Patent Application
20230174754
The present invention relates to a thermoplastic resin composition and a modifier. More specifically, the present invention relates to a thermoplastic resin composition and a modifier, obtained by blending a polyethylene, a polyamide, and a compatibilizer.
Techniques for obtaining a thermoplastic resin composition having excellent impact resistance using three components, i.e., a polyolefin, a polyamide, and a compatibilizer, are disclosed in Patent Literature 1 and 2.
Patent Literatures 1 and 2 disclose that a modified elastomer having a reactive group that reacts with a polyamide is used as a compatibilizer, that a melt-kneaded product obtained by melt-kneading a compatibilizer and a polyamide separately from a polyolefin is used, that the obtained melt-kneaded product and the polyolefin are melt-kneaded to obtain a thermoplastic resin composition as a target product, and that a plant-derived polyamide 11 can be used as the polyamide.
In recent years, building of a sustainable society and reduction in environmental load associated therewith have been highlighted, and there is an increasing demand for coping with such a situation also in the technical field of materials. Specifically, from the viewpoint of reducing CO2 emission, a technique using a plant-derived raw material instead of a fossil-derived raw material such as petroleum has attracted attention, and, as general-purpose resins, plant-derived products of not only polyamides but also polyolefins have been put on the market. However, there is an actual situation in which, as compared with fossil-derived resins that have been used for a long time, both of them have few grades and have not been adjusted to suit various uses. For this reason, there is no situation in which the fossil-derived resins that have been conventionally used can be directly replaced with plant-derived resins, and various difficulties problematically exist in increasing the proportion of the plant-derived resins.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a thermoplastic resin composition capable of achieving both high impact resistance and high fluidity using three components, i.e., a polyolefin, a polyamide, and a compatibilizer, while realizing a reduction in environmental load, a method for producing the same, and a molded body using the thermoplastic resin composition. Another object of the present invention is to provide a modifier which contains three components, i.e., a polyethylene, a polyamide, and a compatibilizer, and can impart impact resistance to a polyethylene while realizing a reduction in environmental load. Still another object of the present invention is to provide a method for producing a molded body using the modifier.
The present invention is as follows.
[1] A thermoplastic resin composition of the present invention is a thermoplastic resin composition obtained by blending a polyethylene, a polyamide, and a compatibilizer,
wherein the compatibilizer is a modified elastomer having a reactive group that reacts with the polyamide, and
wherein the polyethylene and the polyamide have a bio-based carbon content rate of 80% or more according to ISO 16620-2.
[2] In the thermoplastic resin composition of the present invention, the polyethylene can have an MFR (230° C./2.16 kg) of 20 g/10 min or less.
[3] The thermoplastic resin composition of the present invention can have an MFR (230° C./2.16 kg) of 3 g/10 min or more.
[4] In the thermoplastic resin composition of the present invention, the compatibilizer can have a copolymerized chain derived from ethylene and an α-olefin other than ethylene as a main skeleton, and the reactive group can be an acid-modified group.
[5] In the thermoplastic resin composition of the present invention,
when a total amount of the polyethylene, the polyamide, and the compatibilizer is 100 mass %, an amount of the compatibilizer can be 1 to 30 mass %, and
when a mass proportion of the polyethylene is RPE mass % and a mass proportion of the polyamide is RPA mass % when a total mass proportion of the polyethylene, the polyamide, and the compatibilizer is 100 mass %, RPE/RPA can be 0.3 to 3.5.
[6] The molded body of the present invention is composed of the thermoplastic resin composition of the present invention.
[7] A method for producing the thermoplastic resin composition of the present invention includes: a melt-kneading step of melt-kneading a melt-kneaded product of the polyamide and the compatibilizer with the polyethylene.
[8] A modifier of the present invention is a modifier which modifies a polyethylene (PE1) as a resin to be modified and is capable of improving impact resistance of the resin to be modified,
the modifier containing a polyethylene (PE2), a polyamide, and a compatibilizer,
wherein the compatibilizer is a modified elastomer having a reactive group that reacts with the polyamide, and
wherein the polyethylene (PE2) and the polyamide have a bio-based carbon content rate of 80% or more according to ISO 16620-2.
[9] In the modifier of the present invention, when a total mass proportion of the polyethylene (PE2), the polyamide, and the compatibilizer is 100 mass %, a mass proportion of the polyethylene (PE2) is RPE2 mass %, a mass proportion of the polyamide is RPA mass %, and a mass proportion of the compatibilizer is RCB mass %,
1≤RCB (mass %)≤70 and 0.3≤RPE2/RPA≤3.5 can be established.
[10] In the modifier of the present invention, the polyethylene (PE2) can be a high density polyethylene.
[11] In the modifier of the present invention, the polyethylene (PE2) can have an MFR (230° C./2.16 kg) of 20 g/10 min or less.
[12] In the modifier of the present invention, the polyamide can have a structure in which a hydrocarbon group sandwiched between adjacent amide bonds in a main chain has a carbon number of a linear-chain part of 6 or more.
[13] In the modifier of the present invention, the compatibilizer can have a copolymerized chain derived from ethylene and an α-olefin other than ethylene as a main skeleton, and the reactive group can be an acid-modified group.
[14] In the modifier of the present invention, the polyethylene (PE1) can be a high density polyethylene.
[15] The modifier of the present invention can have an MFR (230° C./2.16 kg) of 3 g/10 min or more.
