Method for producing modifier and molded body

Abstract

To provide a modifier which contains three components of polyethylene, polyamide and a compatibilizer, and can impart impact resistance to the polyethylene while achieving reduction in environmental loads, and a method for manufacturing a molding using the modifier.SOLUTION: A modifier whose modification target resin is polyethylene PE1 and can improve impact resistance of the modification target resin, and contains polyethylene PE2, polyamide and a compatibilizer, where the compatibilizer is a modified elastomer having a reactive group to the polyamide, and bio-based carbon percentage contents according to ISO 16620-2 of the polyethylene PE2 and the polyamide are 80% or more. The method includes a molding step of molding a raw material obtaining by dry-blending a modification target resin and the modifier described in any one of Claims 1 to 9.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a method for producing a modifier and a molded article. More specifically, the present invention relates to a modifier containing polyethylene, polyamide, and a compatibilizer, and further to a method for producing a molded article using the same.

Background Art

[0002] Techniques for obtaining a thermoplastic resin composition excellent in impact resistance using three components of a polyolefin, a polyamide, and a compatibilizer are disclosed in Patent Documents 1 and 2 below.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] Patent Documents 1 and 2 disclose the use of a modified elastomer having a reactive group with respect to polyamide as a compatibilizer, the use of a melt kneaded product of a compatibilizer separately melt kneaded from a polyolefin and polyamide, the melt kneading of the obtained melt kneaded product and a polyolefin to obtain a target thermoplastic resin composition, and the use of plant-derived polyamide 11 as a polyamide.

[0005] By the way, in recent years, the construction of a sustainable society and the accompanying reduction of environmental impact have been in the spotlight, and in the field of materials technology as well, the corresponding measures have been increasingly strongly desired. Specifically, from the perspective of reducing CO2 emissions, technologies that use plant-derived raw materials instead of fossil-derived raw materials such as petroleum have attracted attention, and in general-purpose resins, not only polyamides but also plant-derived products of polyolefins have come to be marketed. However, compared with fossil-derived resins that have been used for a long time, there is a fact that there are fewer grades and the adjustment to suit various applications has not progressed. For this reason, there is a problem that there are various difficulties in increasing the proportion of plant-derived resins because the fossil-derived resins that have been conventionally used cannot be directly replaced with plant-derived resins.

[0006] The present invention has been made in view of the above situation, and an object thereof is to provide a modifier that contains three components of polyethylene, polyamide, and a compatibilizer and can impart impact resistance to polyethylene while achieving a reduction in environmental impact. Furthermore, an object thereof is to provide a method for manufacturing a molded article using this modifier.

Means for Solving the Problems

[0007] That is, the present invention is as follows. [1] The modifier of the present invention is a modifier that can improve the impact resistance of a resin to be modified, where the resin to be modified is polyethylene (PE1), and contains polyethylene (PE2), polyamide, and a compatibilizer, wherein the compatibilizer is a modified elastomer having a reactive group with respect to the polyamide, and the gist is that the bio-based carbon content rate of the polyethylene (PE2) and the polyamide according to ISO16620-2 is 80% or more. [2] In the modifier of the present invention, the total of the polyethylene (PE2), the polyamide, and the compatibilizer is 100% by mass, and the mass ratio of the polyethylene (PE2) is R PE2 % by mass, the mass ratio of the polyamide is R PA % by mass, and the mass ratio of the compatibilizer is RCB When it is mass%, 1 ≤ R CB (mass%) ≤ 70 and 0.3 ≤ R PE2 / R PA ≤ 3.5 can be achieved. [3] In the modifier of the present invention, the polyethylene (PE2) can be made into high-density polyethylene. [4] In the modifier of the present invention, the MFR (230 ° C / 2.16 kg) of the polyethylene (PE2) can be made 20 g / 10 minutes or less. [5] In the modifier of the present invention, the polyamide can be made into one having a structure in which the straight-chain carbon number of the hydrocarbon group sandwiched between adjacent amide bonds in the main chain is 6 or more. [6] In the modifier of the present invention, the compatibilizer can be made into one having a copolymer chain derived from ethylene and other α-olefins as the main skeleton, and the reactive group is an acid-modified group. [7] In the modifier of the present invention, the polyethylene (PE1) can be made into high-density polyethylene. [8] In the modifier of the present invention, the MFR (230 ° C / 2.16 kg) can be made 3 g / 10 minutes or more. [9] In the modifier of the present invention, it can be obtained by melt-kneading a melt-kneaded product of the polyamide and the compatibilizer and the polyethylene (PE2).

[10] The gist of the method for producing a molded article of the present invention is to include a molding step of molding a raw material obtained by dry-blending polyethylene (PE1) which is a resin to be modified and the modifier of the present invention.

[11] In the method for producing a molded article of the present invention, when the total of the resin to be modified and the modifier is 100% by mass, the modifier can be 30 to 70% by mass.

Advantages of the Invention

[0008] According to the modifier of the present invention, impact resistance can be imparted to polyethylene while reducing the environmental load. According to the method for manufacturing a molded body of the present invention, a molded body of a polyethylene substrate having excellent impact resistance can be easily obtained with a small number of steps while reducing the environmental load, without going through a preliminary kneading step.

Brief Description of Drawings

[0009]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Embodiments for Carrying Out the Invention

[0010] The matters shown here are illustrative and for exemplarily explaining the embodiments of the present invention, and are described for the purpose of providing an explanation that can most effectively and without difficulty understand the principles and conceptual features of the present invention. In this regard, it is not intended to show the structural details of the present invention to a greater extent than necessary for a fundamental understanding of the present invention, and it is to clarify for those skilled in the art how some forms of the present invention are actually embodied by the description combined with the drawings. In addition, in this specification, the description of "XX~YY" means "XX or more and YY or less".

[0011] [1] Modifying agent The modifier of the present invention is a modifier for polyethylene where the resin to be modified is polyethylene (PE1). By blending the modifier of the present invention, it is possible to achieve the modification of improving the impact resistance of polyethylene (PE1). In particular, even when selecting plant-derived polyethylene (plant-derived PE) with a bio-based carbon content of 80% or more according to ISO 16620-2 as polyethylene (PE1), an excellent effect of imparting impact resistance can be obtained.

[0012] The modifier of the present invention contains polyethylene (PE2), polyamide, and a compatibilizer. Among these, the compatibilizer is a modified elastomer having a reactive group with respect to polyamide. Further, polyethylene (PE2) has a bio-based carbon content of 80% or more according to ISO 16620-2. That is, it is plant-derived polyethylene (plant-derived PE). Furthermore, the polyamide has a bio-based carbon content of 80% or more according to ISO 16620-2. That is, it is plant-derived polyamide (plant-derived PA).

[0013] 〈1〉 Polyethylene PE2 Polyethylene PE2 has a bio-based carbon content of 80% or more measured according to the standard of ISO 16620-2 (in this specification, this polyethylene is also simply referred to as "plant-derived PE2"). This bio-based carbon content is a value calculated based on the proportion of 14 C in all constituent carbons, which is the carbon content derived from plants (bio-based carbon content). The plant-derived PE2 used in the present invention may have a bio-based carbon content of 80% or more (it may be 100%), further, it may be plant-derived PE2 with 85% or more, or even further, it may be plant-derived PE2 with 90% or more. In addition, as the bio-based carbon content, in addition to ISO 16620-2, a value measured according to the standard of ASTM D6866 can also be used. Usually, the values according to these standards are substantially the same.

[0014] Plant-derived PE2 is a polymer having a structure in which methylene groups (-CH2-) are linked (methylene chain) as a main skeleton. The methylene chain is a structural unit particularly derived from ethylene. In addition, plant-derived PE2 includes a homopolymer of ethylene and a copolymer of ethylene and other olefins. These may be used alone or in combination of two or more. When plant-derived PE2 is a copolymer, the non-ethylene-derived units (other olefin-derived units) are preferably 50% or less (more preferably 30% or less, even more preferably 10% or less) of the total number of structural units. This is because a lower proportion of non-ethylene-derived units can increase the bio-based carbon content. That is, as plant-derived PE2, a substance with a low proportion of non-ethylene-derived units (for example, 10% or less), which is substantially a homopolymer of ethylene, is preferred.

[0015] Incidentally, examples of the above-mentioned other olefins include olefins having 3 carbon atoms (propylene), olefins having 4 carbon atoms (1-butene, etc.), olefins having 5 carbon atoms (3-methyl-1-butene, 1-pentene, etc.), olefins having 6 carbon atoms (3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, etc.), olefins having 8 carbon atoms (1-octene, etc.). These may be used alone or in combination of two or more.

