Modifier and method for producing 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 polyolefin (excluding polyethylene) 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 the above 1 to 9.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a modifier and a method for producing 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 technology]

[0002] The following Patent Documents 1 and 2 disclose techniques for obtaining a thermoplastic resin composition having excellent impact resistance using three components: a polyolefin, a polyamide, and a compatibilizer. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2013-094763 Brochure [Patent Document 2] International Publication No. 2013-094764 Brochure Summary of the Invention [Problem to be solved by the invention]

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

[0005] Recently, the creation of a sustainable society and the associated reduction of environmental impact have been gaining attention, and there is an increasing demand for responses in the field of materials technology. Specifically, from the perspective of reducing CO2 emissions, technology that uses plant-derived materials instead of fossil-derived materials such as petroleum has attracted attention, and plant-derived products have been launched on the market for general-purpose resins, not only polyamides but also polyolefins. However, compared to the fossil-derived resins that have been used for a long time, there are only a limited number of grades available, and they have not yet been tailored to suit various applications. For this reason, it is not yet possible to directly replace traditionally used fossil-derived resins with plant-derived resins, and there are various difficulties in increasing the proportion of plant-derived resins.

[0006] The present invention has been made in view of the above circumstances, and aims to provide a modifier that contains three components: polyethylene, polyamide, and a compatibilizer, and that can impart impact resistance to polyolefins (excluding polyethylene) while reducing the environmental impact. Another aim is to provide a method for producing a molded article using this modifier. [Means for solving the problem]

[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 that is a polyolefin (excluding polyethylene), Contains polyethylene (PE2), polyamide and compatibilizer, the compatibilizer is a modified elastomer having a group reactive with the polyamide, The gist is that the polyethylene (PE2) and polyamide have a bio-based carbon content of 80% or more according to ISO 16620-2. [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 mass%, and the mass ratio of the polyamide is R PAmass%, and the mass ratio of the compatibilizer is R CB In the case of mass%, 1≦R CB (mass%)≦70 and 0.3≦R PE2 / R PA It can be ≦3.5. [3] The modifier of the present invention can convert the polyethylene (PE2) into high-density polyethylene. [4] The modifier of the present invention can reduce the MFR (230°C / 2.16 kg) of the polyethylene (PE2) to 20 g / 10 min or less. [5] In the modifier of the present invention, the polyamide can have a structure in which the hydrocarbon groups sandwiched between adjacent amide bonds in the main chain have a linear carbon number of 6 or more. [6] In the modifier of the present invention, the compatibilizer may have a main skeleton of a copolymer chain derived from ethylene and other α-olefins, and the reactive group may be an acid-modified group. [7] In the modifier of the present invention, the polyolefin can be a block polypropylene. [8] The modifier of the present invention can achieve an MFR (230°C / 2.16 kg) of 3 to 17 g / 10 min. [9] The modifier of the present invention can be obtained by melt-kneading a melt-kneaded mixture of the polyamide and the compatibilizer with the polyethylene (PE2).

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

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

[0008] The modifier of the present invention can impart impact resistance to polyolefins other than polyethylene while reducing the environmental load. According to the method for producing a molded article of the present invention, a polyethylene substrate molded article having excellent impact resistance can be obtained easily with a small number of steps without going through a pre-mixing step, while reducing the environmental load. [Brief explanation of the drawings]

[0009] [Figure 1] Phase structure obtained by magnifying the surface of the test piece in Experimental Example 1 by 5000 times [Figure 2] Phase structure obtained by magnifying the surface of the test piece in Experimental Example 1 by 10,000 times [Figure 3] Phase structure obtained by magnifying the surface of the test piece in Experimental Example 1 by 20,000 times [Figure 4] Phase structure obtained by magnifying the surface of the test piece in Experimental Example 5 by 5000 times [Figure 5] Phase structure obtained by magnifying the surface of the test piece in Experimental Example 5 by 10,000 times [Figure 6] Phase structure obtained by magnifying the surface of the test piece in Experimental Example 5 by 20,000 times DETAILED DESCRIPTION OF THE INVENTION

[0010] The matters set forth herein are for illustrative purposes only and are intended to provide an illustrative description of the embodiments of the present invention, with the aim of providing what is believed to be the most effective and easily understandable explanation of the principles and conceptual features of the present invention. In this respect, it is not intended to show structural details of the present invention beyond the extent necessary for a fundamental understanding of the present invention, and the description, taken together with the drawings, will make clear to those skilled in the art how some aspects of the present invention may be actually embodied. In this specification, the expression "XX to YY" means "XX or more and YY or less."

[0011] [1] Modifier The modifier of the present invention is a polyolefin modifier for polyolefins (excluding polyethylene) whose resin is to be modified. By blending the modifier of the present invention, it is possible to improve the impact resistance of polyolefins other than polyethylene.

[0012] The modifier of the present invention comprises polyethylene (PE2), polyamide, and a compatibilizer, which is a modified elastomer having a group reactive with polyamide. Furthermore, polyethylene (PE2) has a bio-based carbon content of 80% or more according to ISO 16620-2. In other words, 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, meaning it is a plant-derived polyamide (plant-derived PA).

[0013] <1> Polyethylene PE2 The polyethylene PE2 has a bio-based carbon content of 80% or more as measured in accordance with the ISO 16620-2 standard (in this specification, this polyethylene is also referred to simply as "plant-derived PE2"). This bio-based carbon content is the percentage of the total carbon content. 14 This is the plant-derived carbon content (bio-based carbon content) calculated based on the proportion of C. The plant-derived PE2 used in the present invention may have a bio-based carbon content of 80% or more (or 100%), and may further have a bio-based carbon content of 85% or more, or even 90% or more. In addition to ISO 16620-2, values ​​measured in accordance with ASTM D6866 can also be used for the bio-based carbon content. Generally, the values ​​measured in accordance with these standards are essentially the same.

[0014] Plant-derived PE2 is a polymer whose main backbone is a structure (methylene chain) consisting of a series of methylene groups (-CH2-). The methylene chain is a structural unit derived specifically from ethylene. Furthermore, plant-derived PE2 includes ethylene homopolymers and copolymers of ethylene and other olefins. These may be used alone or in combination of two or more. When plant-derived PE2 is a copolymer, non-ethylene-derived units (units derived from other olefins) preferably account for 50% or less (more preferably 30% or less, and even more preferably 10% or less) of the total number of constituent units. This is because a lower proportion of non-ethylene-derived units can increase the bio-based carbon content. In other words, plant-derived PE2 is preferably a substantially ethylene homopolymer with a low proportion of non-ethylene-derived units (for example, 10% or less).

[0015] Examples of the 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.), etc. These may be used alone or in combination of two or more.