[16] The modifier of the present invention can be obtained by melt-kneading a melt-kneaded product of the polyamide and the compatibilizer with the polyethylene (PE2).
[17] A method for producing a molded body of the present invention can include a molding step of molding a raw material obtained by dry-blending a polyethylene (PE1) as a resin to be modified with the modifier of the present invention.
[18] In the method for producing a molded body of the present invention, when a total amount of the resin to be modified and the modifier is 100 mass %, an amount of the modifier can be 30 to 70 mass %.
According to the thermoplastic resin composition of the present invention and the method for producing the same, it is possible to achieve both high impact resistance and high fluidity by using three components, i.e., a polyolefin, a polyamide, and a compatibilizer while realizing a reduction in environmental load.
According to the molded body of the present invention, it is possible to realize a reduction in environmental load while forming a molded body having high impact resistance by using three components, i.e., a polyolefin, a polyamide, and a compatibilizer.
According to the modifier of the present invention, impact resistance can be imparted to a polyethylene while realizing a reduction in environmental load.
According to the method for producing a molded body of the present invention, it is possible to easily obtain a polyethylene-based molded body having excellent impact resistance while realizing a reduction in environmental load through a small number of steps without undergoing a preliminary kneading step.
The particulars described herein are given by way of example and for the purpose of illustrative discussion of the embodiments of the present invention, and are presented for the purpose of providing what is believed to be the description from which the principles and conceptual features of the present invention can be most effectively and readily understood. In this regard, no attempt is made to show structural details of the present invention in more detail than is necessary for the fundamental understanding of the present invention, and the description is taken with the drawings making apparent to those skilled in the art how several forms of the present invention may be embodied in practice.
In the present specification, the description “XX to YY” means “XX or more and YY or less”.
The thermoplastic resin composition of the present invention is a thermoplastic resin composition obtained by blending a polyethylene, a polyamide, and a compatibilizer. Among these components, the compatibilizer is a modified elastomer having a reactive group that reacts with the polyamide. Furthermore, the polyethylene and the polyamide have a bio-based carbon content rate of 80% or more according to ISO 16620-2.
<1> Polyethylene (Plant-Derived PE)
The polyethylene has a bio-based carbon content rate of 80% or more, as measured according to the standard ISO 16620-2 (in the present specification, the polyethylene is also simply described as “plant-derived PE”). The bio-based carbon content rate is a value obtained by calculating a plant-derived carbon content rate (bio-based carbon content rate) based on a proportion of 14C in total constituent carbon.
The plant-derived PE used in the present invention has only to have a bio-based carbon content rate of 80% or more (may have a bio-based carbon content rate of 100%), may further have a bio-based carbon content rate of 85% or more, and may further have a bio-based carbon content rate of 90% or more.
The bio-based carbon content rate can be a value as measured according to the standard ASTM D6866, in addition to ISO 16620-2. Usually, values according to these standards are substantially the same.
The plant-derived PE is a polymer having a structure (methylene chain) in which methylene groups (—CH2—) are linked as a main skeleton. The methylene chain is a constitutional unit derived particularly from ethylene. Therefore, the plant-derived PE includes a homopolymer of ethylene and a copolymer of ethylene and another olefin. In a case of a copolymer, usually 50% or more of a total number of constitutional units is derived from ethylene. Examples of another olefin include an olefin having 3 carbon atoms (propylene), an olefin having 4 carbon atoms (e.g., 1-butene), an olefin having 5 carbon atoms (3-methyl-1 butene, 1-pentene, etc.), an olefin having 6 carbon atoms (3-methyl-1 pentene, 4-methyl-1 pentene, 1-hexene, etc.), and an olefin having 8 carbon atoms (e.g., 1-octene). These may be used singly, or two or more thereof may be used in combination.
Specifically, examples of the plant-derived PE as a copolymer include an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, an ethylene-1-octene copolymer, and an ethylene-4-methyl-1-pentene copolymer. These may be used singly, or two or more thereof may be used in combination. Further, when two or more of these copolymers are used, both pellets made of a mixed resin and a pellet mixture are included.
In addition, regardless of whether the plant-derived PE is a homopolymer of ethylene or a copolymer of ethylene and another olefin, the plant-derived PE becomes plant-derived due to the fact that a monomer that forms these polymers is derived from a plant raw material. A total amount of the monomer may be a plant-derived monomer, or only a part thereof may be a plant-derived monomer (that is, a fossil-derived monomer may be contained in the other part). That is, as a result, the plant-derived PE has only to have a bio-based carbon content rate of 80% or more.
Although various properties of the plant-derived PE are not limited, it is preferable that the plant-derived PE be a high-density polyolefin having a density of 0.942 g/cm3 or more and have an MFR (230° C./2.16 kg) of 35 g/10 min or less. The MFR of the plant-derived PE is 35 g/10 min or less (usually, 1 g/10 min or more), so that the fluidity can be increased while excellent impact resistance properties of the resulting thermoplastic resin composition is obtained. Further, the MFR is preferably 20 g/10 min or less, and more preferably 15 g/10 min or less. A lower limit is not limited, but is preferably 2 g/10 min or more, and more preferably 3 g/10 min or more, from the viewpoint of ease of melt-kneading.
In the present invention, the MFR (230° C./2.16 kg) of the plant-derived PE is a value as measured according to the standard ISO 1133 or ASTM D1238. Values according to these standards are usually substantially the same.