[0016] Although the various properties of plant-derived PE2 are not limited, it is preferably high-density polyethylene with a density of 0.942 g / cm 3 or more. Also, the MFR (230 °C / 2.16 kg) of plant-derived PE2 is preferably 35 g / 10 min or less. When the MFR of plant-derived PE2 is 35 g / 10 min or less (usually 1 g / 10 min or more), as a result, the obtained modifier can have excellent modification performance. This MFR is more preferably 20 g / 10 min or less, and even more preferably 15 g / 10 min or less. The lower limit is not limited, but from the viewpoint of ease of melt-kneading, 2 g / 10 min or more is preferred, and 3 g / 10 min or more is more preferred. In the present invention, the MFR (230°C / 2.16 kg) of polyethylene is the value measured according to the standards of ISO 1133 or ASTM D1238. The values according to these standards are usually substantially the same value.

[0017] Also, as described above, the density of plant-derived PE2 is 0.942 g / cm 3 or more, and more preferably 0.950 g / cm 3 or more. The upper limit of the density is not limited, but it is preferably 0.954 g / cm 3 or less. The compatibility of the above-described MFR and density can be adjusted by the linearity, branching amount, molecular weight, etc. of polyethylene. In the present invention, the density of polyethylene is the value measured according to the standards of ISO 1183 or ASTM D792. The values according to these standards are usually substantially the same value.

[0018] Furthermore, the MFR (230°C / 2.16 kg) of plant-derived PE2 is preferably small. Specifically, it is preferably closer to the MFR of the melt-kneaded product obtained from plant-derived PA and compatibilizer described later. That is, in the kneading of plant-derived PA and compatibilizer, it is considered that both can be promoted by the reaction, and they are less affected by the MFR difference in the kneading. On the other hand, in the kneading of plant-derived PE2 and the melt-kneaded product (melt-kneaded product of plant-derived PA and compatibilizer), since they do not react with each other, it is considered that they are easily affected by the MFR difference between them. Therefore, by bringing the MFR of plant-derived PE2 closer to the MFR of the melt-kneaded product, the kneadability can be improved, and accordingly, the impact resistance can be improved.

[0019] Specifically, when the MFR (230°C / 2.16 kg) of plant-derived PE2 is M PE2 (g / 10 min) and the MFR (230°C / 2.16 kg) of the melt-kneaded product of plant-derived PA and compatibilizer is M PX (g / 10 min), the ratio M PE2 / PX (= M PE2 / M PX) satisfies 0.5 ≦ M PE2 / PX ≦ 20, preferably 1 ≦ M PE2 / PX ≦ 17, more preferably 2 ≦ M PE2 / PX ≦ 13, still more preferably 5 ≦ M PE2 / PX ≦ 10, particularly preferably. In addition, although the range of M PX is not limited, for example, 0.1 ≦ M PX (g / 10 min) ≦ 10 can be set, and further 0.5 ≦ M PX (g / 10 min) ≦ 5 can be set, and further 1 ≦ M PX (g / 10 min) ≦ 3 can be set.

[0020] 〈2〉Polyamide The polyamide has a bio-based carbon content of 80% or more as measured according to the standard of ISO16620-2 (in this specification, the polyamide is also simply referred to as "plant-derived PA"). This bio-based carbon content is a value calculated based on the proportion of 14 C in all constituent carbons, representing the carbon content derived from plants (bio-based carbon content). The plant-derived PA used in the present invention may have a bio-based carbon content of 80% or more (it may be 100%), and further, it may be a plant-derived PA of 90% or more, or even a plant-derived PA of 95% or more. In addition, for the bio-based carbon content, in addition to ISO16620-2, the value measured according to the standard of ASTM D6866 can also be used. Usually, the values obtained by these standards are substantially the same.

[0021] The plant-derived PA is a polymer having a structure in which hydrocarbon groups (especially methylene chains) are connected through amide bonds (-NH-CO-) as the main skeleton. Examples of the monomers constituting the plant-derived PA include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and para-aminomethylbenzoic acid, and lactams such as ε-caprolactam, undecanolactam, and ω-lauryl lactam. Only one of these may be used, or two or more of them may be used in combination. Among these, from the viewpoint of a high bio-based carbon content rate, it is preferable that the plant-derived 11-aminoundecanoic acid is contained in a large amount.

[0022] Furthermore, the plant-derived PA can also be obtained by copolymerization of diamine and dicarboxylic acid. In this case, examples of the diamine as a monomer include aliphatic diamines such as ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diamino-undecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, 2-methyl-1,5-diaminopentane, and 2-methyl-1,8-diaminooctane, alicyclic diamines such as cyclohexanediamine and bis-(4-aminocyclohexyl)methane, and aromatic diamines such as xylylenediamine (such as p-phenylenediamine and m-phenylenediamine). Only one of these may be used, or two or more of them may be used in combination. Among these, from the viewpoint of a high bio-based carbon content rate, it is preferable that the plant-derived 1,10-diaminodecane and / or 1,5-diaminopentane is contained in a large amount.

[0023] Furthermore, examples of the dicarboxylic acid as a monomer include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassilic acid, tetradecanedioic acid, pentadecanedioic acid, octadecanedioic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid; and furthermore, furandicarboxylic acid and the like. These may be used alone or in combination of two or more. Among these, from the viewpoint of high bio-based carbon content rate, it is preferable that sebacic acid, furandicarboxylic acid, and / or glutaric acid derived from plants are contained in a large amount.

[0024] Furthermore, it is preferable that the plant-derived PA has a structure in which the linear carbon number of the hydrocarbon group sandwiched between adjacent amide bonds in its main chain is 6 or more. Therefore, examples of the plant-derived PA include polyamide 11 (PA11), polyamide 1010 (PA1010), polyamide 1012 (PA1012), polyamide 610 (PA610), polyamide 510 (PA510), polyamide (PA410), polyamide (PA10T), polyamide 11T (PA11T), polyamide MXD10 (MXD10), and the like. These polyamides may be used alone or in combination of two or more. Furthermore, in the case of two or more, both pellets and pellet mixtures made of a mixed resin are included.

[0025] In addition, regardless of whether the plant-derived PA is a homopolymer of an amino acid or lactam, or a copolymer of a diamine and a dicarboxylic acid, it becomes a plant-derived PA when the monomers forming these polymers are derived from plant raw materials. The monomers may be entirely plant-derived monomers, or only a part thereof may be plant-derived monomers (that is, the other part may contain monomers derived from fossils). That is, as a result, the plant-derived PA may have a bio-based carbon content rate of 80% or more.

[0026] Although the various properties of plant-derived PA are not limited, the density is 1.15 g / cm 3 It is preferably the following polyamide, and the MFR (230 ° C / 2.16 kg) is preferably 50 g / 10 minutes or less. When the MFR of the plant-derived PA is 50 g / 10 minutes or less (usually 1 g / 10 minutes or more), as a result, the obtained modifier can have excellent modification performance. This MFR is more preferably 40 g / 10 minutes or less, and even more preferably 35 g / 10 minutes or less. The lower limit is not limited, but from the viewpoint of ease of melt-kneading, 3 g / 10 minutes or more is preferable, and 5 g / 10 minutes or more is more preferable. In the present invention, the MFR (230 ° C / 2.16 kg) of the plant-derived PA is a value measured according to the standards of ISO1133 or ASTM D1238. The values according to these standards are usually substantially the same.

[0027] Also, as described above, the density of the plant-derived PA is 1.15 g / cm 3 The following is preferable, and more preferably, the density is 1.08 g / cm 3 The following is even more preferable. The lower limit of the density is not limited, but it is preferably 0.98 g / cm 3 or more. The compatibility of these MFR and density can be adjusted by the linearity, branching amount, molecular weight, etc. of the plant-derived PA. In the present invention, the density of the plant-derived PA is a value measured according to the standards of ISO1183 or ASTM D792. The values according to these standards are usually substantially the same.

[0028] 〈3〉Compatibilizer The compatibilizer is a modified elastomer having a reactive group with respect to the plant-derived PA. Further, the compatibilizer is preferably a component having an affinity for the plant-derived PE2. In this case, it becomes a component having a compatibilizing action with respect to the plant-derived PE2 and the plant-derived PA. That is, it is preferably a compatibilizer for the plant-derived PE2 and the plant-derived PA. Also, the compatibilizer may be entirely reacted with the plant-derived PA in the present modifier, or only a part thereof may be reacted.