[0016] The properties of plant-derived PE2 are not limited, but include a density of 0.942 g / cm 3 Preferably, the plant-derived PE2 is a high-density polyethylene of 35 g / 10 min or higher. Furthermore, the MFR (230°C / 2.16 kg) of the plant-derived PE2 is preferably 35 g / 10 min or lower. By ensuring that the plant-derived PE2 has an MFR of 35 g / 10 min or lower (usually 1 g / 10 min or higher), the resulting modifier can have excellent modifying performance. This MFR is preferably 20 g / 10 min or lower, and more preferably 15 g / 10 min or lower. While there are no lower limits, from the viewpoint of ease of melt-kneading, it is preferably 2 g / 10 min or higher, and more preferably 3 g / 10 min or higher. In the present invention, the MFR (230°C / 2.16 kg) of polyethylene is a value measured in accordance with the standard of ISO 1133 or ASTM D 1238. The values ​​according to these standards are usually substantially the same.

[0017] As mentioned above, the density of plant-derived PE2 is 0.942 g / cm 3 or more, and more preferably, a density of 0.950 g / cm 3 The upper limit of the density is not limited, but is preferably 0.954 g / cm 3 It is preferable that: The compatibility of the above-mentioned MFR and density can be adjusted by adjusting the linearity, branching amount, molecular weight, etc. of the polyethylene. In the present invention, the density of polyethylene is a value measured in accordance with the standard ISO 1183 or ASTM D 792. The values ​​according to these standards are usually substantially the same.

[0018] Furthermore, the MFR (230°C / 2.16 kg) of the plant-derived PE2 is preferably small. Specifically, it is preferable that the MFR be closer to the MFR (230°C / 2.16 kg) of the melt-kneaded product obtained from the plant-derived PA and the compatibilizer, which will be described later. That is, the kneading of the plant-derived PA and the compatibilizer is thought to be promoted by the reaction between the two, and the kneading of the two is less affected by the difference in MFR. In contrast, the kneading of the plant-derived PE2 and the melt-kneaded product (the melt-kneaded product of the plant-derived PA and the compatibilizer) is thought to be more affected by the difference in MFR because the two do not react. Therefore, by making the MFR of the plant-derived PE2 closer to the MFR of the melt-kneaded product, the kneading ability improves, and impact resistance is thought to be improved accordingly.

[0019] Specifically, the MFR (230°C / 2.16 kg) of plant-derived PE2 was calculated as PE2 (g / 10 min), and the MFR (230°C / 2.16 kg) of the melt-kneaded mixture of plant-derived PA and compatibilizer was M PX (g / 10 min), the ratio M PE2 / PX (=M PE2 / M PX ) is 0.5≦M PE2 / PX ≦20, and 1≦M PE2 / PX ≦17, more preferably 2≦M PE2 / PX ≦13, and more preferably 5≦M PE2 / PX It is particularly preferred that it is ≦10. Furthermore, M PX The range of is not limited, but for example, 0.1≦M PX (g / 10 min)≦10, and further, 0.5≦M PX (g / 10 min)≦5, and further, 1≦M PX (g / 10 min)≦3.

[0020] <2> Polyamide The polyamide has a bio-based carbon content of 80% or more as measured in accordance with the ISO16620-2 standard (in this specification, the polyamide is also referred to simply as "plant-derived PA"). This bio-based carbon content is the percentage of the total carbon content. 14 This is the plant-derived carbon content (bio-based carbon content) calculated based on the proportion of C. The plant-derived PA used in the present invention may have a bio-based carbon content of 80% or more (or 100%), and may further have a bio-based carbon content of 90% or more, or even 95% or more. In addition to ISO 16620-2, values ​​measured in accordance with ASTM D6866 can also be used for the bio-based carbon content. Generally, the values ​​measured in accordance with these standards are essentially the same.

[0021] Plant-derived PA is a polymer whose main skeleton consists of hydrocarbon groups (especially methylene chains) linked together via amide bonds (-NH-CO-). Examples of monomers constituting 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, undecanelactam, and ω-lauryllactam. These may be used alone or in combination of two or more. Among these, from the viewpoint of a high biobased carbon content, it is preferable that the plant-derived 11-aminoundecanoic acid is contained in large amounts.

[0022] Furthermore, plant-derived PA can also be obtained by copolymerization of diamine and dicarboxylic acid. In this case, examples of diamine as a monomer include 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-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminopentane, 1,17-diaminopentane, 1,18-diaminopentane, 1,19-diaminopentane, 1,20-diaminopentane, 1,21-diaminopentane, 1,22-diaminopentane, 1,23-diaminopentane, 1,24-diaminopentane, 1,25-diaminopentane, 1,26-diaminopentane, 1,27-diaminopentane, 1,28-diaminopentane, 1,29-diaminopentane, 1,30-diaminopentane, 1,31-diaminopentane, 1,32-diaminopentane, 1,33-diaminopentane, 1,34-diaminopentane, 1,35-diaminopentane, 1,36-diaminopentane, 1,37-diaminopentane, 1,38-diaminopentane, 1,39-diaminopentane, 1,40-diaminopentane, 1,41-diaminopentane, 1,42-diaminopentane, 1,43-diaminopentane, 1,44-diaminopentane, 1,45-diaminopentane, Examples of suitable diamines include aliphatic diamines such as 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 xylylenediamines (e.g., p-phenylenediamine and m-phenylenediamine). These may be used alone or in combination. Among these, from the viewpoint of a high biobased carbon content, it is preferable to use a large amount of plant-derived 1,10-diaminodecane and / or 1,5-diaminopentane.

[0023] Further, examples of dicarboxylic acids as monomers 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, brassicic acid, tetradecanedioic acid, pentadecanedioic acid, and octadecanedioic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; and furandicarboxylic acid. These may be used alone or in combination of two or more. Among these, from the viewpoint of a high biobased carbon content, it is preferable that plant-derived sebacic acid, furandicarboxylic acid, and / or glutaric acid are contained in large amounts.

[0024] Furthermore, the plant-derived PA preferably has a structure in which the hydrocarbon groups sandwiched between adjacent amide bonds in the main chain have a linear carbon number of 6 or more. Therefore, examples of 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), and polyamide MXD10 (MXD10). These polyamides may be used alone or in combination of two or more. Furthermore, when two or more types are used, this includes both pellets made of mixed resins and pellet mixtures.

[0025] Furthermore, 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, the plant-derived PA is formed when the monomers that form these polymers are derived from plant materials. The entire amount of the monomers may be plant-derived monomers, or only a portion of the monomers may be plant-derived monomers (i.e., the remaining portion may contain fossil-derived monomers). In other words, the plant-derived PA is sufficient as long as it ultimately has a bio-based carbon content of 80% or more.

[0026] Although the properties of plant-derived PA are not limited, the density is 1.15 g / cm 3 Preferably, the polyamide is one of the above polyamides and has an MFR (230°C / 2.16 kg) of 50 g / 10 min or less. By ensuring that the plant-derived PA has an MFR of 50 g / 10 min or less (usually 1 g / 10 min or more), the resulting modifier will have excellent modifying performance. This MFR is preferably 40 g / 10 min or less, and more preferably 35 g / 10 min or less. While there are no restrictions on the lower limit, from the viewpoint of ease of melt-kneading, it is preferably 3 g / 10 min or more, and more preferably 5 g / 10 min or more. In the present invention, the MFR (230°C / 2.16 kg) of the plant-derived PA is a value measured in accordance with the standard of ISO 1133 or ASTM D 1238. The values ​​according to these standards are usually substantially the same.