As described above, the density of the plant-derived PE is preferably 0.942 g/cm3 or more, and, further, more preferably 0.950 g/cm3 or more. An upper limit of the density is not limited, but is preferably 0.954 g/cm3 or less.
Achievement of both the MFR and the density described above can be adjusted by linearity, a branching amount, a molecular weight, and the like of the plant-derived PE.
In the present invention, the density of the plant-derived PE is a value as measured according to the standard ISO 1183 or ASTM D792. Values according to these standards are usually substantially the same.
Furthermore, the MFR (230° C./2.16 kg) of the plant-derived PE is preferably small. Specifically, the MFR is preferably closer to an MFR (230° C./2.16 kg) of a melt-kneaded product obtained from a plant-derived PA and a compatibilizer, which will be described later. That is, it is considered that, as for kneading of the plant-derived PA and the compatibilizer can be promoted by a reaction between them, and the kneading of them is hardly affected by a difference in MFR. On the other hand, in kneading of the plant-derived PE and the melt-kneaded product (the melt-kneaded product of the plant-derived PA and the compatibilizer), they are not reacted. Thus, it is considered that the kneading of them is easily affected by a difference in MFR therebetween. Therefore, it is considered that kneadability is improved by bringing the MFR of the plant-derived PE and the MFR of the melt-kneaded product close to each other, and that the impact resistance can be improved accordingly.
Specifically, when the MFR (230° C./2.16 kg) of the plant-derived PE is MPE (g/10 min) and the MFR (230° C./2.16 kg) of the melt-kneaded product of the plant-derived PA and the compatibilizer is MPX (g/10 min), a ratio between them, MPE/PX (=MPE/MPX), is preferably 0.5≤MPE/PX≤20, more preferably 1≤MPE/PX≤17, even more preferably 2≤MPE/PX≤13, and particularly preferably 5≤MPE/PX≤10.
Although a range of MPX is not limited, for example, 0.1≤MPX (g/10 min)≤10 can be set, further 0.5≤MPX (g/10 min)≤5 can be set, and further 1≤MPX (g/10 min)≤3 can be set.
<2> Polyamide (Plant-Derived PA)
The polyamide has a bio-based carbon content rate of 80% or more, as measured according to the standard ISO 16620-2 (in the present specification, the polyamide is also simply described as “plant-derived PA”). The bio-based carbon content rate is a value obtained by calculating a plant-derived carbon content rate (bio-based carbon content rate) based on a proportion of 14C in total constituent carbon.
The plant-derived PA used in the present invention has only to have a bio-based carbon content rate of 80% or more (may have a bio-based carbon content rate of 100%), may further have a bio-based carbon content rate of 90% or more, and may further have a bio-based carbon content rate of 95% or more.
The bio-based carbon content rate can be a value as measured according to the standard ASTM D6866, in addition to ISO 16620-2. Usually, values according to these standards are substantially the same.
The plant-derived PA is a polymer having a structure in which hydrocarbon groups (in particular, methylene chain) are linked via amide bonds (—NH—CO—) as a main skeleton.
Examples of a monomer 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, undecane lactam, and ω-lauryl lactam. These may be used singly, or two or more thereof may be used in combination. Among them, from the viewpoint of a high bio-based carbon content rate, the plant-derived PA preferably contains a large amount of plant-derived 11-aminoundecanoic acid.
Furthermore, the plant-derived PA can also be obtained by copolymerization of a diamine and a dicarboxylic acid. In this case, examples of diamines as monomers 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-diaminoundecane, 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 (p-phenylenediamine, m-phenylenediamine, etc.). These may be used singly, or two or more thereof may be used in combination. Among them, from the viewpoint of a high bio-based carbon content rate, the plant-derived PA preferably contains a large amount of plant-derived 1,10-diaminodecane and/or 1,5-diaminopentane.
Further, 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, brasylic acid, tetradecanedioic acid, pentadecanoic acid, and octadecanedioic acid; alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid; and aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid; and, further, furandicarboxylic acid. These may be used singly, or two or more thereof may be used in combination. Among them, from the viewpoint of a high bio-based carbon content rate, the plant-derived PA preferably contains a large amount of plant-derived sebacic acid, furandicarboxylic acid, and/or glutaric acid.
Furthermore, the plant-derived PA preferably has a structure in which a hydrocarbon group sandwiched between adjacent amide bonds in a main chain has a carbon number of a linear-chain part of 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), and polyamide MXD10 (MXD10). These polyamides may be used singly, or two or more thereof may be used in combination. Further, when two or more of these copolymers are used, both pellets made of a mixed resin and a pellet mixture are included.
In addition, regardless of whether the plant-derived PA is a homopolymer of an amino acid or alactam or a copolymer of a diamine and a dicarboxylic acid, the plant-derived PA becomes plant-derived due to the fact that a monomer that forms these polymers is derived from a plant raw material. A total amount of the monomer may be a plant-derived monomer, or only apart thereof may be a plant-derived monomer (that is, a fossil-derived monomer may be contained in the other part). That is, as a result, the plant-derived PA has only to have a bio-based carbon content rate of 80% or more.