[0029] The reactive groups possessed by the modified elastomer only need to have reactivity with plant-derived PA. For example, acid anhydride groups (-CO-O-OC-), carboxyl groups (-COOH), epoxy groups {-C2O (a three-membered ring structure composed of two carbon atoms and one oxygen atom)}, oxazoline groups (-C3H4NO), isocyanate groups (-NCO), etc. may be mentioned. Only one of these may be used, or two or more may be used in combination. The amount of modification of the modified elastomer by the reactive group is not limited, and it only needs to have one or more reactive groups in one molecule of the modified elastomer. Further, it preferably has 1 or more and 50 or less reactive groups, more preferably 3 or more and 30 or less reactive groups, and particularly preferably 5 or more and 20 or less reactive groups.

[0030] Examples of the modified elastomer include polymers using various monomers into which reactive groups can be introduced (modified elastomers obtained by polymerization using monomers into which reactive groups can be introduced), oxidative decomposition products of various polymers (modified elastomers in which reactive groups are formed by oxidative decomposition), graft polymers of organic acids to various polymers (modified elastomers in which reactive groups are introduced by graft polymerization of organic acids), etc. Only one of these may be used, or two or more may be used in combination. Only one of these may be used, or two or more may be used in combination.

[0031] Examples of the monomer into which a reactive group can be introduced include monomers having a polymerizable unsaturated bond and an acid anhydride group, monomers having a polymerizable unsaturated bond and a carboxyl group, monomers having a polymerizable unsaturated bond and an epoxy group, etc. Specifically, acid anhydrides such as maleic anhydride, itaconic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, butenyl succinic anhydride, and carboxylic acids such as maleic acid, itaconic acid, fumaric acid, acrylic acid, methacrylic acid, etc. may be mentioned. Only one of these may be used, or two or more may be used in combination. Among these compounds, acid anhydrides are preferred, maleic anhydride and itaconic anhydride are more preferred, and maleic anhydride is particularly preferred.

[0032] Furthermore, the type of resin constituting the skeleton of the modified elastomer (hereinafter referred to as "skeleton resin") is not particularly limited, and various thermoplastic resins can be used. As this skeleton resin, an olefin-based elastomer (olefin-based thermoplastic elastomer) and / or a styrene-based elastomer (styrene-based thermoplastic elastomer) can be used.

[0033] Among these, examples of the olefin-based elastomer include those obtained by copolymerizing two or more olefins. Examples of the olefin include ethylene, propylene, and α-olefins having 4 to 8 carbon atoms. Among these, examples of the α-olefin having 4 to 8 carbon atoms include 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, and the like.

[0034] Among these, as the olefin-based elastomer, a copolymer of ethylene and another α-olefin is preferable. That is, as the compatibilizer, a modified elastomer having a copolymer chain derived from ethylene and another α-olefin as the main skeleton and having a reactive group with respect to the plant-derived PA is preferable. When such an olefin-based elastomer is used, a thermoplastic resin composition capable of providing a molded article having particularly excellent impact resistance characteristics can be obtained. And as the α-olefin other than ethylene, an α-olefin having 3 to 8 carbon atoms is preferable, and an α-olefin having 4 to 8 carbon atoms is more preferable.

[0035] Among the above, examples of the copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms include ethylene-propylene copolymer (EPR), ethylene-1-butene copolymer (EBR), ethylene-1-pentene copolymer, and ethylene-1-octene copolymer (EOR). Examples of the copolymer of propylene and an α-olefin having 4 to 8 carbon atoms include propylene-1-butene copolymer (PBR), propylene-1-pentene copolymer, and propylene-1-octene copolymer (POR). These may be used alone or in combination of two or more. Further, when two or more are used, both pellets made of a mixed resin and a pellet mixture are included.

[0036] On the other hand, the styrenic thermoplastic elastomer is a styrenic thermoplastic elastomer having a styrene skeleton. When this styrenic thermoplastic elastomer is used, a molded article having particularly excellent impact resistance characteristics can be produced. More specific examples of the styrenic thermoplastic elastomer include block copolymers of a styrenic compound and a conjugated diene compound, and hydrogenated products thereof. Among these, examples of the styrenic compound include alkylstyrenes such as styrene, α-methylstyrene, p-methylstyrene, and p-t-butylstyrene, p-methoxystyrene, vinylnaphthalene, and the like. These may be used alone or in combination of two or more. On the other hand, examples of the conjugated diene compound include butadiene, isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene, and the like. These may be used alone or in combination of two or more.

[0037] That is, examples of styrenic thermoplastic elastomers include styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), styrene-ethylene / butylene-styrene copolymer (SEBS), styrene-ethylene / propylene-styrene copolymer (SEPS), and the like. These may be used alone or in combination of two or more. Further, when two or more are used, both pellets made of a mixed resin and a pellet mixture are included. Among these, SEBS is preferred.

[0038] Although various properties of the compatibilizer are not limited, the density is 0.90 g / cm 3 It is the following modified elastomer and preferably has an MFR (230 °C / 2.16 kg) of 10 g / 10 min or less. When the MFR of the compatibilizer is 10 g / 10 min or less (usually 0.5 g / 10 min or more), as a result, the obtained modifier can have excellent modification performance. This MFR is more preferably 7 g / 10 min or less, and even more preferably 5 g / 10 min or less. The upper limit is not limited, but from the viewpoint of ease of melt-kneading, 0.5 g / 10 min or more is preferred, and 1.0 g / 10 min or more is more preferred. In the present invention, the MFR (230 °C / 2.16 kg) of the compatibilizer is a value measured according to the standards of ISO1133 or ASTM D1238. The values according to these standards are usually substantially the same.

[0039] Also, the density of the compatibilizer is preferably 0.90 g / cm 3 or less as described above, and more preferably 0.89 g / cm 3 or less. The lower limit of the density is not limited, but it is preferably 0.85 g / cm 3 or more. The compatibility of these MFR and density can be adjusted by the linearity, branching amount, molecular weight, modification amount, etc. of the compatibilizer. In the present invention, the density of the compatibilizer is a value measured according to the standards of ISO1183 or ASTM D792. The values according to these standards are usually substantially the same.

[0040] The molecular weight of the modified elastomer is not particularly limited, but the weight average molecular weight is preferably 10,000 or more and 500,000 or less, more preferably 35,000 or more and 500,000 or less, and particularly preferably 35,000 or more and 300,000 or less. The weight average molecular weight is measured by the GPC method (in terms of standard polystyrene).

[0041] 〈4〉Blending of each component When the total of plant-derived PE2, plant-derived PA, and compatibilizer constituting the modifier of the present invention is 100% by mass, the mass ratio of plant-derived PE2 is R PE2 % by mass, the mass ratio of plant-derived PA is R PA % by mass, and the mass ratio of the compatibilizer is R CB % by mass. In this case, the mass ratio R CB (% by mass) of the compatibilizer is preferably 1 to 70% by mass, more preferably 2 to 60% by mass, still more preferably 2 to 50% by mass, still more preferably 3 to 40% by mass, still more preferably 3 to 35% by mass, and still more preferably 4 to 30% by mass.

[0042] Also, the ratio (R PE2 ) of the mass ratio R PA of plant-derived PE2 to the mass ratio R PE2 of plant-derived PA (R PA / R PE2 / R PA ) is preferably 0.3 to 3.5. This ratio (R PE2 / R PA ) can be further 0.4 to 2.0, can be 0.35 to 2.00, can be 0.40 to 1.50, and can be 0.45 to 1.20. On the other hand, when the resin to be modified of the present invention is polyethylene PE1, the modification effect tends to be significantly improved by R PE2 ≧R PA . More specifically, the ratio (R PE2 / R PA ) is preferably 1 to 3.5, more preferably 1.0 to 3.3, still more preferably 1.2 to 3.0, still more preferably 1.5 to 2.5, and still more preferably 1.8 to 2.3. And this ratio (R PE / R PA is particularly effective in the range where the mass ratio R CB of the compatibilizer is 30% by mass or less.

