness measured under the conditions described below is preferably in the range of 40 to 100%.

The porous sheet can be used without restrictions for the applications of conventional polyester sheets, but due to its excellent light reflection performance, it can be suitably used for various reflective sheet applications such as reflective sheets for flat image display devices such as liquid crystal displays, reflective sheets for illuminated signs, and rear reflective sheets for solar cells. The porous sheet can also be used as synthetic paper.

<Method of manufacturing porous sheet>
The method for producing the porous sheet is not particularly limited, and examples thereof include a production method including a step of drying the polyester resin, mixing the dried polyester resin, the 4-methyl-1-pentene polymer, and other components, and then melt-kneading the mixture (melt-kneading step), and a step of molding the resin composition obtained in the melt-kneading step (molding step).
Each step included in the method for producing a porous sheet will be described below.

<<Melt kneading process>>
The method of melt-kneading in the melt-kneading step is not particularly limited, and the melt-kneading can be carried out using a melt-kneading device such as an extruder that is generally available on the market.
In the case of melt kneading, for example, the cylinder temperature of the part of the kneading machine where kneading is performed is preferably 250 to 310° C., more preferably 260 to 290° C., from the viewpoint of sufficient kneading and suppressing thermal decomposition of the polyester resin and the 4-methyl-1-pentene polymer.
The kneading time is usually 0.1 to 30 minutes, particularly preferably 1 to 5 minutes, from the viewpoints of sufficient melt-kneading and suppressing thermal decomposition of the polyester resin and the 4-methyl-1-pentene polymer.

The resin composition produced in this manner usually exhibits a state in which at least a portion of the 4-methyl-1-pentene polymer is finely dispersed in the resin composition.

<<Molding process>>
The method for molding the resin composition is not particularly limited as long as a sheet-like product (unstretched sheet) made of the resin composition can be formed, and any known production method can be used.

The method for producing the unstretched sheet is not particularly limited, and can be carried out using a generally commercially available device. Examples of the method for producing the unstretched sheet include a method in which pellets of a resin composition containing a polyester resin, a 4-methyl-1-pentene polymer, and other components as necessary are dried by vacuum drying or the like as necessary, and then fed to an extruder having a T-die and extruded. Alternatively, the polyester resin, the 4-methyl-1-pentene polymer, and other components may each be fed to an extruder to prepare a resin composition in the extruder, and then extrusion molding may be carried out to produce an unstretched sheet.
The unstretched sheet obtained in the molding step may be a single-layer sheet or a laminated sheet including a layer of the resin composition.

<<Stretching process>>
The method for producing a porous sheet preferably includes a step of stretching the resin composition (stretching step).
Specifically, for example, a step of stretching a sheet-like material (unstretched sheet) made of a resin composition obtained by various molding methods is preferably exemplified. The stretching step is more preferably a step of biaxially stretching a sheet-like material obtained by extrusion molding.
The sheet obtained in the stretching step has many fine voids. It is presumed that the stretching step causes peeling at the interface between the polyester resin in the unstretched sheet made of the resin composition obtained in the melt-kneading step and the 4-methyl-1-pentene polymer finely dispersed in the polyester resin, forming many fine voids in the sheet obtained.

In the stretching process, it is preferable to stretch the unstretched sheet using a stretching device, and it is more preferable to stretch the unstretched sheet biaxially using a biaxial stretching device.

The conditions for the stretching process are not particularly limited, but for example, when polyethylene terephthalate (PET) is used as the polyester resin, it is preferable to heat the unstretched sheet to 70 to 90°C, and then stretch it 2 to 5 times in the longitudinal direction and 2 to 5 times in the direction perpendicular to the longitudinal direction.

The stretching method is not particularly limited, and examples thereof include methods of stretching using a commonly available commercially available device.
For example, in the case of biaxial stretching, the film may be stretched successively in the longitudinal direction and in a direction perpendicular to the longitudinal direction, or may be stretched simultaneously in the longitudinal direction and the perpendicular direction.