Although various properties of the plant-derived PA are not limited, it is preferable that the plant-derived PA is a polyamide having a density of 1.15 g/cm3 or less and have an MFR (230° C./2.16 kg) of 50 g/10 min or less. The MFR of the plant-derived PA is 50 g/10 min or less (usually, 1 g/10 min or more), so that the fluidity can be increased while excellent impact resistance properties of the resulting thermoplastic resin composition is obtained. The MFR is even more preferably 40 g/10 min or less, and more preferably 35 g/10 min or less. A lower limit is not limited, but is preferably 3 g/10 min or more, and more preferably 5 g/10 min or more, from the viewpoint of ease of melt-kneading.
In the present invention, the MFR (230° C./2.16 kg) of the plant-derived PA is a value as measured according to the standard ISO 1133 or ASTM D1238. Values according to these standards are usually substantially the same.
As described above, the density of the plant-derived PA is preferably 1.15 g/cm3 or less, and, further, more preferably 1.08 g/cm3 or less. A lower limit of the density is not limited, but is preferably 0.98 g/cm3 or more.
Achievement of both the MFR and the density can be adjusted by linearity, a branching amount, a molecular weight, and the like of the plant-derived PA.
In the present invention, the density of the plant-derived PA is a value as measured according to the standard ISO 1183 or ASTM D792. Values according to these standards are usually substantially the same.
<3> Compatibilizer
The compatibilizer is a modified elastomer having a reactive group that reacts with the plant-derived PA. Furthermore, the compatibilizer is preferably a component having affinity for the plant-derived PE. In this case, the compatibilizer is a component having a compatibilizing effect on the plant-derived PE and the plant-derived PA. That is, the compatibilizer is preferably a compatibilizer for the plant-derived PE and the plant-derived PA.
In the present thermoplastic resin composition, the compatibilizer may be reacted entirely with the plant-derived PA, or may be reacted only partially therewith.
The reactive group of the modified elastomer has only to have reactivity with the plant-derived PA, and examples thereof include an acid anhydride group (—CO—O—OC—), a carboxyl group (—COOH), an epoxy group {—C2O (a three-membered ring structure composed of two carbon atoms and one oxygen atom)}, an oxazoline group (—C3H4NO), and an isocyanate group (—NCO). These may be used singly, or two or more thereof may be used in combination.
A modification amount of the modified elastomer by the reactive group is not limited. The modified elastomer has only to have one or more reactive groups, and, further, preferably has 1 or more and 50 or less reactive groups, more preferably has 3 or more and 30 or less reactive groups, and particularly preferably has 5 or more and 20 or less reactive groups, in one molecule.
Examples of the modified elastomer include polymers using various monomers capable of introducing a reactive group (modified elastomers obtained by polymerization using monomers capable of introducing a reactive group), oxidative decomposition products of various polymers (modified elastomers in which a reactive group is formed by oxidative decomposition), and graft polymers of organic acids to various polymers (modified elastomers in which a reactive group is introduced by graft polymerization of organic acids). These may be used singly, or two or more thereof may be used in combination. These may be used singly, or two or more thereof may be used in combination.
Examples of the monomer capable of introducing a reactive group 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.
Examples of the monomer 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 singly, or two or more thereof 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.
Furthermore, the type of resin constituting the skeleton of the modified elastomer (hereinafter, referred to as “backbone resin”) is not particularly limited, and various thermoplastic resins can be used. As the skeleton resin, an olefin-based elastomer (olefin-based thermoplastic elastomer) and/or a styrenic elastomer (styrenic thermoplastic elastomer) can be used.
Among them, examples of the olefin-based elastomer include those obtained by copolymerizing two or more of olefins.
Examples of the olefins include ethylene, propylene, and an α-olefin having 4 to 8 carbon atoms. Among them, examples of the α-olefin having 4 to 8 carbon atoms include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, and 1-octene.
Among these, as the olefin-based elastomer, a copolymer of ethylene and an α-olefin other than ethylene is preferred. That is, as the compatibilizer, a modified elastomer having a copolymerized chain derived from ethylene and an α-olefin other than ethylene as a main skeleton and having a reactive group that reacts with the plant-derived PA is preferable. When such an olefin-based elastomer is used, a thermoplastic resin composition that gives a molded body having particularly excellent impact resistance properties can be obtained. The α-olefin other than ethylene is preferably an α-olefin having 3 to 8 carbon atoms, and more preferably an α-olefin having 4 to 8 carbon atoms.
Among those described above, examples of the copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms include an ethylene-propylene copolymer (EPR), an ethylene-1-butene copolymer (EBR), an ethylene-1-pentene copolymer, and an ethylene-1-octene copolymer (EOR). Examples of the copolymer of propylene and an α-olefin having 4 to 8 carbon atoms include a propylene-1-butene copolymer (PBR), a propylene-1-pentene copolymer, and a propylene-1-octene copolymer (POR). These may be used singly, or two or more thereof may be used in combination. Further, when two or more of these copolymers are used, both pellets made of a mixed resin and a pellet mixture are included.
On the other hand, the styrene thermoplastic elastomer is a styrenic thermoplastic elastomer having a styrene skeleton. When the styrenic thermoplastic elastomer is used, a molded body having particularly excellent impact resistance properties can be produced.
More specific examples of the styrenic thermoplastic elastomer include a block copolymer of a styrenic compound and a conjugated diene compound, and a hydrogenated product thereof.
Of them, examples of the styrenic compound include alkylstyrenes such as styrene, α-methylstyrene, p-methylstyrene, and p-t-butylstyrene; p-methoxystyrene, and vinylnaphthalene. These may be used singly, or two or more thereof may be used in combination.