[0043] Also, the mass ratio R PE2 (mass %) of plant-derived PE2 is preferably 10 to 90% by mass, more preferably 13 to 85% by mass, still more preferably 17 to 80% by mass, still more preferably 20 to 75% by mass, still more preferably 23 to 70% by mass, and still more preferably 25 to 65% by mass. Furthermore, the total ratio R PA+CB (mass %) of plant-derived PA and the compatibilizer is preferably 10 to 90% by mass, more preferably 15 to 87% by mass, still more preferably 20 to 83% by mass, still more preferably 25 to 80% by mass, still more preferably 30 to 77% by mass, and still more preferably 35 to 75% by mass. Also, the mass ratio R PA (mass %) of plant-derived PA is preferably 1 to 80% by mass, more preferably 3 to 75% by mass, still more preferably 5 to 70% by mass, still more preferably 10 to 75% by mass, still more preferably 15 to 70% by mass, and still more preferably 20 to 65% by mass.

[0044] Furthermore, when the total of plant-derived PA and the compatibilizer is 100% by mass, the mass ratio of the compatibilizer is preferably 3 to 70% by mass, more preferably 4 to 65% by mass, still more preferably 5 to 60% by mass, still more preferably 6 to 55% by mass, still more preferably 7 to 45% by mass, and still more preferably 8 to 40% by mass.

[0045] Also, particularly when the mass ratio R PA of plant-derived PA PE2 is less than the mass ratio R PA of plant-derived PE2 (i.e., R PE2 < R PE2 : R PA : R CBis preferably 50 to 80% by mass: 20 to 45% by mass: 1 to 25% by mass, more preferably 52 to 70% by mass: 24 to 40% by mass: 3 to 18% by mass, and particularly preferably 55 to 65% by mass: 27 to 35% by mass: 6 to 14% by mass. Within the above ranges, the Charpy impact strength of polyethylene PE1 can be improved by a factor of 3 or more by modification.

[0046] Although the fluidity of the modifier of the present invention is not limited, the density is 0.93 to 1.00 g / cm 3 and the MFR (230 ° C / 2.16 kg) can be made 3 g / 10 min or more (usually 30 g / 10 min or less). This MFR can be further increased to 6 g / 10 min or more, further increased to 12 g / 10 min or more, and further increased to 17 g / 10 min or more. The upper limit is not limited, but can be made 27 g / 10 min or less. In particular, it can be made 3 to 30 g / 10 min, further 3 to 27 g / 10 min, further 3 to 17 g / 10 min, and further 3 to 12 g / 10 min. In the present invention, the MFR (230 ° C / 2.16 kg) of the compatibilizer is a value measured according to the standards of ISO1133 or ASTM D1238. The values according to these standards are usually substantially the same.

[0047] The phase structure of the modifier of the present invention is not limited, but usually has specific phase structures (1) to (3). Specifically, it can have a phase structure in which plant-derived PA is the continuous phase (A) and plant-derived PE2 is the dispersed phase (B) (see FIGS. 1 to 3). Further, the dispersed phase (B) can have a continuous phase (B1) containing plant-derived PE2 (that is, a continuous phase B1 within the dispersed phase) and a finely dispersed phase (B2) dispersed in the continuous phase B1 within the dispersed phase (that is, a dispersed phase B2 within the dispersed phase) (see FIG. 3).

[0048] In addition, it can have a phase structure in which plant-derived PE2 is the continuous phase (A) and plant-derived PA is the dispersed phase (B) (see FIGS. 4 to 6). Furthermore, the dispersed phase (B) can have a continuous phase (B1) containing plant-derived PA (i.e., the continuous phase B1 within the dispersed phase) and a finely dispersed phase (B2) dispersed in the continuous phase B1 within the dispersed phase (i.e., the dispersed phase B2 within the dispersed phase) (see FIG. 6). In particular, an excellent impact resistance property can be obtained by the phase structure having the finely dispersed phase (B2).

[0049] Furthermore, as the phase structure of (3), it can exhibit a co-continuous structure in which the phase structures of (1) and (2) are mixed. In particular, when exhibiting the phase structures of (1) and (2) above, an excellent impact resistance property can be obtained by the phase structure having the finely dispersed phase (B2). Also, similarly, an excellent impact resistance property can be obtained even when having the co-continuous structure of (3).

[0050] When having the aforementioned phase structure, the size of the dispersed phase contained in the continuous phase is not limited, but its average diameter (average particle diameter) is preferably 10000 nm or less, more preferably 50 to 8000 nm, and still more preferably 100 to 4000 nm. This average diameter of the dispersed phase is the average value (nm) of the maximum lengths of 50 randomly selected dispersed phases in an image obtained using an electron microscope.

[0051] In addition, when having the dispersed phase within the dispersed phase as described above, the size of the finely dispersed phase contained in the dispersed phase is not limited, but its average diameter (average particle diameter) is preferably 5 to 1000 nm, more preferably 5 to 600 nm, still more preferably 10 to 400 nm, and particularly preferably 15 to 350 nm. This average diameter of the finely dispersed phase is the average value (nm) of the maximum lengths of 100 randomly selected finely dispersed phases in an image obtained using an electron microscope.

[0052] 〈5〉 Other components The thermoplastic resin composition of the present invention can contain other components in addition to the above-described plant-derived PE2, plant-derived PA, and compatibilizer. When other components are thermoplastic polymers that can behave in the same manner as plant-derived PE2, plant-derived PA, and compatibilizers (excluding components that function as fillers, fillers, etc.), when the total of plant-derived PE2, plant-derived PA, and compatibilizer is 100 parts by mass, it is preferable that the other component, the thermoplastic polymer, is 20 parts by mass or less. The lower limit value when other components are included is not limited, but for example, it can be 1 part by mass.

[0053] Examples of other components that are thermoplastic polymers include fossil-derived polyolefins with a bio-based carbon content of less than 80% according to ISO 16620-2 (polyolefins not included in the aforementioned plant-derived PE2). Fossil-derived polyolefins include homopolymers of olefins and / or copolymers of olefins. The olefins constituting the fossil-derived polyolefins are not limited, and examples include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, etc. These may be used alone or in combination of two or more. That is, examples of fossil-derived polyolefins include polyethylene, polypropylene, poly-1-butene, poly-1-hexene, poly-4-methyl-1-pentene, etc. These polymers may be used alone or in combination of two or more. Furthermore, when there are two or more, it includes both pellets made of a mixed resin and a pellet mixture.

[0054] Examples of the above polyethylene include ethylene homopolymers and copolymers of ethylene and other olefins. Examples of the latter include ethylene·1-butene copolymers, ethylene·1-hexene copolymers, ethylene·1-octene copolymers, ethylene·4-methyl-1-pentene copolymers, etc. In addition, in the copolymer of ethylene and other olefins, 50% or more of all the constituent units are units derived from ethylene.

[0055] In addition, examples of the polypropylene include a propylene homopolymer and a copolymer of propylene and another olefin. Examples of the latter include a propylene-ethylene copolymer, a propylene-1-butene copolymer, a propylene-1-hexene copolymer, a propylene-1-octene copolymer, and a propylene-4-methyl-1-pentene copolymer. The copolymer of propylene and another olefin may be a random copolymer or a block copolymer. Among these, a block copolymer can be used from the viewpoint of excellent impact resistance. In particular, a propylene-ethylene block copolymer in which the other olefin is ethylene can be used. The propylene-ethylene block copolymer is a block copolymer polypropylene having an ethylene block as a dispersed phase. That is, it is a polypropylene resin in which a homopolypropylene is a continuous phase and a dispersed phase containing polyethylene exists in this continuous phase. Such a block copolymer polypropylene having an ethylene block as a dispersed phase is also referred to as, for example, an impact copolymer, a polypropylene impact copolymer, a heterophasic polypropylene, or a heterophasic block polypropylene. This block copolymer polypropylene is preferable from the viewpoint of excellent impact resistance. In addition, in the copolymer of propylene and another olefin, 50% or more of all the constituent units are units derived from propylene.

[0056] Examples of other components that are thermoplastic polymers include fossil-derived polyamides (polyamides not included in the aforementioned plant-derived PAs) with a bio-based carbon content of less than 80% according to ISO 16620-2. Examples of fossil-derived polyamides include polyamide 6, polyamide 66, polyamide 11, polyamide 610, polyamide 612, polyamide 614, polyamide 12, polyamide 6T, polyamide 6I, polyamide 9T, polyamide M5T, polyamide 1010, polyamide 1012, polyamide 10T, polyamide MXD6, polyamide 6T / 66, polyamide 6T / 6I, polyamide 6T / 6I / 66, polyamide 6T / 2M-5T, polyamide 9T / 2M-8T, and the like. These polyamides may be used alone or in combination of two or more. Further, in the case of two or more, both pellets and pellet mixtures made of a mixed resin are included.