[0027] In addition, as mentioned above, the density of plant-derived PA is 1.15 g / cm 3 Preferably, the density is 1.08 g / cm or less. 3 The lower limit of the density is not limited, but is preferably 0.98 g / cm. 3 It is preferable that this is equal to or greater than this. The compatibility of 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 in accordance with the standard ISO 1183 or ASTM D 792. The values ​​according to these standards are usually substantially the same.

[0028] <3> Compatibilizer The compatibilizer is a modified elastomer having a group reactive with plant-derived PA. Furthermore, the compatibilizer is preferably a component having affinity for plant-derived PE2. In this case, the compatibilizer is a component having a compatibilizing effect on plant-derived PE2 and plant-derived PA. That is, the compatibilizer is preferably a compatibilizer for plant-derived PE2 and plant-derived PA. Furthermore, the compatibilizer may be reacted entirely with the plant-derived PA within the present modifier, or only a portion of it may be reacted.

[0029] The reactive group possessed by the modified elastomer should be reactive with the plant-derived PA, and examples thereof include an acid anhydride group (-CO-O-OC-), a carboxyl group (-COOH), an epoxy group {-CO (a three-membered ring structure consisting of two carbon atoms and one oxygen atom)}, an oxazoline group (-C3H4NO), an isocyanate group (-NCO), etc. These may be used alone or in combination of two or more. The amount of modification of the modified elastomer with the reactive groups is not limited, and it is sufficient that the modified elastomer has one or more reactive groups in one molecule. Furthermore, it is preferable that the modified elastomer has 1 to 50 reactive groups, more preferably 3 to 30 reactive groups, and particularly preferably 5 to 20 reactive groups.

[0030] Examples of modified elastomers include polymers made with various monomers capable of introducing reactive groups (modified elastomers obtained by polymerization using monomers capable of introducing reactive groups), oxidative decomposition products of various polymers (modified elastomers in which reactive groups are formed by oxidative decomposition), and graft polymers of organic acids onto various polymers (modified elastomers in which reactive groups are introduced by graft polymerization of organic acids). These may be used alone or in combination of two or more. These may be used alone or in combination of two or more.

[0031] Examples of the monomer into which a reactive group can be introduced include a monomer having a polymerizable unsaturated bond and an acid anhydride group, a monomer having a polymerizable unsaturated bond and a carboxyl group, and a monomer having a polymerizable unsaturated bond and an epoxy group. Specific examples include acid anhydrides such as maleic anhydride, itaconic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, and butenyl succinic anhydride, and carboxylic acids such as maleic acid, itaconic acid, fumaric acid, acrylic acid, and methacrylic acid. These may be used alone or in combination of two or more. Of these compounds, acid anhydrides are preferred, with maleic anhydride and itaconic anhydride being more preferred, and maleic anhydride being 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, the olefin-based elastomers include those obtained by copolymerizing two or more kinds of olefins. Examples of the olefin include ethylene, propylene, and α-olefins having 4 to 8 carbon atoms. Among these, examples of the α-olefins 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, and 1-octene.

[0034] Among these, copolymers of ethylene and other α-olefins are preferred as olefin-based elastomers. That is, as compatibilizers, modified elastomers having copolymer chains derived from ethylene and other α-olefins as the main skeleton and having groups reactive with plant-derived PA are preferred. When such olefin-based elastomers are used, it is possible to obtain thermoplastic resin compositions that give molded articles with particularly excellent impact resistance. Furthermore, as α-olefins other than ethylene, α-olefins having 3 to 8 carbon atoms are preferred, and α-olefins having 4 to 8 carbon atoms are more preferred.

[0035] Among the above, copolymers of ethylene and α-olefins 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). Furthermore, copolymers of propylene and α-olefins 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. Furthermore, when two or more types are used, this includes both pellets made of mixed resins and pellet mixtures.

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

[0037] That is, examples of styrene-based thermoplastic elastomers include styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), styrene-ethylene / butylene-styrene copolymer (SEBS), and styrene-ethylene / propylene-styrene copolymer (SEPS). These may be used alone or in combination of two or more. Furthermore, when two or more types are used, this includes both pellets made of mixed resins and pellet mixtures. Among these, SEBS is preferred.

[0038] The properties of the compatibilizer are not limited, but the density is 0.90 g / cm 3 The modified elastomer is preferably one of the following, and has an MFR (230°C / 2.16 kg) of 10 g / 10 min or less. By making the MFR of the compatibilizer 10 g / 10 min or less (usually 0.5 g / 10 min or more), the resulting modifier can have excellent modifying performance. This MFR is more preferably 7 g / 10 min or less, and more preferably 5 g / 10 min or less. There is no upper limit, but from the viewpoint of ease of melt-kneading, it is preferably 0.5 g / 10 min or more, and more preferably 1.0 g / 10 min or more. In the present invention, the MFR (230°C / 2.16 kg) of the compatibilizer is a value measured in accordance with the standard of ISO 1133 or ASTM D 1238. The values ​​according to these standards are usually substantially the same.

[0039] The density of the compatibilizer is 0.90 g / cm as mentioned above. 3 Preferably, it is 0.89 g / cm or less, and more preferably, it is 0.89 g / cm or less 3 The lower limit of the density is not limited, but is preferably 0.85 g / cm. 3 It is preferable that this is equal to or greater than this. The compatibility of 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 in accordance with the standard of ISO 1183 or ASTM D 792. 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 from 10,000 to 500,000, more preferably from 35,000 to 500,000, and particularly preferably from 35,000 to 300,000. The weight-average molecular weight is measured by the GPC method (standard polystyrene equivalent).

[0041] <4> Composition of each ingredient When the total of the plant-derived PE2, plant-derived PA, and compatibilizer constituting the modifier of the present invention is taken as 100 mass%, the mass ratio of the plant-derived PE2 is R PE2 mass%, and the mass ratio of plant-derived PA is R PA mass%, and the mass ratio of the compatibilizer is R CB Expressed as mass %. In this case, the mass ratio R of the compatibilizer CB The content (mass %) is preferably 1 to 70 mass %, more preferably 2 to 60 mass %, more preferably 2 to 50 mass %, more preferably 3 to 40 mass %, more preferably 3 to 35 mass %, and even more preferably 4 to 30 mass %.

[0042] In addition, the mass ratio R of plant-derived PE2 PE2 and the mass fraction of plant-derived PA R PA Ratio to (R PE2 / R PA ) is preferably 0.3 to 3.5. PE2 / R PA) can further be set to 0.4 to 2.0, 0.35 to 2.00, 0.40 to 1.50, or 0.45 to 1.20.