The method for producing a porous sheet preferably further comprises a step of heat treating the sheet obtained in the above-mentioned stretching step at 150 to 240° C. for 1 to 120 seconds (heat treatment step) in a state where the sheet end portions are fixed with clips or the like, from the viewpoint of promoting oriented crystallization and removing stretching strain to enhance mechanical strength, dimensional stability, etc. This heat treatment step is also called heat setting.
The heat treatment step may include a relaxation treatment of 1 to 10% in the longitudinal and perpendicular directions, if necessary.

In addition, a coating layer may be provided on the sheet obtained through the stretching process to impart functions such as light stability and anti-blocking properties. Furthermore, the obtained sheet may be laminated with the same or different type of sheet.

The present disclosure will be explained in more detail below based on examples, but the present disclosure is not limited to these examples.

[Biomass ratio]
The biomass degree was measured according to the method described in ASTM D6866. That is, the proportion of 14C (pMC content) in the total carbon atoms contained in the 4-methyl-1-pentene polymer or the resin composition containing the polymer (evaluation pellets) ^obtained in the examples and comparative examples was measured, and the proportion of carbon derived from biomass was calculated to obtain the biomass degree.

[Content of structural units]
The content of the structural unit (P) derived from 4-methyl-1-pentene and the content (mol %) of the structural unit (Q) derived from at least one α-olefin selected from ethylene and an α-olefin having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) (hereinafter also referred to as "structural unit (Q) derived from an α-olefin") in the 4-methyl-1-pentene polymer were calculated from a ^13C -NMR spectrum using the following apparatus and conditions.

Using a Bruker Biospin AVANCEIII cryo-500 nuclear magnetic resonance apparatus, the solvent was a mixed solvent of o-dichlorobenzene/benzene-d6 (4/1 v/v), the sample concentration was 55 mg/0.6 mL, the measurement temperature was 120°C, the observation nucleus was ¹³ C (125 MHz), the sequence was single pulse proton broadband decoupling, the pulse width was 5.0 μsec (45° pulse), the repetition time was 5.5 sec, and the number of accumulations was 64. The chemical shift was measured at 128 ppm of benzene-d6 as the reference value.
The content (mol %) of the structural unit (Q) derived from an α-olefin was calculated using the integral value of the main chain methine signal according to the following formula.

Content (mol %) of structural unit (Q) derived from α-olefin
= [q / (p + q)] × 100
In the above formula, q represents the total peak area of the α-olefin main chain methine signals, and p represents the total peak area of the 4-methyl-1-pentene main chain methine signals.

<Meso dyad fraction>
The meso diad isotacticity (meso diad fraction) (m) of a biomass-derived 4-methyl-1-pentene polymer is defined as the proportion of isobutyl branches in the same direction when any two head-to-tail bonded 4-methyl-1-pentene unit sequences in the polymer chain are expressed as a planar zigzag structure, and was calculated ^from the C-NMR spectrum using the following formula:
Mesodiad isotacticity (m) (%) = [m/(m+r)] x 100 [wherein m and r represent the absorption intensity derived from the main chain methylene of the 4-methyl-1-pentene unit bonded head-to-tail represented by the following structural formula.]

^13C -NMR spectrum was measured using a Bruker Biospin AVANCEIII cryo-500 nuclear magnetic resonance apparatus with a mixed solvent of o-dichlorobenzene/benzene-d6 (4/1 v/v), a sample concentration of 60 mg/0.6 mL, a measurement temperature of 120°C, an observation nucleus of ^13C (125 MHz), a single pulse proton broadband decoupling sequence, a pulse width of 5.0 μsec (45° pulse), a repetition time of 5.5 sec, and a chemical shift reference value of 128 ppm for benzene-d6.