[0057] 〈6〉Production of modifier The modifier of the present invention may be produced in any manner, but can be obtained by melt-kneading a melt-kneaded product of plant-derived PA and a modified elastomer, and plant-derived PE2. That is, the modifier of the present invention can be obtained by a production method comprising a melt-kneading step of melt-kneading a melt-kneaded product of plant-derived PA and a compatibilizer, and plant-derived PE2.

[0058] The melt-kneaded product of plant-derived PA and a compatibilizer may be a composition in a molten state, a composition in a softened state, or a solidified product by pelletization or the like. Also, in the melt-kneading step, any melt-kneading device may be used. For example, an extruder (single-screw extruder, twin-screw kneading extruder, etc.), a kneader, a mixer (high-speed flow mixer, paddle mixer, ribbon mixer, etc.), etc. can be used. These devices may be used alone or in combination of two or more. Further, when two or more are used, they may be operated continuously or batchwise (in a batch mode). Furthermore, each raw material may be mixed all at once or added and charged in multiple times (multi-stage compounding) and mixed. The kneading temperature in the melt-kneading process is not particularly limited, but is preferably 190 to 350°C, more preferably 200 to 300°C, and still more preferably 205 to 260°C.

[0059] In the above method, a melt-kneaded product is used. When obtaining this melt-kneaded product, kneading is performed when the plant-derived PA and the compatibilizer react. Therefore, due to the compatibilizer having reactive groups, reactive groups are added to the surface of the plant-derived PA, and it is considered that a plant-derived PA with the compatibilizer bound to the surface is formed. Then, by further kneading, the plant-derived PA bound to the surface is sheared, and the surface of the unreacted plant-derived PA appears. Then, it is considered that the unreacted compatibilizer further reacts with this unreacted surface. By repeating the shearing of the plant-derived PA to which the compatibilizer is bound, the appearance of the surface of the unreacted plant-derived PA, and the reaction of the unreacted compatibilizer with this unreacted surface, it is considered that smaller reaction products of the plant-derived PA and the compatibilizer can be stably formed without relying on a high share. And when the amount of the compatibilizer that can be supplied in the above process is small, it is considered that the plant-derived PA to which the compatibilizer is bound is difficult to become small, and when the amount of the compatibilizer that can be supplied is sufficiently large, the plant-derived PA to which the compatibilizer is bound is likely to become small.

[0060] 〈7〉Resin to be modified (polyethylene PE1) The resin to be modified by the modifier of the present invention is polyethylene PE1. Polyethylene PE1 can be used regardless of its raw material origin. That is, it may be fossil-derived polyethylene, plant-derived polyethylene, or polyethylene having both origins, but among these, plant-derived polyethylene is preferred. By using polyethylene PE1 as plant-derived polyethylene, a raw material for a molded article and a molded article of a polyethylene substrate having excellent mechanical properties can be obtained while improving the bio-based carbon content.

[0061] When polyethylene PE1 is plant-derived polyethylene (i.e., plant-derived PE1), its bio-based carbon content is not limited. However, similar to plant-derived PE2, it is preferably 80% or more (it may be 100%) in terms of the bio-based carbon content measured according to the standard of ISO 16620-2. The bio-based carbon content of plant-derived PE1 may further be 85% or more, or 90% or more. In addition, similar to plant-derived PE2, in the case of plant-derived PE1, the bio-based carbon content can use the value measured according to the standard of ASTM D6866 in addition to ISO 16620-2. Usually, the values according to these standards are substantially the same.

[0062] Polyethylene PE1 is a polymer having a structure in which methylene groups (-CH2-) are linked (methylene chain) as the main skeleton. The methylene chain is a structural unit particularly derived from ethylene. In addition, polyethylene PE1 includes a homopolymer of ethylene and a copolymer of ethylene and other olefins. These may be used alone or in combination of two or more. When polyethylene PE1 is a copolymer, the non-ethylene-derived units (other olefin-derived units) are preferably 50% or less (more preferably 30% or less, even more preferably 10% or less) of the total number of structural units. This is because a lower proportion of non-ethylene-derived units can increase the bio-based carbon content. That is, as polyethylene PE1, a polymer with a low proportion of non-ethylene-derived units (for example, 10% or less), which is substantially a homopolymer of ethylene, is preferred.

[0063] In addition, examples of the above-mentioned other olefins include olefins having 3 carbon atoms (propylene), olefins having 4 carbon atoms (1-butene, etc.), olefins having 5 carbon atoms (3-methyl-1-butene, 1-pentene, etc.), olefins having 6 carbon atoms (3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, etc.), olefins having 8 carbon atoms (1-octene, etc.). These may be used alone or in combination of two or more.

[0064] The properties of polyethylene PE1 are not limited, but it is preferably high-density polyethylene with a density of 0.942 g / cm 3 or higher. Also, the MFR (230 °C / 2.16 kg) of polyethylene PE1 is preferably 35 g / 10 min or less. When the MFR of polyethylene PE1 is 35 g / 10 min or less (usually 1 g / 10 min or more), as a result, better impact resistance properties can be obtained in the molded article. This MFR is more preferably 20 g / 10 min or less, and even more preferably 15 g / 10 min or less. The lower limit is not limited, but from the viewpoint of ease of melt-kneading, 2 g / 10 min or more is preferable, and 3 g / 10 min or more is more preferable. In the present invention, the MFR (230 °C / 2.16 kg) of polyethylene shall be the value measured according to the standards of ISO 1133 or ASTM D1238. The values according to these standards are usually substantially the same.

[0065] Also, the density of polyethylene PE1 is preferably 0.942 g / cm 3 or higher, and more preferably 0.950 g / cm 3 or higher. The upper limit of the density is not limited, but it is preferably 0.954 g / cm 3 or less. The compatibility of the above-mentioned MFR and density can be adjusted by the linearity, branching amount, molecular weight, etc. of polyethylene. In the present invention, the density of polyethylene shall be the value measured according to the standards of ISO 1183 or ASTM D792. The values according to these standards are usually substantially the same.

[0066] Furthermore, the MFR (230 °C / 2.16 kg) of polyethylene PE1 is preferably small. Specifically, it is preferably closer to the MFR (230 °C / 2.16 kg) of the modifier. By making the MFR of polyethylene PE1 close to the MFR of the modifier, the kneadability becomes good, and it is considered that the impact resistance can be improved accordingly.

[0067] Further, polyethylene PE1 and plant-derived PE2 may be different polyethylenes, but are preferably the same polyethylene. This can improve the bio-based carbon content of the entire molded article thus obtained. When polyethylene PE1 and plant-derived PE2 are the same polyethylene, polyethylene PE1 is plant-derived PE1. And both plant-derived PE1 and plant-derived PE2 are high-density polyethylene and have substantially the same bio-based carbon content, MFR (230 °C / 2.16 kg), and density (g / cm 3 ).

[0068] 〈8〉Use as a carrier for an additive of a modifier The modifier of the present invention can be blended for the purpose of improving the impact resistance of the resin to be modified, and can also be used as a carrier for adding an additive to the resin to be modified. In this case, the additive can be simultaneously added to the obtained molded article while improving the impact resistance (modification). In this case, the modifier of the present invention is a carrier for adding an additive to a resin to be added, where the resin to be added is polyethylene (PE1), and includes an additive, polyethylene (PE2), polyamide, and a compatibilizer, the compatibilizer is a modified elastomer having a reactive group with respect to the polyamide, and can be paraphrased as a carrier in which the bio-based carbon content of the polyethylene (PE2) and the polyamide according to ISO16620-2 is 80% or more.

[0069] The type of the additive is not limited, and examples thereof include a flame retardant, a flame retardant aid, a filler, a colorant, an antibacterial agent, an antistatic agent, and the like. These may be used alone or in combination of two or more. Further, when the modifier of the present invention is used as a carrier for an additive, when the total of plant-derived PE2, plant-derived PA, and the compatibilizer is 100 parts by mass, the additive can be blended, for example, in an amount of 500 parts by mass or less. The lower limit of the amount of the additive contained is not limited, but can be, for example, 1 part by mass.