[0043] On the other hand, when the resin to be modified is polypropylene (particularly block polypropylene), the modifier of the present invention is R PE2 <R PA than R PE2 ≧R PA The modified resin composition obtained tends to have excellent impact resistance while increasing the total amount of polyolefin in the resulting modified resin composition. That is, since polyamides have higher impact resistance than polyolefins, excellent impact resistance can usually be obtained by increasing the blending ratio of polyamide. However, in the modifier of the present invention, modifiers containing less polyolefin have better impact resistance imparting performance than modifiers containing more polyamide. More specifically, the ratio (R PE2 / R PA ) is preferably 1 to 3.5, more preferably 1.0 to 3.3, more preferably 1.2 to 3.0, more preferably 1.5 to 2.5, and even more preferably 1.8 to 2.3. PE / R PA ) is the mass fraction of the compatibilizer, R CB It is particularly effective when the content is in the range of 30 mass % or less.

[0044] In addition, the mass ratio R of plant-derived PE2 PE2 The content (mass %) is preferably 10 to 90 mass %, more preferably 13 to 85 mass %, more preferably 17 to 80 mass %, more preferably 20 to 75 mass %, more preferably 23 to 70 mass %, and more preferably 25 to 65 mass %. Furthermore, the total ratio R of plant-derived PA and compatibilizer PA+CB The content (mass %) is preferably 10 to 90 mass %, more preferably 15 to 87 mass %, more preferably 20 to 83 mass %, more preferably 25 to 80 mass %, more preferably 30 to 77 mass %, and more preferably 35 to 75 mass %. In addition, the mass ratio of plant-derived PA R PAThe content (mass %) is preferably 1 to 80 mass %, more preferably 3 to 75 mass %, more preferably 5 to 70 mass %, more preferably 10 to 75 mass %, more preferably 15 to 70 mass %, and more preferably 20 to 65 mass %.

[0045] Furthermore, when the total of the plant-derived PA and the compatibilizer is 100% by mass, the mass proportion of the compatibilizer is preferably 3 to 70% by mass, more preferably 4 to 65% by mass, more preferably 5 to 60% by mass, more preferably 6 to 55% by mass, more preferably 7 to 45% by mass, and more preferably 8 to 40% by mass.

[0046] In particular, the mass ratio R of plant-derived PA PA is the mass ratio of plant-derived PE2, R PE2 The range (i.e., R PA <R PE2 ) to obtain a modifier that can provide high impact resistance, PE2 :R PA :R CB are preferably 50-80 mass%: 20-45 mass%: 1-25 mass%, more preferably 52-70 mass%: 24-40 mass%: 3-18 mass%, and particularly preferably 55-65 mass%: 27-35 mass%: 6-14 mass%. Within the above ranges, the Charpy impact strength of polyolefin (particularly polypropylene) can be improved by three times or more, and further improved by four times or more, by modification.

[0047] The fluidity of the modifier of the present invention is not limited, but the density is preferably 0.93 to 1.00 g / cm 3 At the same time, the MFR (230°C / 2.16 kg) can be 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, 12 g / 10 min or more, or even 17 g / 10 min or more. There is no upper limit, but it can be 27 g / 10 min or less. Furthermore, it can be particularly increased to 3 to 30 g / 10 min, further increased to 3 to 27 g / 10 min, further increased to 3 to 17 g / 10 min, or further increased to 3 to 12 g / 10 min. In the present invention, the MFR (230°C / 2.16 kg) of the compatibilizer is a value measured in accordance with the standard of ISO 1133 or ASTM D 1238. The values ​​according to these standards are usually substantially the same.

[0048] The phase structure of the modifier of the present invention is not limited, but typically has specific phase structures (1) to (3). Specifically, (1) the modifier 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 Figures 1 to 3). Furthermore, the dispersed phase (B) can have a continuous phase (B1) containing plant-derived PE2 (i.e., 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., dispersed phase B2 within the dispersed phase) (see Figure 3).

[0049] Also, (2) 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 Figures 4 to 6). Furthermore, the dispersed phase (B) can have a continuous phase (B1) containing the plant-derived PA (i.e., 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., dispersed phase B2 within the dispersed phase) (see Figure 6). In particular, the phase structure having the finely dispersed phase (B2) can provide excellent impact resistance.

[0050] Furthermore, the phase structure (3) can exhibit a bicontinuous structure in which the phase structures (1) and (2) are mixed. In particular, when the phase structures (1) and (2) are present, excellent impact resistance can be obtained due to the phase structure having the finely dispersed phase (B2).Similarly, when the co-continuous structure (3) is present, excellent impact resistance can also be obtained.

[0051] When the phase structure described above is used, the size of the dispersed phase contained in the continuous phase is not limited, but its average diameter (average particle diameter) is preferably 10,000 nm or less, more preferably 50 to 8,000 nm, and even more preferably 100 to 4,000 nm. The average diameter of the dispersed phase is the average value (nm) of the maximum lengths of 50 dispersed phase particles randomly selected in an image obtained using an electron microscope.

[0052] In the case of the dispersed phase within the dispersed phase, the size of the finely dispersed phase contained within the dispersed phase is not limited, but the average diameter (average particle diameter) is preferably 5 to 1000 nm, more preferably 5 to 600 nm, even more preferably 10 to 400 nm, and particularly preferably 15 to 350 nm. The average diameter of the finely dispersed phase is the average value (nm) of the maximum lengths of 100 finely dispersed phase particles randomly selected in an image obtained using an electron microscope.

[0053] <5> Manufacturing of modifiers The modifier of the present invention may be produced in any manner, but can be obtained by melt-kneading a melt-kneaded mixture of plant-derived PA and modified elastomer with plant-derived PE 2. That is, the modifier of the present invention can be obtained by a production method including a melt-kneading step of melt-kneading a melt-kneaded mixture of plant-derived PA and compatibilizer, and plant-derived PE 2.

[0054] The melt-kneaded mixture of the plant-derived PA and the compatibilizer may be a composition in a molten state or a softened state, or may be solidified by pelletizing or the like. In addition, any melt-kneading device may be used in the melt-kneading step. For example, an extruder (such as a single-screw extruder or a twin-screw kneading extruder), a kneader, or a mixer (such as a high-speed fluid mixer, a paddle mixer, or a ribbon mixer) may be used. These devices may be used alone or in combination of two or more. When two or more types are used, they may be operated continuously or in batches (batchwise). Furthermore, the raw materials may be mixed all at once, or may be added and mixed in multiple batches (multi-stage blending). The kneading temperature in the melt-kneading step is not particularly limited, but is preferably 190 to 350°C, more preferably 200 to 300°C, and even more preferably 205 to 260°C.