On the other hand, examples of the conjugated diene compound include butadiene, isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, and 4,5-diethyl-1,3-octadiene. These may be used singly, or two or more thereof may be used in combination.
Specifically, examples of the styrenic elastomer include a styrene-butadiene-styrene copolymer (SBS), a styrene-isoprene-styrene copolymer (SIS), a styrene-ethylene/butylene-styrene copolymer (SEBS), and a styrene-ethylene/propylene-styrene copolymer (SEPS). These may be used singly, or two or more thereof may be used in combination. Further, when two or more of these copolymers are used, both pellets made of a mixed resin and a pellet mixture are included. Among these, SEBS is preferred.
Although various properties of the compatibilizer are not limited, it is preferable that the compatibilizer is a modified elastomer having a density of 0.90 g/cm3 or less and have an MFR (230° C./2.16 kg) of 10 g/10 min or less. The MFR of the compatibilizer is 10 g/10 min or less (usually, 0.5 g/10 min or more), so that the fluidity can be increased while excellent impact resistance properties of the resulting thermoplastic resin composition is obtained. Further, the MFR is preferably 7 g/10 min or less, and more preferably 5 g/10 min or less. An upper limit is not limited, but is preferably 0.5 g/10 min or more, and more preferably 1.0 g/10 min or more, from the viewpoint of ease of melt-kneading.
In the present invention, the MFR (230° C./2.16 kg) of the compatibilizer is a value as measured according to the standard ISO 1133 or ASTM D1238. Values according to these standards are usually substantially the same.
As described above, the density of the compatibilizer is preferably 0.90 g/cm3 or less, and, further, more preferably 0.89 g/cm3 or less. A lower limit of the density is not limited, but is preferably 0.85 g/cm3 or more.
Achievement of both the MFR and the density can be adjusted by linearity, a branching amount, a molecular weight, a modification amount, and the like of the compatibilizer.
In the present invention, the density of the compatibilizer is a value as measured according to the standard ISO 1183 or ASTM D792. Values according to these standards are usually substantially the same.
The molecular weight of the modified elastomer is not particularly limited, but a 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 a GPC method (in terms of standard polystyrene).
<4> Blending of Each Component
When a total mass proportion of the plant-derived PE, the plant-derived PA, and the compatibilizer is 100 mass %, a mass proportion of the plant-derived PE (hereinafter, this mass proportion is also referred to as “RPE”) is preferably 10 to 90 mass %, more preferably 13 to 85 mass %, even more preferably 17 to 80 mass %, still even more preferably 20 to 75 mass %, still even more preferably 23 to 70 mass %, and still even more preferably 25 to 65 mass %.
That is, when a total proportion of the plant-derived PE, the plant-derived PA, and the compatibilizer is 100 mass %, a total proportion (hereinafter, this mass proportion is also referred to as “RPA+CB”) of the plant-derived PA and the compatibilizer is preferably 10 to 90 mass %, more preferably 15 to 87 mass %, even more preferably 20 to 83 mass %, still even more preferably 25 to 80 mass %, still even more preferably 30 to 77 mass %, and still even more preferably 35 to 75 mass %.
When the total mass proportion of the plant-derived PE, the plant-derived PA, and the compatibilizer is 100 mass %, a mass proportion of the plant-derived PA (hereinafter, this mass proportion is also referred to as “RPA”) is preferably 1 to 80 mass %, more preferably 3 to 75 mass %, even more preferably 5 to 70 mass %, still even more preferably 10 to 75 mass %, still even more preferably 15 to 70 mass %, and still even more preferably 20 to 65 mass %.
When the total mass proportion of the plant-derived PE, the plant-derived PA, and the compatibilizer is 100 mass %, a mass proportion of the compatibilizer (hereinafter, this mass proportion is also referred to as “RCB”) is preferably 1 to 70 mass %, more preferably 2 to 60 mass %, even more preferably 2 to 50 mass %, still even more preferably 3 to 40 mass %, still even more preferably 3 to 35 mass %, and still even more preferably 4 to 30 mass %.
When a total mass proportion of the plant-derived PA and the compatibilizer is 100 mass %, a mass proportion of the compatibilizer is preferably 3 to 70 mass %, more preferably 4 to 65 mass %, even more preferably 5 to 60 mass %, still even more preferably 6 to 55 mass %, still even more preferably 7 to 45 mass %, and still even more preferably 8 to 40 mass %.
Furthermore, when the total mass proportion of the plant-derived PE, the plant-derived PA, and the compatibilizer is 100 mass %, and the mass proportion RCB of the compatibilizer is 1 to 30 mass %, a ratio (RPE/RPA) of the mass proportion RPE of the plant-derived PE to the mass proportion RPA of the plant-derived PA is preferably 0.3 to 3.5. Further, the ratio (RPE/RPA) is more preferably 0.4 to 2.0, even more preferably 0.35 to 2.00, still even more preferably 0.40 to 1.50, and particularly preferably 0.45 to 1.20.
In the above ranges, a thermoplastic resin composition having a Charpy impact strength of 70 to 95 kJ/m2 (further, 73 to 90 kJ/m2, in particular 75 to 87 kJ/m2) and an MFR (230° C./2.16 kg) of 12 to 28 g/10 min (further 16 to 27 g/10 min, in particular 17 to 26 g/10 min) can be obtained.