[0070] [2]Method for manufacturing a molded article The method for manufacturing a molded article of the present invention is characterized by comprising a molding step of molding a raw material obtained by dry-blending a resin to be modified and the modifier of the present invention described above. That is, the method for manufacturing this molded article can be paraphrased as a modification method. In this modification, dry blending can be utilized. That is, after mixing the modifier with the raw material particles (pellets, granular materials, etc.) of polyethylene PE1, which is the resin to be modified, by dry blending, a modified molded article (for example, a shaped article) can be obtained by molding the mixed particles. Generally, in the case of modification, a melt-kneaded product obtained by melt-kneading both is pelletized, and a modified molded article (for example, a shaped article) is obtained by molding the obtained modified pellets. However, in this method, melt-kneading is not required, and an excellent modification effect can be obtained by dry blending. That is, according to this method, a molded article having a polyethylene substrate with excellent impact resistance can be easily obtained with a small number of steps while reducing the environmental load without going through a preliminary kneading step.

[0071] The amount of the modifier used in this method is not limited, but when the total of the resin to be modified and the modifier is 100% by mass, the modifier can be used so as to be 30 to 70% by mass. Further, the modifier is preferably used so as to be 35 to 65% by mass, and more preferably used so as to be 40 to 60% by mass.

[0072] In particular, in the method for manufacturing a molded article of the present invention, the resin to be modified is plant-derived PE1, and by using a modifier satisfying R PE2 ≧R PA a molded article with a high modification effect can be obtained. Furthermore, in the range where the mass ratio R CB of the compatibilizer is 30% by mass or less, the ratio (R PE2 / R PA) By using a modifier having a value of 1 to 3.5, more preferably 1.0 to 3.3, still more preferably 1.2 to 3.0, still more preferably 1.5 to 2.5, and still more preferably 1.8 to 2.3, it is possible to obtain a molded article imparted with a particularly high modification effect. Further, in this case, as described above, when the total of the resin to be modified and the modifier is 100% by mass, by using the modifier in an amount of 30 to 70% by mass, it is possible to obtain a molded article imparted with a particularly high modification effect. Furthermore, as described above, the modifier is preferably used in an amount of 35 to 65% by mass, and more preferably 40 to 60% by mass.

[0073] When molding, any known molding method can be used. Specifically, injection molding, extrusion molding (sheet extrusion, profile extrusion), T-die molding, blow molding, injection blow molding, inflation molding, hollow molding, vacuum molding, foam molding, compression molding, press molding, stamping mold molding, transfer molding, insert molding, etc. are exemplified. These may be used alone or in combination of two or more.

[0074] The shape, size, thickness, etc. of the molded article are not particularly limited, and its use is also not particularly limited. The molded article is used, for example, as various articles used for vehicles such as automobiles, railway vehicles (entire vehicles), aircraft fuselages (entire fuselages), ships and hulls (entire hulls), bicycles (entire bodies), etc. Among these, automotive supplies include exterior parts, interior parts, engine parts, electrical parts, etc. Specifically, as exterior parts for automobiles, there are roof rails, fenders, fender liners, garnishes, bumpers, door panels, roof panels, hood panels, trunk lids, fuel lids, door mirror stays, spoilers, hood louvers, wheel covers, wheel caps, grille apron cover frames, lamp bezels, door handles (pull handles), door moldings, rear finishers, wipers, engine undercovers, floor undercovers, rocker moldings, cowl louvers, cowls (motorcycles), etc.

[0075] As automotive interior parts, there are trim parts such as door trim substrates (FR, RR, BACK), pockets, armrests, switch bases, decorative panels, ornament panels, EA materials, speaker grilles, quarter trim substrates, etc.; pillar garnishes; cowl side garnishes (cowl side trims); seat parts such as shields, back boards, dynamic dampers, parts around side airbags, etc.; instrument panel parts such as center clusters, registers, center boxes (doors), grab doors, cup holders, parts around airbags, etc.; center consoles; overhead consoles; sun visors; deck boards (luggage boards), under trays; package trays; high mount stop lamp covers; CRS covers; seat side garnishes; scuff plates; dome lights; assist grips; safety belt parts; register blades; washer levers; window regulator handles; knobs of window regulator handles; passing light levers, etc.

[0076] As automotive engine parts, there are alternator terminals, alternator connectors, IC regulators, potentiometer bases for light diodes, exhaust gas valves, fuel pipes, cooling pipes, brake pipes, wiper pipes, exhaust pipes, intake pipes, hoses, tubes, air intake nozzle snorkels, intake manifolds, fuel pumps, engine cooling water joints, carburetor main bodies, carburetor spacers, exhaust gas sensors, cooling water sensors, oil temperature sensors, brake pad wear sensors, throttle position sensors, crankshaft position sensors, air flow meters, brake pad wear sensors, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, torque control levers, etc.

[0077] As automotive electrical components, there are various components such as battery peripheral components, thermostats for air conditioners, heating warm air flow control valves, brush holders for radiator motors, water pump impellers, turbine vanes, components related to wiper motors, dust distributors, starter switches, starter relays, wire harnesses for transmissions, window washer nozzles, air conditioner panel switch substrates, coils for fuel-related solenoid valves, wire harness connectors, SMJ connectors, PCB connectors, door grommet connectors, connectors for fuses and other various connectors, horn terminals, electrical component insulating boards, stepping motor rotors, lamp sockets, lamp reflectors, lamp housings, cleaner cases, filter cases, power trains, etc.

[0078] Furthermore, the molded body is also used as various supplies, etc. in non-vehicle applications other than the above-mentioned vehicles. That is, for example, industrial and industrial materials such as ropes, spunbonds, abrasive brushes, industrial brushes, filters, transport containers, trays, transport carts, and other general materials; Electronic components such as connectors, coils, sensors, LED lamps, sockets, resistors, relay cases, small switches, coil bobbins, capacitors, varicon cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, small speed gears, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related components, etc.; Electrical equipment such as generators, motors, transformers, current converters, voltage regulators, rectifiers, inverters, relays, electrical contacts for power use, switches, cut-off machines, knife switches, other pole rods, electrical component cabinets, etc.;

[0079] Housings of industrial robots, housings of care robots, housings of drones (flying objects that fly by remote control, flying objects that fly autonomously), Household appliances and office products such as VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, audio LD parts, CD·DVD parts, lighting parts, refrigerator parts, washing machine parts, air conditioner parts, typewriter·word processor parts, office computer parts, PCs, game consoles, tablet terminals, mobile phones, smartphones, telephones and related parts, fax machine parts, copier parts, cleaning and washing equipment, motor parts, etc.; Optical and precision instruments such as cameras, watches, microscopes, binoculars, telescopes, glasses, etc.; Storage cases such as food trays, storage boxes, storage trays, attaché cases, suitcases, helmets, water cylinders, bottles, etc., toiletries, writing utensils, stationery, bookends, skin care appliances, utensils, tableware, washing utensils, cleaning utensils, clothes hangers, food containers, lids (such as glass bottles), etc., daily necessities and household items;

[0080] Toys and other entertainment products; Housings and covers of lawn mowers, housings and covers of power tools, various clips, etc., metalworking, general machinery and parts; Sports supplies such as tennis racket strings, ski boards, protectors (for baseball, soccer, motor sports), shoes, shoe soles (for shoe bottoms, sports shoes), outdoor and mountain climbing equipment, etc.; Furniture-related products such as garment cases, tables, chairs, shoe boxes, kitchen utensils, toilet utensils, bathing utensils, etc.; Residential and civil engineering-related products such as interior and exterior walls, roofs, insulation materials, door-related parts, window material-related parts, floor material-related parts, seismic isolation and vibration damping parts, shutters, rain gutters, water supply and sewerage-related parts (related to lifelines), parking garages, gas and electricity-related parts (related to lifelines), civil engineering-related parts, signal equipment, road signs, pylons, center poles, guardrails (guard wires), construction equipment, etc.; Medical-related products such as mouthpieces, medical devices, medicine containers, etc.; Clothing-related products such as shoes, etc., Agricultural, forestry and fisheries-related products such as agricultural implements, farming tools, flower pots, fishing gear, aquaculture-related equipment, forestry tools, etc. And so on.