[0055] The above method uses a melt-kneaded product. To obtain this melt-kneaded product, kneading is performed when the plant-derived PA and the compatibilizer react. Therefore, it is believed that the compatibilizer, which has a reactive group, adds a reactive group to the surface of the plant-derived PA, forming a plant-derived PA with the compatibilizer bonded to its surface. Further kneading then shears the surface-bonded plant-derived PA, revealing the surface of the unreacted plant-derived PA. It is believed that the unreacted compatibilizer then further reacts with this unreacted surface. By repeating this process of shearing the plant-derived PA with the compatibilizer bonded to it, revealing the surface of the unreacted plant-derived PA, and then reacting the unreacted compatibilizer with this unreacted surface, it is believed that a smaller reaction product between the plant-derived PA and the compatibilizer can be stably formed without relying on high shear. Furthermore, if the amount of compatibilizer that can be supplied during the above-mentioned process is small, it is thought that the plant-derived PA to which the compatibilizer is bonded will not easily become small, and if the amount of compatibilizer that can be supplied is sufficiently large, it will be easy for the plant-derived PA to which the compatibilizer is bonded to become small.

[0056] <6> Resins to be modified (polyolefins excluding polyethylene) The resins to be modified with the modifier of the present invention are polyolefins other than polyethylene. Polyethylene refers to all polyethylenes regardless of their origin. That is, it may be fossil-derived polyethylene, plant-derived polyethylene, or polyethylene with both origins.

[0057] The polyolefin may be a fossil-derived polyolefin having a bio-based carbon content of less than 80% according to ISO16620-2, or a plant-derived polyolefin having a bio-based carbon content of 80% or more. The olefin constituting the polyolefin is not limited, and examples thereof include ethylene, 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.), etc. These may be used alone or in combination of two or more. That is, examples of polyolefins include polypropylene, poly-1-butene, poly-1-hexene, and poly-4-methyl-1-pentene. These polymers may be used alone or in combination of two or more. Furthermore, when two or more types are used, this includes both pellets made of mixed resins and pellet mixtures.

[0058] Of the above, polypropylene includes propylene homopolymers and copolymers of propylene with other olefins. Examples of the latter include propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-1-hexene copolymers, propylene-1-octene copolymers, and propylene-4-methyl-1-pentene copolymers. Furthermore, copolymers of propylene and other olefins may be random copolymers or block polypropylenes (block copolymers). Among these, block polypropylenes are preferred because of their excellent impact resistance. In particular, propylene-ethylene block copolymers, in which the other olefin is ethylene, are preferred. Propylene-ethylene block copolymers are block copolymer polypropylenes with ethylene blocks as the dispersed phase. That is, they are polypropylene resins in which a homopolypropylene serves as the continuous phase and a dispersed phase containing polyethylene exists within this continuous phase. Block copolymer polypropylenes with ethylene blocks as the dispersed phase are also known as impact copolymers, polypropylene impact copolymers, heterophasic polypropylenes, and heterophasic block polypropylenes. These block polypropylenes are preferred because of their excellent impact resistance. In the copolymer of propylene and another olefin, 50% or more of the total number of constituent units are units derived from propylene.

[0059] The properties of the polyolefin are not limited. For example, in the case of polypropylene, the density is 0.85 to 0.95 g / cm 3 (Furthermore, the density is 0.88 to 0.92 g / cm 3 ) block polypropylene can be used. Its MFR (230°C / 2.16 kg) is not limited, but is preferably 15 g / 10 min or more. By making the MFR of the polypropylene 15 g / 10 min or more (usually 100 g / 10 min or less), it is possible to obtain better impact resistance properties in the molded article. This MFR is more preferably 20 g / 10 min or more, and more preferably 25 g / 10 min or more. Although the upper limit is not limited, from the viewpoint of ease of melt-kneading, it is preferably 80 g / 10 min or less, and more preferably 50 g / 10 min or less. In the present invention, the MFR (230°C / 2.16 kg) of polyolefins is a value measured in accordance with ISO 1133 or ASTM D1238. The values ​​according to these standards are usually substantially the same. The compatibility of MFR and density can be adjusted by the linearity, branching amount, molecular weight, etc. of the polyolefin.

[0060] <7> Use as a carrier for modifier additives The modifier of the present invention can be blended with the resin to be modified for the purpose of improving its impact resistance, and can also be used as a carrier for adding additives to the resin to be modified. In this case, the additives can be added to the resulting molded article at the same time as improving (modifying) the impact resistance. In this case, the modifier of the present invention is a carrier for adding an additive to a resin to which the additive is added, the resin being a polyolefin (excluding polyethylene), Contains additives, polyethylene (PE2), polyamide and compatibilizers. the compatibilizer is a modified elastomer having a group reactive with the polyamide, In other words, the polyethylene (PE2) and polyamide are carriers having a bio-based carbon content of 80% or more according to ISO 16620-2.

[0061] The type of additive is not limited, and examples thereof include flame retardants, flame retardant assistants, fillers, colorants, antibacterial agents, antistatic agents, etc. These may be used alone or in combination of two or more. Furthermore, when the modifier of the present invention is used as a carrier for additives, the additives can be blended in an amount of, for example, 500 parts by mass or less, assuming that the total amount of plant-derived PE2, plant-derived PA, and compatibilizer is 100 parts by mass. The lower limit of the amount of additives contained is not limited, but can be, for example, 1 part by mass.

[0062] [2] Manufacturing method for molded body The method for producing 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. In other words, the method for producing a molded article of the present invention can be said to be a modification method. Dry blending can be utilized for this modification. That is, the modifier is mixed with raw material particles (pellets, granules, etc.) of the polyolefin (excluding polyethylene), which is the resin to be modified, by dry blending, and then the mixed particles are molded to obtain a modified molded body (e.g., a shaped body). Generally, during modification, the two are melt-kneaded, the resulting melt-kneaded product is pelletized, and the resulting modified pellets are molded to obtain a modified molded body (e.g., a shaped body). However, this method does not require melt-kneading, and excellent modification effects can be obtained by dry blending. That is, this method makes it possible to obtain a molded body of a polyolefin substrate with excellent impact resistance in a simple manner with a few steps, without going through a pre-kneading step, while reducing the environmental impact.

[0063] The amount of modifier used in this method is not limited, but can be 30 to 70 mass % when the total of the resin to be modified and the modifier is 100 mass %.Moreover, the modifier is preferably used in an amount of 35 to 65 mass %, and more preferably 40 to 60 mass %.

[0064] In particular, in the method for producing a molded article of the present invention, the resin to be modified is block polypropylene, and R PE2 ≧R PA By using a modifier having a high polyolefin content, a molded article having excellent impact resistance can be obtained. CB In the range of 30 mass% or less, the ratio (R PE2 / R PA ) is 1 to 3.5, preferably 1.0 to 3.3, further 1.2 to 3.0, further 1.5 to 2.5, or even 1.8 to 2.3, a molded article with a higher polyolefin content and excellent impact resistance can be obtained. In this case, as described above, when the total of the resin to be modified and the modifier is taken as 100% by mass, the modifier is used in an amount of 30 to 70% by mass, a molded article with a higher polyolefin content and excellent impact resistance can be obtained. 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.

[0065] Any known molding method can be used for molding. Specific examples include 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 molding, transfer molding, and insert molding. These methods may be used alone or in combination of two or more.