In addition, in particular, in a range in which the mass proportion RPA of the plant-derived PA is higher than the mass proportion RPE of the plant-derived PE (that is, RPA>RPE), when an attempt is made to obtain a thermoplastic resin composition having high impact resistance and high fluidity, RPE:RPA:RCB is preferably 20 to 45 mass %:50 to 80 mass %:1 to 25 mass %, more preferably 24 to 40 mass %:52 to 70 mass %:3 to 18 mass %, and particularly preferably 27 to 35 mass %:55 to 65 mass %:6 to 14 mass %.
In the above ranges, a thermoplastic resin composition having a Charpy impact strength of 70 to 95 kJ/m2 (further, 73 to 90 kJ/m2, in particular 75 to 87 kJ/m2) and an MFR (230° C./2.16 kg) of 12 to 28 g/10 min (further 16 to 27 g/10 min, in particular 17 to 26 g/10 min) can be obtained.
Furthermore, also in the above ranges, when the total mass proportion of the plant-derived PA and the compatibilizer is 100 mass %, the mass proportion of the compatibilizer is preferably 4 to 24 mass %, more preferably 7 to 20 mass %, and even more preferably 11 to 17 mass %.
Furthermore, in particular, in a range in which the mass proportion RPA of the plant-derived PA is lower than the mass proportion RPE of the plant-derived PE (that is, RPA<RPE), when an attempt is made to obtain a thermoplastic resin composition having high impact resistance and high fluidity, RPE:RPA:RCB is preferably 35 to 65 mass %:30 to 60 mass %:1 to 20 mass %, more preferably 40 to 60 mass %:36 to 55 mass %:2 to 13 mass %, and particularly preferably 47 to 55 mass %:42 to 48 mass %:3 to 8 mass %.
In the above ranges, a thermoplastic resin composition having a Charpy impact strength of 10 to 50 kJ/m2 (further, 15 to 40 kJ/m2, in particular 17 to 30 kJ/m2) and an MFR (230° C./2.16 kg) of 10 to 28 g/10 min (further 12 to 25 g/10 min, in particular 14 to 20 g/10 min) can be obtained.
Furthermore, also in the above range, when the total mass proportion of the plant-derived PA and the compatibilizer is 100 mass %, the mass proportion of the compatibilizer is preferably 5 to 24 mass %, more preferably 6 to 18 mass %, and even more preferably 7 to 13 mass %.
Although the fluidity of the thermoplastic resin composition of the present invention is not limited, the density is 0.93 to 1.00 g/cm3, and the MFR (230° C./2.16 kg) can be set to 3 g/10 min or more (usually, 30 g/10 min or less). The MFR can be further set to 6 g/10 min or more, further set to 12 g/10 min or more, and further set to 17 g/10 min or more. An upper limit value is not limited, but can be 27 g/10 min or less.
In the present invention, the MFR (230° C./2.16 kg) of the compatibilizer is a value as measured according to the standard ISO 1133 or ASTM D1238. Values according to these standards are usually substantially the same.
The thermoplastic resin composition of the present invention (molded body formed using the thermoplastic resin composition of the present invention) can have specific phase structures (1) to (3).
Specifically, it can have (1) a phase structure including a continuous phase (A) of the plant-derived PA and a dispersed phase (B) of the plant-derived PE (see
Also, it can have (2) a phase structure including a continuous phase (A) of the plant-derived PE and a dispersed phase (B) of the plant-derived PA (see
Furthermore, as a phase structure (3), a co-continuous structure in which the phase structures (1) and (2) are mixed can be exhibited.
In particular, when the phase structures (1) and (2) described above are exhibited, excellent impact resistance properties can be obtained by the phase structure having the finely dispersed phase (B2). Similarly, in a case where the thermoplastic resin composition has the co-continuous structure (3), excellent impact resistance properties can be obtained.
In a case where thermoplastic resin composition has any of the phase structures described above, a size of the dispersed phase contained in the continuous phase is not limited, and an average diameter (average particle diameter) thereof is preferably 10,000 nm or less, more preferably 50 to 8000 nm, and even more preferably 100 to 4000 nm. The average diameter of the dispersed phase is an average value (nm) of maximum lengths of 50 dispersed phases randomly selected in an image obtained using an electron microscope.
In addition, in a case where the thermoplastic resin composition has the dispersed phase described above, a size of the finely dispersed phase contained in the dispersed phase is not limited, and an average diameter (average particle diameter) thereof 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 an average value (nm) of maximum lengths of 100 finely dispersed phases randomly selected in an image obtained using an electron microscope.
<5> Other Components
The thermoplastic resin composition of the present invention can contain any other component, in addition to the plant-derived PE, the plant-derived PA, and the compatibilizer described above.
When the other component is a thermoplastic polymer which can act similarly to the plant-derived PE, the plant-derived PA, and the compatibilizer (provided that components functioning as filling materials, fillers, and the like are excluded), an amount of the thermoplastic polymer as the other component is preferably 20 parts by mass or less when the total amount of the plant-derived PE, the plant-derived PA, and the compatibilizer is 100 parts by mass. A lower limit value of the amount of the other component, when contained in the thermoplastic resin composition, is not limited, but can be, for example, 1 part by mass.
The other component that is a thermoplastic polymer include fossil-derived polyolefins having a bio-based carbon content rate of less than 80% according to ISO 16620-2 (polyolefins not included in the plant-derived PE described above). The fossil-derived polyolefins include homopolymers of olefins and/or copolymers of olefins.