Examples

[0081] Hereinafter, the present invention will be specifically described by way of examples. [1] Each raw material component (1) Plant-derived PE2 As the plant-derived PE2, the following polyethylene was prepared. HDPE (manufactured by Braskem, product name "SHC7260"), density 0.953 g / cm 3 , MFR (230 °C / 2.16 kg) 12 g / 10 min, bio-based carbon content 94% or more

[0082] (2) Plant-derived PA As the plant-derived PA, the following polyamide was prepared. PA11 (manufactured by Arkema, product name "Rilsan BMN O"), density 1.03 g / cm 3 , MFR (230 °C / 2.16 kg) 32 g / 10 min, bio-based carbon content 99% or more

[0083] (3) Compatibilizer As the compatibilizer, the following ethylene-1-butene copolymer was prepared. Maleic anhydride-modified EBR (manufactured by Mitsui Chemicals, product name "Tafmer MH7020"), density 0.866 g / cm 3 , MFR (230 °C / 2.16 kg) 1.5 g / 10 min

[0084] (4) Resin to be modified As the resin to be modified, the following plant-derived PE1 and non-plant-derived PP were prepared. Plant-derived PE1: HDPE (manufactured by Braskem, product name "SHA7260"), density 0.955 g / cm 3 , MFR (230 °C / 2.16 kg) 32 g / 10 min, bio-based carbon content 94% or more Non-plant-derived PP: Block polypropylene (manufactured by Prime Polymer Co., Ltd., product name "J817U"), density 0.90 g / cm 3 , MFR (230 °C / 2.16 kg) 31 g / 10 min, bio-based carbon content 0%

[0085] [2] Preparation of the melt-kneaded product The above plant-derived PA and the above compatibilizer were dry-blended at a blending ratio (by mass) of 6:1 or 3:1, and then charged into a twin-screw melt-kneading extruder (manufactured by Plastic Engineering Laboratory Co., Ltd., screw diameter 30 mm, L / D = 42). Melt-kneading was carried out under the conditions of a kneading temperature of 210 °C, an extrusion speed of 3.0 kg / hour, and a screw rotation speed of 200 revolutions per minute. Through a pelletizer, pellets of the melt-kneaded product were obtained. The MFR (230 °C / 2.16 kg) of the obtained melt-kneaded product was 5.9 g / 10 minutes for the melt-kneaded product A in which the plant-derived PA:compatibilizer was 6:1, and 0.98 g / 10 minutes for the melt-kneaded product B in which the plant-derived PA:compatibilizer was 3:1.

[0086] [3] Preparation of the modifier (1) Preparation of the modifier for Experimental Example 1 and Experimental Example 9 The melt mixture A obtained in the above [2] and the plant-derived PE2 were dry-blended at a blending ratio (by mass) of 7:3, and then charged into a twin-screw melt-kneading extruder (manufactured by Plastic Engineering Laboratory Co., Ltd., screw diameter 30 mm, L / D = 42). Mixing was carried out under the conditions of a kneading temperature of 210 °C, an extrusion speed of 3.0 kg / hour, and a screw rotation speed of 200 revolutions per minute. Through a pelletizer, the modifiers (pellets) for Experimental Example 1 and Experimental Example 9 were obtained. The obtained modifier had a density of 0.99 g / cm 3 and an MFR (230 °C / 2.16 kg) of 22.8 g / 10 minutes.

[0087] (2) Preparation of the modifier for Experimental Example 5 and Experimental Example 13 The melt mixture B obtained in the above [2] and the plant-derived PE2 were dry-blended at a blending ratio (by mass) of 4:6, and then charged into a twin-screw melt-kneading extruder (manufactured by Plastic Engineering Laboratory Co., Ltd., screw diameter 30 mm, L / D = 42). Mixing was carried out under the conditions of a kneading temperature of 210 °C, an extrusion speed of 3.0 kg / hour, and a screw rotation speed of 200 revolutions per minute. Through a pelletizer, the modifiers (pellets) for Experimental Example 5 and Experimental Example 13 were obtained. The obtained modifier had a density of 0.94 g / cm 3 and an MFR (230 °C / 2.16 kg) of 4.9 g / 10 minutes.

[0088] [4] Manufacturing of Molded Bodies (1) Manufacturing of Molded Bodies in Experimental Examples 2 - 3 The modifier of Experimental Example 1 obtained in [3] above and the plant - derived PE1, which is the resin to be modified, were dry - blended at a blending ratio of 1:1 (Experimental Example 2) and a blending ratio of 1:4 (Experimental Example 3). After that, the obtained dry - blended raw material was put into the hopper of an injection molding machine (100 - ton injection molding machine), and injection - molded under injection conditions of a set temperature of 210°C and a mold temperature of 60°C to obtain the molded bodies (evaluation - use molded bodies) of Experimental Examples 2 - 3.

[0089] (2) Manufacturing of Molded Bodies in Experimental Examples 6 - 7 The modifier of Experimental Example 5 obtained in [3] above and the plant - derived PE1, which is the resin to be modified, were dry - blended at a blending ratio of 1:1 (Experimental Example 6) and a blending ratio of 1:4 (Experimental Example 7). After that, the obtained dry - blended raw material was put into the hopper of an injection molding machine (100 - ton injection molding machine), and injection - molded under injection conditions of a set temperature of 210°C and a mold temperature of 60°C to obtain the molded bodies (evaluation - use molded bodies) of Experimental Examples 6 - 7.

[0090] (3) Molded Bodies of Experimental Examples 1 and 5 The modifiers of Experimental Examples 1 and 5 obtained in [3] above were put into the hopper of an injection molding machine (100 - ton injection molding machine), and injection - molded under injection conditions of a set temperature of 210°C and a mold temperature of 60°C to mold the molded bodies (evaluation - use molded bodies) of Experimental Examples 1 and 5. Note that the molded bodies of Experimental Examples 1 and 9 are the same. Furthermore, the molded bodies of Experimental Examples 5 and 13 are the same.

[0091] (4) Molded Bodies of Experimental Examples 4 and 8 The plant - derived PE1 (high - density polyethylene) prepared in [1](4) above was put into the hopper of an injection molding machine (100 - ton injection molding machine), and injection - molded under injection conditions of a set temperature of 210°C and a mold temperature of 60°C to mold the molded bodies (evaluation - use molded bodies) of Experimental Examples 4 and 8. Note that the molded bodies of Experimental Examples 4 and 8 are the same.

[0092]

Table 1

[0093] (5) Molded articles of Experimental Example 10 and Experimental Example 11 The modifier of Experimental Example 9 obtained in [3] above and non-plant-derived PP, which is the resin to be modified, were dry-blended at a blending ratio of 1:1 (Experimental Example 10) and a blending ratio of 1:4 (Experimental Example 11). After that, the obtained dry-blended raw material was put into the hopper of an injection molding machine (100-ton injection molding machine), and injection molding was performed under injection conditions of a set temperature of 210°C and a mold temperature of 60°C to obtain molded articles (evaluation molded articles) of Experimental Examples 10 to 11.

[0094] (6) Molded articles of Experimental Example 14 and Experimental Example 15 The modifier of Experimental Example 13 obtained in [3] above and non-plant-derived PP, which is the resin to be modified, were dry-blended at a blending ratio of 1:1 (Experimental Example 14) and a blending ratio of 1:4 (Experimental Example 15). After that, the obtained dry-blended raw material was put into the hopper of an injection molding machine (100-ton injection molding machine), and injection molding was performed under injection conditions of a set temperature of 210°C and a mold temperature of 60°C to obtain molded articles (evaluation molded articles) of Experimental Examples 14 to 15.

[0095] (7) Molded articles of Experimental Example 9 and Experimental Example 13 The modifiers of Experimental Example 9 and Experimental Example 13 obtained in [3] above were put into the hopper of an injection molding machine (100-ton injection molding machine), and injection molding was performed under injection conditions of a set temperature of 210°C and a mold temperature of 60°C to obtain molded articles (evaluation molded articles) of Experimental Example 9 and Experimental Example 13. Note that the molded articles of Experimental Example 9 and Experimental Example 1 are the same. Furthermore, the molded articles of Experimental Example 13 and Experimental Example 5 are the same.

[0096] (8) Molded articles of Experimental Example 12 and Experimental Example 16 The plant-derived PE prepared in [1](4) above was put into the hopper of an injection molding machine (100-ton injection molding machine), and injection molding was performed under injection conditions of a set temperature of 210°C and a mold temperature of 60°C to mold molded articles (evaluation molded articles) of Experimental Example 12 and Experimental Example 16. Note that the molded articles of Experimental Example 12 and Experimental Example 16 are the same.