The peak region was divided into a region from 41.5 to 43.3 ppm by the minimum point of the peak profile, and the high magnetic field side was classified into a first region and the low magnetic field side into a second region.
In the first region, the main chain methylene in two consecutive 4-methyl-1-pentene units shown by (m) resonates, and the integrated value assuming it to be a 4-methyl-1-pentene homopolymer was taken as "m". In the second region, the main chain methylene in two consecutive 4-methyl-1-pentene units shown by (r) resonates, and the integrated value was taken as "r". Note that less than 0.01% was taken as the detection limit.

[Intrinsic viscosity [η]]
The intrinsic viscosity [η] of the 4-methyl-1-pentene polymer was measured at 135° C. using decalin solvent. That is, about 20 mg of the polymer powder, pellets or resin mass was dissolved in 15 mL of decalin, and the specific viscosity η _sp was measured in an oil bath at 135° C. This decalin solution was diluted with 5 mL of decalin solvent, and the specific viscosity η _sp was measured in the same manner. This dilution procedure was repeated two more times, and the value of η _sp /C when the concentration (C) was extrapolated to 0 was calculated as the intrinsic viscosity (see the formula below).
[η] = lim (η _sp / C) (C → 0)

[Molecular weight distribution (Mw/Mn)]
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the 4-methyl-1-pentene polymer were measured by GPC (gel permeation chromatography) to determine the molecular weight distribution (Mw/Mn). The GPC measurement was carried out under the following conditions. The weight average molecular weight (Mw) and number average molecular weight (Mn) were calculated based on the following conversion method using a calibration curve prepared using a commercially available monodisperse standard polystyrene.
(Measurement condition)
Apparatus: Gel permeation chromatograph HLC-8321 GPC/HT type (manufactured by Tosoh Corporation)
Organic solvent: o-dichlorobenzene Column: 2 TSKgel GMH6-HT columns, 2 TSKgel GMH6-HTL columns (both manufactured by Tosoh Corporation)
Flow rate: 1.0 ml/min Sample: 0.15 mg/mL o-dichlorobenzene solution Temperature: 140° C.
Molecular weight conversion: PS conversion/universal calibration method. For the calculation of universal calibration, the coefficients of the Mark-Houwink viscosity equation were used. The Mark-Houwink coefficients of PS were the values described in the literature (J. Polym. Sci., Part A-2, 8, 1803 (1970)).

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

〔density〕
The density (kg/m ³ ) of the 4-methyl-1-pentene polymer was measured in accordance with JIS K7112 (density gradient tube method).
Here, a low density means that the polymer and the molded article obtained from it are light in weight.

[Melting point (Tm) and heat of fusion (ΔHm)]
Using a DSC measuring device for 4-methyl-1-pentene polymer (Seiko Instruments, model number: DSC220C), about 5 mg of the sample was packed in an aluminum sample pan for measurement, and the temperature was raised to 280°C at 10°C/min. After holding at 280°C for 5 minutes, the temperature was lowered to 20°C at 10°C/min. After holding at 20°C for 5 minutes, the temperature was raised to 280°C at 10°C/min. The temperature at which the apex of the crystalline melting peak observed during the second heating appeared was taken as the melting point (Tm). The heat of fusion (ΔHm) was calculated from the integrated value of this crystalline melting peak. When multiple peaks were detected during the measurement, the temperature at the peak detected on the highest temperature side and the integrated value of the peak were taken as the melting point and the heat of fusion, respectively.

[Sheet brightness]
The sheet luminance was evaluated using the sheets produced in the examples and comparative examples. The reflectance of the light having a wavelength of 550 nm was measured in the longitudinal direction and in the direction perpendicular to the longitudinal direction of the sheet using a spectrophotometer (manufactured by Hitachi High-Tech Science Corporation), and the average value was used.
It can be determined that the higher the light reflectance value, the more excellent the sheet brightness.

[Stretchability]
The sheets produced in the examples and comparative examples were used to evaluate stretchability.
The surface of the sheet was visually inspected, and if there was unevenness in appearance due to non-uniform stretching or uneven thickness (uneven thickness), it was rated as "no good." If no such irregularities were observed, it was rated as "good."