[0066] The shape, size, thickness, etc. of the molded article are not particularly limited, and the use thereof is also not particularly limited. The molded article is used, for example, as various parts used in vehicles such as automobiles, railway vehicles (vehicles in general), aircraft bodies (aircraft bodies in general), ships and hulls (hulls in general), and bicycles (vehicle bodies in general). Among these, automotive parts include exterior parts, interior parts, engine parts, electrical parts, etc. Specific examples of automotive exterior parts include 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, hubcaps, grill 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.

[0067] Automotive interior parts include trim parts such as door trim substrates (FR, RR, BACK), pockets, armrests, switch bases, decorative panels, ornament panels, EA materials, speaker grilles, and quarter trim substrates; pillar garnishes; cowl side garnishes (cowl side trim); seat parts such as shields, back boards, dynamic dampers, and side airbag peripheral parts; instrument panel parts such as center clusters, registers, center boxes (doors), grab doors, cup holders, and airbag peripheral parts; center consoles; overhead consoles; sun visors; deck boards (luggage boards), undertrays; package trays; high-mount stop lamp covers; CRS covers; seat side garnishes; scuff plates; room lamps; assist grips; safety belt parts; register blades; washer levers; window regulator handles; window regulator handle knobs; passing light levers, etc.

[0068] Automotive engine parts include alternator terminals, alternator connectors, IC regulators, light dimmer potentiometer bases, 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 coolant joints, carburetor main bodies, carburetor spacers, exhaust gas sensors, coolant 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, and torque control levers.

[0069] Automotive electrical parts include battery peripheral parts, air conditioner thermostats, heating warm air flow control valves, radiator motor brush holders, water pump impellers, turbine vanes, wiper motor related parts, distributors, starter switches, starter relays, transmission wire harnesses, windshield washer nozzles, air conditioner panel switch boards, fuel-related electromagnetic valve coils, wire harness connectors, SMJ connectors, PCB connectors, door grommet connectors, various connectors such as fuse connectors, horn terminals, electrical part insulating plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, cleaner cases, filter cases, power trains, etc.

[0070] Furthermore, the molded article can be used for various non-vehicular applications other than the above-mentioned vehicles, such as industrial materials such as ropes, spunbonds, abrasive brushes, industrial brushes, filters, transport containers, trays, transport dollies, and other general materials; Connectors, coils, sensors, LED lamps, sockets, resistors, relay cases, small switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, small variable speed gears, magnetic head bases, power modules, semiconductors, liquid crystal displays, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts, and other electronic components; Electrical equipment such as generators, electric motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, circuit breakers, knife switches, other pole rods, electrical component cabinets;

[0071] Housings for industrial robots, housings for nursing care robots, housings for drones (flying objects that fly by remote control, flying objects that fly autonomously), VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic 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 devices, mobile phones, smartphones, telephones and related parts, facsimile parts, copier parts, cleaning / washing equipment, motor parts and other home appliances and office products; Optical and precision instruments such as cameras, watches, microscopes, binoculars, telescopes, and eyeglasses; Food trays, storage boxes, storage trays, attaché cases, suitcases, helmets, storage cases for water bottles, bottles, etc., toiletries, writing implements, stationery, book stands, skin care products, tools, tableware, laundry tools, cleaning tools, clothes hangers, food containers, opening and closing lids (glass bottles, etc.), and other daily necessities and household items;

[0072] toys and other entertainment items; Lawn mower housings, covers, power tool housings, covers, various clips and other general machinery and parts; Tennis racket strings, skis and boards, protectors (baseball, soccer, motorsports), shoes, shoe soles (sole, sole for sports shoes), outdoor and mountain climbing equipment, and other sporting goods; Furniture related items such as clothing cases, tables, chairs, shoeboxes, kitchen utensils, toilet utensils, bathing equipment, etc. Interior and exterior walls and roofs, insulation materials, doors and door-related parts, window-related parts, flooring-related parts, seismic isolation and vibration control parts, rain shutters, rain gutters, water supply and sewage-related parts (lifeline-related), parking garages, gas and electricity-related parts (lifeline-related), civil engineering parts, traffic lights, road signs, pylons, center poles, guardrails (guard wires), construction equipment, and other housing and civil engineering-related products; Medical supplies such as mouthpieces, medical devices, and medicine containers; Shoes and other clothing items, Examples include agricultural machinery, farming tools, flower pots, fishing equipment, aquaculture equipment, forestry tools, and other agricultural, forestry, and fishery related products. [Example]

[0073] The present invention will be specifically described below with reference to examples. [1]Each raw material component (1) Plant-derived PE2 The following polyethylene was prepared as plant-derived PE2. HDPE (Braskem, product name "SHC7260"), density 0.953 g / cm 3 , MFR (230℃ / 2.16kg) 12g / 10min, bio-based carbon content 94% or more

[0074] (2) Plant-derived PA The following polyamides were prepared as plant-derived PAs. PA11 (Arkema, product name "Rilsan BMN O"), density 1.03 g / cm 3 , MFR (230℃ / 2.16kg) 32g / 10min, bio-based carbon content 99% or more

[0075] (3) Compatibilizer The following ethylene-1-butene copolymer was prepared as a compatibilizer. Maleic anhydride-modified EBR (Mitsui Chemicals, product name "Tafmer MH7020"), density 0.866 g / cm 3 , MFR(230℃ / 2.16kg)1.5g / 10min

[0076] (4) Resin to be modified The following non-plant-derived PP and plant-derived PE were prepared as resins to be modified. Non-plant-derived PP: Block polypropylene (Prime Polymer Co., Ltd., product name "J817U"), density 0.90 g / cm 3 , MFR (230℃ / 2.16kg) 31g / 10min, bio-based carbon content 0% Plant-derived PE: HDPE (manufactured by Braskem, product name "SHA7260"), density 0.955 g / cm 3 , MFR (230℃ / 2.16kg) 32g / 10min, bio-based carbon content 94% or more

[0077] [2] Preparation of molten mixture The plant-derived PA and the compatibilizer were dry-blended at a 6:1 or 3:1 ratio (by mass), then loaded into a twin-screw melt-kneading extruder (Plastic Engineering Research Institute, Inc., screw diameter 30 mm, L / D = 42) and melt-kneaded at a mixing temperature of 210°C, an extrusion rate of 3.0 kg / h, and a screw rotation speed of 200 rpm. The melt-kneaded mixture was pelletized using a pelletizer. The MFR (230°C / 2.16 kg) of the resulting melt-kneaded mixtures was 5.9 g / 10 min for Melt-kneaded Product A, which had a plant-derived PA:compatibilizer ratio of 6:1, and 0.98 g / 10 min for Melt-kneaded Product B, which had a plant-derived PA:compatibilizer ratio of 3:1.