[0097]

Table 2

[0098] [5] Evaluation of the molded body for evaluation (1) Measurement of density The density was measured in accordance with ISO 1183. Test temperature: 23°C Drying conditions: Vacuum drying at 80°C for 8 hours or more

[0099] (2) Measurement of MFR MFR (230°C / 2.16 kg) was measured in accordance with ISO 1133. Test apparatus: Melt indexer (manufactured by Toyo Seiki Seisakusho, Ltd., model "F-F01") Test temperature: 230°C Test load: 2.16 kgf Drying conditions: Vacuum drying at 80°C for 8 hours or more

[0100] (3) Measurement of Charpy impact strength Using the molded bodies of Experimental Examples 1 to 16 obtained in [4] above, the Charpy impact strength (test temperature 23°C) was measured in accordance with ISO 179. The results are shown in Table 1 and Table 2. In addition, in this measurement of Charpy impact strength, a test piece with a notch (type A) was used, and the impact was measured by the edgewise test method at a temperature of 23°C.

[0101] In addition, the impact resistance magnification in Table 1 and Table 2 indicates the magnification of the Charpy impact strength in the corresponding experimental example when the Charpy impact strength of the resin to be modified (plant-derived PE or non-plant-derived PP) is set to 1.0. Also, the total polyolefin amount indicates the total amount of polyolefin (plant-derived PE, plant-derived PE2, non-plant-derived PP) contained in each experimental example.

[0102] [6] Morphology The phase structure was observed using each test piece of Experimental Example 1 (Experimental Example 9) and Experimental Example 5 (Experimental Example 13). This phase structure was obtained by observing the processed surface of each test piece, which had been subjected to oxygen plasma etching treatment (oxygen plasma etching treatment at 100 W for 1 minute) and further osmium coating treatment, with a field emission scanning electron microscope (FE-SEM).

[0103] Among the obtained SEM images, an image of the surface of Experimental Example 1 magnified 5000 times is shown in Fig. 1, an image of the surface of Experimental Example 1 magnified 10000 times is shown in Fig. 2, and an image of the surface of Experimental Example 1 magnified 20000 times is shown in Fig. 3. Furthermore, an image of the surface of Experimental Example 5 magnified 5000 times is shown in Fig. 4, an image of the surface of Experimental Example 5 magnified 10000 times is shown in Fig. 5, and an image of the surface of Experimental Example 5 magnified 20000 times is shown in Fig. 6.

[0104] [7] Effects of Experimental Examples From the results in Table 1 and from the results of Experimental Example 3 and Experimental Example 7, it can be seen that when a modifier is blended with plant-derived PE1 at a blending ratio of 4:1 (by mass), although it is difficult to obtain a sufficient modification effect, from the results of Experimental Example 2 and Experimental Example 6, it can be seen that when a modifier is blended with plant-derived PE1 at a blending ratio of 1:1 (by mass), a high modification effect can be obtained. Also, from the results of Experimental Example 2 and Experimental Example 6, the total polyolefin amount of Experimental Example 2 with a Charpy impact strength of 13 kJ / m 2 is 65% by mass, while the total polyolefin amount of Experimental Example 6 with a Charpy impact strength of 23 kJ / m 2 reaches 80% by mass. And it can be seen that the impact resistance of Experimental Example 2 is 2.2 times that of Experimental Example 4, while the impact resistance of Experimental Example 6 reaches 3.8 times that of Experimental Example 8. Therefore, it can be seen that as a modifier, the modification performance of a modifier with a larger blending ratio of plant-derived PE2 is excellent. On the other hand, from the results in Table 2, the result is not that the modification performance of a modifier with a larger blending ratio of plant-derived PE2 is excellent, and a result is obtained suggesting that the utilization of plant-derived PE1 acts specifically.

[0105] Furthermore, from the results of FIGS. 1 to 3, it can be seen that the modifier of Experimental Example 1 has a phase structure in which plant-derived PA is the continuous phase A, plant-derived PE is the dispersed phase B, and furthermore, within the dispersed phase B, there are a continuous phase B1 within the dispersed phase and a finely dispersed phase B2. Furthermore, from the results of FIGS. 4 to 6, it can be seen that the modifier of Experimental Example 5 has a phase structure in which plant-derived PE is the continuous phase A, plant-derived PA is the dispersed phase B, and furthermore, within the dispersed phase B, there are a continuous phase B1 within the dispersed phase and a finely dispersed phase B2.

[0106] In addition, in the present invention, it is not limited to those described in the above specific examples, and various modified examples within the scope of the present invention can be provided according to the purpose and use.

[0107] The above examples are for illustrative purposes only and are not to be construed as limiting the present invention. Although the present invention has been described by way of examples of typical embodiments, the language used in the description and illustration of the present invention is to be understood as explanatory and illustrative rather than restrictive. As detailed herein, changes can be made within the scope of the appended claims without departing from the scope or spirit of the invention in its form. Here, specific structures, materials, and examples have been referred to in the detailed description of the present invention, but it is not intended to limit the present invention to the disclosed matters herein. Rather, the present invention is intended to cover all functionally equivalent structures, methods, and uses within the scope of the appended claims.

Explanation of Reference Numerals

[0108] A; Continuous phase, B; Dispersed phase, B1; Continuous phase (continuous phase within the dispersed phase B), B2; Finely dispersed phase (dispersed phase within the dispersed phase B).

Claims

1. The resin to be modified is polyethylene (PE １ ), and when the total with the resin to be modified is 100% by mass, it is a modifier that can improve the impact resistance of the resin to be modified by blending 30 to 70% by mass, Polyethylene (PE ２ ), polyamide, and a compatibilizer, and The compatibilizer is a modified elastomer having a reactive group with respect to the polyamide, the bio-based carbon content of the polyamide according to ISO 16620-2 is 80% or more, the polyethylene (PE 2) is a high-density polyethylene having an MFR (230°C / 2.16 kg) of 20 g / 10 min or less and a bio-based carbon content of 80% or more according to ISO 16620-2, and when the total of the polyethylene (PE 2), the polyamide, and the compatibilizer is 100% by mass, with the mass ratio of the polyethylene (PE 2) being RPE2% by mass and the mass ratio of the polyamide being RPA% by mass, a modifier characterized in that RPA < RPE2.

2. The total of the polyethylene (PE ２ ), the polyamide, and the compatibilizer is 100% by mass. When the mass ratio of the polyethylene (PE ２ ) is R ＰＥ２ % by mass, the mass ratio of the polyamide is R ＰＡ % by mass, and the mass ratio of the compatibilizer is R ＣＢ % by mass, 1 ≤ R ＣＢ (mass %) ≤ 70 and 0.3 ≤ R ＰＥ２ / R ＰＡ ≤ 3.5, the modifier according to claim 1

3. The modifier according to claim 1 or 2, wherein when the total of the polyethylene (PE 2), the polyamide, and the compatibilizer is 100% by mass, the mass ratio RCB (mass%) of the compatibilizer is 4 to 30% by mass.

4. The modifier according to any one of claims 1 to 3, wherein when the total of the polyethylene (PE 2), the polyamide, and the compatibilizer is 100% by mass, with the mass ratio of the polyethylene (PE 2) being RPE2% by mass, the mass ratio of the polyamide being RPA% by mass, and the mass ratio of the compatibilizer being RCB% by mass, RPE2:RPA:RCB satisfies 55 to 65:27 to 35:6 to 14.

5. The modifier according to any one of claims 1 to 4, wherein the polyamide has a structure in which the straight-chain carbon number of the hydrocarbon group sandwiched between adjacent amide bonds in the main chain is 6 or more.

6. The modifier according to any one of claims 1 to 5, wherein the compatibilizer has a copolymer chain derived from ethylene and other α-olefins as a main skeleton, and the reactive group is an acid-modified group.

7. The polyethylene (PE １ ) is a modifier according to any one of claims 1 to 6, which is high density polyethylene.

8. The modifier according to any one of claims 1 to 7, wherein the MFR (230°C / 2.16 kg) is 3 g / 10 min or more.

9. The melt kneaded product of the polyamide and the compatibilizer, and the polyethylene (PE ２ ), a modifier according to any one of claims 1 to 8 obtained by melt kneading.

10. Polyethylene (PE), which is the resin to be modified １ ), and a molding step of molding a raw material obtained by dry blending the modifier according to any one of claims 1 to 9. A method for producing a molded article, characterized by comprising:

11. The method for producing a molded article according to claim 10, wherein when the total of the resin to be modified and the modifier is 100% by mass, the modifier is 30 to 70% by mass.

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