〔exterior〕
The appearance of the sheets produced in the Examples and Comparative Examples was evaluated. When fish eyes or foreign matter were found in the appearance of the sheet by visual inspection, it was rated as "poor," and when no fish eyes or foreign matter were found, it was rated as "good."

(Synthesis of 4-methyl-1-pentene from biomass)
Propylene having a biomass content of 100% was obtained and dimerized by the method described in JP-A-61-083135 to synthesize biomass-derived 4-methyl-1-pentene having a biomass content of 100%.

(Synthesis of 4-methyl-1-pentene derived from fossil fuels)
Fossil fuel-derived propylene, i.e., propylene with a biomass content of 0%, was obtained and dimerized by the method described in JP-A-61-083135 to synthesize fossil fuel-derived, i.e., non-biomass-derived 4-methyl-1-pentene with a biomass content of 0%.

(α-Olefins other than 4-methyl-1-pentene)
A commercially available feedstock was used that was derived from fossil fuels, i.e., had a 0% biomass content.

Example 1
(Production of 4-methyl-1-pentene polymer)
Using biomass-derived 4-methyl-1-pentene having a biomass content of 100% as a raw material, the ratios of 4-methyl-1-pentene, 1-decene, 1-hexadecene, 1-octadecene, or hydrogen were changed in accordance with the methods of Comparative Examples 7 and 9 of WO 2006/054613 to obtain the 4-methyl-1-pentene polymers shown in Table 1. The above-mentioned physical properties of the obtained polymers were measured. The results are shown in Table 1.

(Production of resin composition)
Polyethylene terephthalate (PET) (Mitsui PET manufactured by Mitsui Chemicals, Inc., brand name: J005 PC, IV (intrinsic viscosity) = 0.62 dl/g) as a polyester resin was dried at 150°C for 16 hours using a vacuum dryer.
Next, 75 parts by mass of the dried polyethylene terephthalate (PET), 20 parts by mass of the 4-methyl-1-pentene polymer obtained above, and 5 parts by mass of a block copolymer of dried polybutylene terephthalate (PBT) and polyalkylene glycol (PAG) (Hytrel (R) (registered trademark) manufactured by DuPont-Toray Co., Ltd.) as a compatibilizer were mixed to prepare a composition. The obtained composition was granulated in a twin-screw extruder (manufactured by Plastics Engineering Research Institute Co., Ltd., model number: BT-30 (screw diameter 30 mmφ, L/D 46)) under conditions of a set temperature of 270° C., a resin extrusion rate of 60 g/min, and a rotation speed of 200 rpm, to obtain pellets for evaluation.
The biomass ratio of the resin composition was measured using the evaluation pellets. The results are shown in Table 1.

(Preparation of test stretched sheet)
Using the evaluation pellets prepared above, a coat hanger type T-shaped die (lip shape: 270 x 0.8 mm) was attached to a single screw extruder (Thermo Plastics Corporation, screw diameter 20 mmφ, L/D 28). A take-up machine with a chill roll of 100 mmφ was used. Molding was performed at a cylinder and die temperature of 280°C, a chill roll temperature of 80°C, and a winding speed of 1.0 m/min to prepare an unstretched sheet with a thickness of 100 μm.
Furthermore, using a biaxial stretching device (manufactured by Bruckner), the unstretched sheet was heated at 90° C. for 30 seconds, and then successively stretched to 3.2 times in the longitudinal direction and 3.2 times in the direction perpendicular to the longitudinal direction at a stretching speed of 100 mm/sec to produce a stretched sheet. The stretched sheet was then heat-treated at 200° C. for 30 seconds. The obtained sheet was subjected to the above-mentioned evaluations, and the results are shown in Table 1.