[0078] [3] Preparation of modifier (1) Preparation of modifiers for Experimental Examples 1 and 9 The molten mixture A obtained in [2] above and the plant-derived PE2 were dry-blended in a compounding ratio (by mass) of 7:3, then charged into a twin-screw melt kneading extruder (manufactured by Plastics Technology Research Institute Co., Ltd., screw diameter 30 mm, L / D = 42) and mixed under conditions of a kneading temperature of 210°C, an extrusion rate of 3.0 kg / hour, and a screw rotation speed of 200 rpm, and passed through a pelletizer to obtain modifiers (pellets) for Experimental Examples 1 and 9. The resulting modifiers had a density of 0.99 g / cm. 3 The MFR (230°C / 2.16 kg) was 22.8 g / 10 min.

[0079] (2) Preparation of modifiers for Experimental Examples 5 and 13 The molten mixture B obtained in [2] above and the plant-derived PE2 were dry-blended in a compounding ratio (by mass) of 4:6, then charged into a twin-screw melt kneading extruder (manufactured by Plastics Technology Research Institute Co., Ltd., screw diameter 30 mm, L / D = 42) and mixed under conditions of a kneading temperature of 210°C, an extrusion rate of 3.0 kg / hour, and a screw rotation speed of 200 rpm, and passed through a pelletizer to obtain modifiers (pellets) for Experimental Examples 5 and 13. The resulting modifiers had a density of 0.94 g / cm. 3 The MFR (230°C / 2.16 kg) was 4.9 g / 10 min.

[0080] [4] Manufacturing of molded bodies (1) Production of molded bodies in Experimental Examples 2 and 3 The modifier of Experimental Example 1 obtained in [3] above was dry-blended with the non-plant-derived PP (block polypropylene), the resin to be modified, at a blending ratio of 1:1 (Experimental Example 2) and a blending ratio of 1:4 (Experimental Example 3). The resulting dry-blend raw material was then placed in 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 molded bodies (molded bodies for evaluation) of Experimental Examples 2 and 3.

[0081] (2) Production of molded bodies of Experimental Examples 6 and 7 The modifier of Experimental Example 5 obtained in [3] above was dry-blended with the non-plant-derived PP (block polypropylene), the resin to be modified, at a blending ratio of 1:1 (Experimental Example 6) and a blending ratio of 1:4 (Experimental Example 7). The resulting dry-blend raw material was then placed in 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 molded bodies (molded bodies for evaluation) of Experimental Examples 6 to 7.

[0082] (3) Molded bodies of Experimental Examples 1 and 5 The modifiers of Experimental Examples 1 and 5 obtained in [3] above were charged 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 molded articles (molded articles for evaluation) of Experimental Examples 1 and 5. The molded articles of Experimental Examples 1 and 9 are the same. Furthermore, the molded articles of Experimental Examples 5 and 13 are the same.

[0083] (4) Molded bodies of Experimental Examples 4 and 8 The non-plant-derived PP prepared in [1](4) above was placed in 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 produce molded articles (molded articles for evaluation) of Experimental Examples 4 and 8. The molded articles of Experimental Examples 4 and 8 were the same.

[0084] [Table 1]

[0085] (5) Molded bodies of Experimental Examples 10 and 11 The modifier of Experimental Example 9 obtained in [3] above was dry-blended with the plant-derived PE, the resin to be modified, at a mixing ratio of 1:1 (Experimental Example 10) and a mixing ratio of 1:4 (Experimental Example 11). The resulting dry-blended raw material was then placed in 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 molded bodies (molded bodies for evaluation) of Experimental Examples 10 to 11.

[0086] (6) Molded bodies of Experimental Examples 14 and 15 The modifier of Experimental Example 13 obtained in [3] above was dry-blended with the plant-derived PE, the resin to be modified, in a 1:1 blending ratio (Experimental Example 14) and a 1:4 blending ratio (Experimental Example 15). The resulting dry-blended raw material was then placed in 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 molded bodies (molded bodies for evaluation) of Experimental Examples 14 to 15.

[0087] (7) Molded bodies of Experimental Examples 9 and 13 The modifiers of Experimental Examples 9 and 13 obtained in [3] above were charged 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 molded articles (molded articles for evaluation) of Experimental Examples 9 and 13. The molded articles of Experimental Examples 9 and 1 were the same. Furthermore, the molded articles of Experimental Examples 13 and 5 were the same.

[0088] (8) Molded bodies of Experimental Examples 12 and 16 The plant-derived PE prepared in [1](4) above was placed in 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 produce molded articles (molded articles for evaluation) of Experimental Examples 12 and 16. The molded articles of Experimental Examples 12 and 16 were the same.

[0089] [Table 2]

[0090] [5] Evaluation of molded products for evaluation (1) Density measurement The density was measured according to ISO1183. Test temperature: 23℃ Drying conditions: Vacuum drying at 80°C for 8 hours or more

[0091] (2) Measurement of MFR The MFR (230°C / 2.16 kg) was measured in accordance with ISO1133. Testing equipment: Melt indexer (Toyo Seiki Seisakusho Co., Ltd., model "F-F01") Test temperature: 230℃ Test load: 2.16 kgf Drying conditions: Vacuum drying at 80°C for 8 hours or more

[0092] (3) Charpy impact strength measurement Using the molded articles of Experimental Examples 1 to 16 obtained in [4] above, Charpy impact strength (test temperature 23°C) was measured in accordance with ISO 179. The results are shown in Tables 1 and 2. In measuring the Charpy impact strength, test pieces having a notch (Type A) were used, and impact measurements were performed at a temperature of 23°C using the edgewise test method.

[0093] In addition, the impact resistance ratios in Tables 1 and 2 indicate the ratio 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. The total amount of polyolefins indicates the total amount of polyolefins (plant-derived PE, plant-derived PE2, non-plant-derived PP) contained in each experimental example.

[0094] [6] Morphology The phase structure was observed using each test piece of Experimental Examples 1 and 5. The phase structure was obtained by subjecting each test piece to oxygen plasma etching (oxygen plasma etching at 100 W for 1 minute) and then observing the treated surface, which was further subjected to an osmium coating treatment, with a field emission scanning electron microscope (FE-SEM).

[0095] Of the obtained SEM images, an image of the surface of Experimental Example 1 enlarged 5000 times is shown in Figure 1, an image of the surface of Experimental Example 1 enlarged 10000 times is shown in Figure 2, and an image of the surface of Experimental Example 1 enlarged 20000 times is shown in Figure 3. Furthermore, an image of the surface of Experimental Example 5 enlarged 5000 times is shown in Figure 4, an image of the surface of Experimental Example 5 enlarged 10000 times is shown in Figure 5, and an image of the surface of Experimental Example 5 enlarged 20000 times is shown in Figure 6.