The olefins constituting the fossil-derived polyolefins are not particularly limited, and examples thereof include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, and 1-octene. These may be used singly, or two or more thereof may be used in combination.
That is, the fossil-derived polyolefins include polyethylene, polypropylene, poly(1-butene), poly(1-hexene), and poly(4-methyl-1-pentene). These polymers may be used singly, or two or more thereof may be used in combination. Further, when two or more of these copolymers are used, both pellets made of a mixed resin and a pellet mixture are included.
Examples of the polyethylene include an ethylene homopolymer and a copolymer of ethylene and another olefin. Examples of the latter include an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, an ethylene-1-octene copolymer, and an ethylene-4-methyl-1-pentene copolymer. In addition, in the copolymer of ethylene and another olefin, 50% or more of the total number of constitutional units is derived from ethylene.
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.
Further, the copolymer of propylene and another olefin may be a random copolymer or a block copolymer. Of them, a block copolymer can be used from the viewpoint of excellent impact resistance. In particular, a propylene-ethylene block copolymer in which another olefin is ethylene can be used. The propylene-ethylene block copolymer is a block copolymerized polypropylene having an ethylene block as a dispersed phase. That is, it is a polypropylene resin in which homopolypropylene is used as a continuous phase and a dispersed phase containing a polyethylene is present in the continuous phase. Such a block copolymerized 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 copolymerized polypropylene is preferred from the viewpoint of excellent impact resistance.
In addition, in the copolymer of propylene and another olefin, 50% or more of the total number of constitutional units is derived from propylene.
The other component that is a thermoplastic polymer include fossil-derived polyamides having a bio-based carbon content rate of less than 80% according to ISO 16620-2 (polyamides not included in the plant-derived PA described above). Examples of the fossil-derived polyamide 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, and polyamide 9T/2M-8T. These polyamides may be used singly, or two or more thereof may be used in combination. Further, when two or more of these copolymers are used, both pellets made of a mixed resin and a pellet mixture are included.
When the other component is a component which does not act similarly to the plant-derived PE, the plant-derived PA, and the compatibilizer, an amount of the other component is preferably 500 parts by mass or less when the total amount of the plant-derived PE, the plant-derived PA, and the compatibilizer is 100 parts by mass. A lower limit value of the amount of the other component, when contained in the thermoplastic resin composition, is not limited, but can be, for example, 1 part by mass. Examples of such other components include various additives such as a flame retardant, a flame retardant aid, a filling material, a colorant, an antibacterial agent, and an antistatic agent. These may be used singly, or two or more thereof may be used in combination.
The method for producing the thermoplastic resin composition of the present invention includes: a melt-kneading step of melt-kneading a melt-kneaded product of the plant-derived PA and the compatibilizer with the plant-derived PE.
The properties and blending of each of the plant-derived PE, the plant-derived PA, and the compatibilizer are as described above.
The melt-kneading step is a step of melt-kneading a melt-kneaded product of the plant-derived PA and the compatibilizer with the plant-derived PE.
The melt-kneaded product used in this case may be a composition in a molten state or a composition in a softened state, or may be solidified by pelletization or the like.
In this melt-kneading step, any melt-kneading apparatus may be used. For example, it is possible to use an extruder (single screw extruder, twin screw kneading extruder, etc.), a kneader, a mixer (high speed flow mixer, paddle mixer, ribbon mixer, etc.) and the like. These apparatuses may be used singly, or may be used in combination of two or more thereof. In addition, when two or more types of apparatuses are used, they may be operated continuously or batchwise. Furthermore, the raw materials may be mixed all at once, or may be mixed by adding and charging in plural separate parts (multistage compounding).
A 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.
In the present method, a melt-kneaded product melt-kneaded in advance (a melt-kneaded product of the plant-derived PA and the compatibilizer) is used, and thus kneading is performed when the plant-derived PA and the compatibilizer react with each other. Therefore, it is considered that a reactive group is added to a surface of the plant-derived PA due to the compatibilizer having the reactive group, so that the plant-derived PA in which the compatibilizer is bonded to the surface is formed. The plant-derived PA in which the compatibilizer is bonded to the surface is sheared by further kneading, so that an unreacted surface of the plant-derived PA appears. Then, it is considered that an unreacted compatibilizer reacts further with the unreacted surface. It is considered that the plant-derived PA to which the compatibilizer is bound is sheared in this way, an unreacted surface of the plant-derived PA appears, and a reaction of the unreacted compatibilizer with the unreacted surface is repeated, whereby a smaller reaction product of the plant-derived PA and the compatibilizer can be stably formed without relying on a high shear.
It is considered that, when the amount of the compatibilizer that can be supplied in the above-described process is small, the plant-derived PA to which the compatibilizer is bound is difficult to be reduced in size, and that, when the amount of the compatibilizer that can be supplied is sufficiently large, the plant-derived PA to which the compatibilizer is bound is easily reduced in size.
The molded body of the present invention is characterized by being composed of the thermoplastic resin composition of the present invention described above.
When the thermoplastic resin composition is molded, any known molding method can be used. Specifically, examples of molding methods 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 may be used singly, or two or more thereof may be used in combination.