<Examples 2 to 4>
(Production of 4-methyl-1-pentene polymer)
A 4-methyl-1-pentene polymer having a biomass degree shown in Table 1 was obtained in the same manner as in Example 1, except that a 4-methyl-1-pentene polymer having a biomass degree shown in Table 1 was prepared by mixing biomass-derived 4-methyl-1-pentene having a biomass degree of 100% and fossil fuel-derived, i.e., non-biomass-derived 4-methyl-1-pentene having a biomass degree of 0% (4-methyl-1-pentene derived from a fossil fuel). The above-mentioned physical properties of the obtained polymer were measured. The results are shown in Table 1.

(Production of resin composition)
A resin composition (pellets for evaluation) was obtained in the same manner as in Example 1, except that the 4-methyl-1-pentene polymer prepared above was used. The biomass degree of the resin composition was measured using the pellets for evaluation. The results are shown in Table 1.

(Preparation of test stretched sheet)
Using the resin composition obtained above, an unstretched sheet and a stretched sheet were prepared in the same manner as in Example 1. The obtained stretched test sheets were used to carry out the above-mentioned evaluations, and the results are shown in Table 1.

<Examples 5 and 6>
(Production of 4-methyl-1-pentene polymer)
A 4-methyl-1-pentene polymer shown in Table 1 was obtained in the same manner as in Example 1, except that 4-methyl-1-pentene derived from biomass with a biomass degree of 100% was used, and α-olefins other than 4-methyl-1-pentene were derived from fossil fuels, i.e., had a biomass degree of 0%, were used. The above-mentioned physical properties of the obtained polymer were measured. The results are shown in Table 1.

(Production of resin composition)
Using the 4-methyl-1-pentene polymer, a resin composition (pellets for evaluation) was obtained in the same manner as in Example 1. The biomass degree of the resin composition was measured using the pellets for evaluation. The results are shown in Table 1.

(Preparation of test stretched sheet)
Using the resin composition obtained above, an unstretched sheet and a stretched sheet were prepared in the same manner as in Example 1. The obtained stretched test sheets were used to carry out the above-mentioned evaluations, and the results are shown in Table 1.

Example 7
(Production of 4-methyl-1-pentene polymer)
Using 100% biomass-derived 4-methyl-1-pentene as a raw material, a biomass-derived 4-methyl-1-pentene polymer was obtained by synthesis using a metallocene catalyst in accordance with the method of Example 6E described in paragraph [0450] of WO 2014/050817. The above-mentioned physical properties of the obtained polymer were measured. The results are shown in Table 1.

(Production of resin composition)
Using the 4-methyl-1-pentene polymer, a resin composition (pellets for evaluation) was obtained in the same manner as in Example 1. The biomass degree of the resin composition was measured using the pellets for evaluation. The results are shown in Table 1.

(Preparation of test stretched sheet)
An unstretched sheet and a stretched sheet were prepared using the above resin composition in the same manner as in Example 1. The above-mentioned evaluations were carried out using the obtained test stretched sheets. The results are shown in Table 1.

Example 8
(Production of 4-methyl-1-pentene polymer)
A polymer mixture was prepared by blending 50% by mass each of the biomass-derived 4-methyl-1-pentene polymer having a biomass degree of 100% obtained in Example 1 and the non-biomass-derived 4-methyl-1-pentene polymer having a biomass degree of 0% synthesized above. The above-mentioned physical properties of the obtained polymer were measured. The results are shown in Table 1.

(Production of resin composition)
Using the 4-methyl-1-pentene polymer obtained above, a resin composition (pellets for evaluation) was obtained in the same manner as in Example 1. The biomass degree of the resin composition was measured using the pellets for evaluation. The results are shown in Table 1.

(Preparation of test stretched sheet)
An unstretched sheet and a stretched sheet were prepared using the above resin composition in the same manner as in Example 1. The above-mentioned evaluations were carried out using the obtained test stretched sheets. The results are shown in Table 1.