[0096] [7] Experimental results The results of Experimental Examples 3 and 7 in Table 1 show that it is difficult to obtain a sufficient modifying effect when a modifier is blended with non-plant-derived PP (block polypropylene) at a blending ratio (by mass) of 4:1. However, the results of Experimental Examples 2 and 6 show that a high modifying effect can be obtained when a modifier is blended with non-plant-derived PP (block polypropylene) at a blending ratio (by mass) of 1:1. Furthermore, from the results of Experimental Examples 2 and 6, the Charpy impact strength was 71 kJ / m 2 The total amount of plant-derived resin in Experimental Example 2 is 45 mass %. In addition, the Charpy impact strength is 71 kJ / m 2 The total amount of plant-derived resin in Experimental Example 6 is 45% by mass. PA >R PE2 Experimental Example 2, where R PA <R PE2 It can be seen that practically the same impact resistance and environmental performance are obtained in Experimental Example 6, which is

[0097] On the other hand, the results in Table 2 show that the modification effect on plant-derived PE (polyethylene) was 2.2 times in Experimental Example 10 and 3.8 times in Experimental Example 14, while a high modification effect of 4.7 times was obtained in both Experimental Examples 2 and 6, which are the modification modes of the present application.

[0098] 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, a continuous phase B1 within the dispersed phase and a finely dispersed phase B2 within the dispersed phase B. Furthermore, it can be seen from the results of Figures 4 to 6 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, a continuous phase B1 within the dispersed phase and a finely dispersed phase B2 within the dispersed phase B.

[0099] The present invention is not limited to the specific examples described above, and various modifications can be made within the scope of the present invention depending on the purpose and application.

[0100] The foregoing examples are for illustrative purposes only and are not to be construed as limiting the invention. While the invention has been described with reference to exemplary embodiments, it is understood that the language used in describing and illustrating the invention is descriptive and exemplary, rather than limiting. As detailed herein, changes may be made within the purview of the appended claims without departing from the scope or spirit of the invention in its form. While the description of the invention has referred to specific structures, materials, and examples, it is not intended that the invention be limited to the disclosure set forth herein; rather, the invention is intended to cover all functionally equivalent structures, methods, and uses within the scope of the appended claims. [Explanation of symbols]

[0101] A: continuous phase, B; dispersed phase, B1: continuous phase (continuous phase within dispersed phase B), B2; finely dispersed phase (dispersed phase within dispersed phase B);

Claims

1. The resin to be modified is polypropylene, and when the total with the resin to be modified is 100% by mass, a modifier that can improve the impact resistance of the resin to be modified by blending 30% by mass or more, Polyethylene (PE ２ ), a polyamide and a compatibilizer; the compatibilizer is a modified elastomer having a group reactive with the polyamide, The polyamide has a bio-based carbon content according to ISO 16620-2 of 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; A modifier characterized in that, when the total of the polyethylene (PE 2 ), the polyamide and the compatibilizer is 100% by mass, the mass proportion R PE2 (% by mass) of the polyethylene (PE 2 ) and the mass proportion R PA (% by mass) of the polyamide satisfy R PE2 ≧R PA .

2. The polyethylene (PE ２ ), the total of the polyamide and the compatibilizer is 100 mass %, ２ ) mass ratio is R ＰＥ２ mass%, and the mass ratio of the polyamide is R ＰＡ % by mass, and the mass ratio of the compatibilizer is R ＣＢ In the case of mass%, 1≦R ＣＢ (mass%)≦70 and 0.3≦R ＰＥ２ / R ＰＡ 2. The modifier of claim 1, wherein the modifier has a viscosity of ≦3.

5.

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

4. 4. The modifier according to claim 1, wherein the polyamide has a structure in which the hydrocarbon groups sandwiched between adjacent amide bonds in the main chain have a linear carbon number of 6 or more.

5. 5. The modifier according to claim 1, wherein the compatibilizer has a main skeleton of a copolymer chain derived from ethylene and an α-olefin other than ethylene, and the reactive group is an acid-modified group.

6. 6. The modifier according to claim 1, wherein the polypropylene is a block polypropylene.

7. 7. The modifier according to claim 1, wherein the MFR (230° C. / 2.16 kg) is 3 to 17 g / 10 min.

8. A melt-kneaded mixture of the polyamide and the compatibilizer and the polyethylene (PE ２ 8. The modifier according to claim 1, which is obtained by melt-kneading a polyisocyanate copolymer containing 1,2-dichloromethane and 1,2-dichloromethane.

9. The resin to be modified is block polypropylene, and when the total with the resin to be modified is 100% by mass, the modifier can improve the impact resistance of the resin to be modified by blending 30% by mass or more, Polyethylene (PE ２ ), a polyamide and a compatibilizer; the compatibilizer is a modified elastomer having a group reactive with the polyamide, The polyamide has a bio-based carbon content according to ISO 16620-2 of 80% or more, The polyethylene (PE ２ ) is a modifier characterized by being 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.

10. The polyethylene (PE ２ ), the total of the polyamide and the compatibilizer is 100 mass %, ２ ) mass ratio is R ＰＥ２ mass%, and the mass ratio of the polyamide is R ＰＡ % by mass, and the mass ratio of the compatibilizer is R ＣＢ In the case of mass%, 1≦R ＣＢ (mass%)≦70 and 0.3≦R ＰＥ２ / R ＰＡ 10. The modifier of claim 9, wherein the modifier has a viscosity of ≦3.

5.

11. The polyethylene (PE ２ ), the mass ratio R of the compatibilizer when the total of the polyamide and the compatibilizer is 100 mass% ＣＢ The modifier according to claim 9 or 10, wherein (mass%) is 4 to 30 mass%.

12. The polyethylene (PE ２ ), when the total of the polyamide and the compatibilizer is 100 mass%, the polyethylene (PE ２ ) mass ratio R ＰＥ２ (mass%) and the mass ratio R of the polyamide ＰＡ (mass%) and R ＰＥ２ ≧R ＰＡ The modifying agent according to any one of claims 9 to 11, which satisfies the above.

13. 13. The modifier according to claim 9, wherein the polyamide has a structure in which the hydrocarbon groups sandwiched between adjacent amide bonds in the main chain have a linear carbon number of 6 or more.

14. The modifier according to any one of claims 9 to 13, wherein the compatibilizer has a main skeleton of a copolymer chain derived from ethylene and an α-olefin other than ethylene, and the reactive group is an acid-modified group.

15. The modifier according to any one of claims 9 to 14, having an MFR (230°C / 2.16 kg) of 3 to 17 g / 10 min.

16. A melt-kneaded mixture of the polyamide and the compatibilizer and the polyethylene (PE ２ 16. The modifier according to claim 9, which is obtained by melt-kneading a polyisocyanate copolymer containing 1,2-dichloromethane and 1,2-dichloromethane.

17. A method for producing a molded article, comprising a molding step of molding a raw material obtained by dry-blending polypropylene, a resin to be modified, and the modifier according to any one of claims 1 to 8.

18. The method for producing a molded article according to claim 17, wherein the modifier is 30 to 70% by mass when the total of the resin to be modified and the modifier is 100% by mass.

19. A method for producing a molded product, comprising a molding step of molding a raw material obtained by dry-blending a block polypropylene, which is a resin to be modified, and the modifier according to any one of claims 9 to 16.

20. The method for producing a molded body according to claim 19, wherein the modifier is 30 to 70% by mass when the total of the resin to be modified and the modifier is 100% by mass.

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