<Example 9>
An injection blow bottle was obtained using an injection blow molding machine manufactured by Nissei ASB Machinery Co., Ltd., with the resin composition containing the 4-methyl-1-pentene polymer derived from biomass with a biomass content of 100% obtained in Example 1 as a raw material. The stretchability and appearance of the obtained bottle were evaluated. The results are shown in Table 2.

<Comparative Example 1>
A 4-methyl-1-pentene polymer and a resin composition (pellets for evaluation) were prepared in the same manner as in Example 1, except that fossil fuel-derived, i.e., 4-methyl-1-pentene with a biomass content of 0% was used as the raw material. The physical properties of the 4-methyl-1-pentene polymer and the resin composition were measured in the same manner as in Example 1. In addition, a stretched sheet was produced using the obtained pellets in the same manner as in Example 1. The obtained sheet was evaluated, and the results are shown in Table 1.

<Comparative Example 2 and Comparative Example 3>
A 4-methyl-1-pentene polymer and a resin composition (pellets for evaluation) were prepared in the same manner as in Examples 5 and 6, except that fossil fuel-derived, i.e., 4-methyl-1-pentene with a biomass content of 0% was used as the raw material. The physical properties of the 4-methyl-1-pentene polymer and the resin composition were measured in the same manner as in Example 1. The obtained pellets were used to produce a stretched sheet in the same manner as in Example 1. The obtained sheet was evaluated, and the results are shown in Table 1.

<Comparative Example 4>
The resin composition (evaluation pellets) containing the 4-methyl-1-pentene polymer with a biomass content of 0% obtained in Comparative Example 1 was used as a raw material and molded in the same manner as in Example 9 to produce an injection blow bottle. The stretchability and appearance of the obtained bottle were evaluated. The results are shown in Table 2.

As shown in Tables 1 and 2, it was possible to prepare resin compositions containing the biomass-derived 4-methyl-1-pentene polymers of Examples 1 to 9. It was also found that the sheets and bottles made of the resin compositions containing the biomass-derived 4-methyl-1-pentene polymers of Examples 1 to 9 reduced the environmental load compared to the sheets and bottles made of the resin compositions containing the 4-methyl-1-pentene polymers of Comparative Examples 1 to 4.
Therefore, it is understood that the sheet and molded article (injection bottle) made of the resin composition also reduce the environmental load. It is also understood that the sheets formed from the resin compositions containing the biomass-derived 4-methyl-1-pentene polymer of Examples 1 to 8 have sheet brightness, extensibility, and appearance equivalent to or greater than the sheets formed from the resin compositions containing the fossil fuel-derived 4-methyl-1-pentene polymer of Comparative Examples 1 and 2. It is also understood that the molded article (injection bottle) formed from the resin composition containing the biomass-derived 4-methyl-1-pentene polymer of Example 9 has extensibility and appearance equivalent to or greater than the molded article (injection bottle) formed from the resin composition containing the fossil fuel-derived 4-methyl-1-pentene polymer of Comparative Example 4.

Claims (7)

A polyester resin;
A biomass-derived 4-methyl-1-pentene polymer that satisfies the following requirements:
A resin composition comprising:
Requirements: The content of structural units (P) derived from 4-methyl-1-pentene containing a biomass-derived component is 30 to 100 mol %, and the content of structural units (Q) derived from at least one α-olefin selected from ethylene and α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is 0 to 70 mol % (with the proviso that the total number of moles of the structural units (P) and the structural units (Q) is 100 mol %). A molded article made of the resin composition according to claim 1. The molded body according to claim 2, which is porous. The molded body according to claim 3, which is a porous sheet. The molded article according to claim 3, which is a porous bottle. A method for producing a porous sheet made of the resin composition according to claim 1, comprising the steps of:
A method for producing a porous sheet, comprising the step of stretching the resin composition. A method for producing a porous bottle made of the resin composition according to claim 1, comprising the steps of:
A method for producing a porous bottle, comprising the step of blow molding the resin composition.