The shape, size, thickness, and the like of the molded body are not particularly limited, and the application of the molded body is not particularly limited. Examples of the molded body include pellets. When the molded body is a pellet, it can be used as a modifier for performing modification (for example, impact resistance improvement, fluidity improvement, and the like) by being added to another resin. The object to be modified is not limited, and examples thereof include polyolefins. As the polyolefin, a plant-derived PE can be used. In addition, a plant-derived polypropylene (plant-derived PP) similar to the plant-derived PE can be used. Furthermore, the fossil derived polyolefin described above can be used as the other component.
In this modification, dry blending can be utilized by utilizing the present molded body. That is, the present molded body is mixed with a pellet of a resin or the like to be modified by dry blending, and then the mixed pellet is molded, whereby a modified molded body (shaped body which is not in a simple pellet shape or the like) can be obtained. In general, at the time of modification, a modified molded body (shaped body which is not in a simple pellet shape or the like) is obtained by pelletizing a melt-kneaded product obtained by melt-kneading them, and molding the obtained modified pellet. However, when the present molded body (modifier) is used, modification can be performed by dry blending without requiring the melt-kneading.
Further, the molded body is used as various articles and the like used for vehicles such as automobiles, railway vehicles (whole vehicles), aircraft fuselages (whole fuselages), ships/hulls (whole hulls), and bicycles (whole bodies).
Among them, examples of the automobile articles include exterior parts, interior parts, engine parts, and electrical parts. Specific examples of the exterior parts for automobiles include roof rail, fender, fender liner, garnish, bumper, door panel, roof panel, hood panel, trunk lid, fuel lid, door mirror stay, spoiler, hood louver, wheel cover, wheel cap, grill apron cover frame, lamp bezel, door handle (pull handle), door molding, rear finisher, wiper, engine under cover, floor under cover, rocker molding, cowl louver, and cowl (motorcycle).
Examples of the interior parts for automobiles include trim parts such as door trim substrates (FR, RR, and BACK), pockets, armrests, switch bases, decorative panels, ornament panels, EA materials, speaker grilles, and quarter trim substrates; pillar garnish; cowl side garnish (cowl side trim); sheet 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 console; overhead console; sun visor; deck board (luggage board), undertray; package tray; high mount stop lamp cover; CRS cover; seat-side garnish; scuff plate; room lamp; assist grip; safety belt part; register blade; washer lever; window regulator handle; knob of window regulator handle; and passive light lever.
Examples of the engine parts for automobiles include alternator terminal, alternator connector, IC regulator, potential meter base for light diya, exhaust gas valve, fuel pipe, cooling pipe, brake pipe, wiper pipe, exhaust pipe, intake pipe, hose, tube, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wafer sensor, throttle position sensor, crank shaft position sensor, air flow meter, brake pad wear sensor, brake piston, solenoid bobbin, engine oil filter, ignition device case, and torque control lever.
Examples of the electrical parts for automobiles include various connectors such as battery peripheral parts, thermostats for air conditioners, warm air flow control valves, brush holders for radiator motors, water pump impellers, turbine vanes, wiper motor-related parts, distributors, starter switches, starter relays, wire harnesses for transmissions, window washer nozzles, air conditioner switch substrates, coils for fuel-related electromagnetic valves, wire harness connectors, SMJ connectors, PCB connectors, door grommet connectors, and fuse connectors, horn terminals, electrical part insulating plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, cleaner cases, filter cases, and power trains.
Furthermore, the molded body is also used as various articles and the like in non-vehicle applications other than the above-described vehicles. That is, examples of the non-vehicle applications include:
industrial materials such as ropes, spunbonds, polishing brushes, industrial brushes, filters, transport containers, trays, trolleys, and other general materials;
electronic components such as connectors, coils, sensors, LED lamps, sockets, resistors, relay cases, small switches, coil bobbins, capacitors, variable condenser cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, small speed change gears, magnetic head bases, power modules, semiconductors, liquid crystal, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, and computer-related parts;
electric equipment such as generators, motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, breakers, knife switches, multipole rods, and electrical parts cabinets;
housings of industrial robots, housings of care robots, housing of drones (flying objects which fly by remote control, flying objects which fly autonomously),
household and office products such as VTR parts, television parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio and LD parts, CD and DVD parts, lighting parts, refrigerator parts, washing machine parts, air conditioner parts, typewriter and word processor parts, office computer parts, PCs, game machines, tablet terminals, mobile phones, smartphones, telephones and related parts, facsimile parts, copier parts, cleaning and cleaning equipment, and motor parts;
optical and precision instruments such as cameras, watches, microscopes, binoculars, telescopes, and glasses;
daily necessities and daily necessities such as food trays, storage boxes, storage trays, attached cases, suitcases, helmets, water bottles, storage cases such as bottles, toiletries, writing utensils, stationery, book stands, skin care utensils, utensils, tableware, washing utensils, cleaning utensils, clothing hangers, food containers, and opening/closing lids (e.g., glass bottles);
entertainment items such as toys;
machining/general machine parts such as housings of grass cutters, covers, housings of electric tools, covers, and various clips;
sporting goods such as tennis racket strings, ski boards/boards, protectors (baseball, soccer, motor sports), shoes, shoe soles (soles for sports shoes), and outdoor/climbing tools;
furniture-related items such as dress cases, tables, chairs (chairs), shoe boxes, kitchen utensils, toilet utensils, and bathing tools;
residential and civil engineering-related goods such as interior and exterior walls/roofs, heat insulating materials, door/door-related parts, window material-related parts, flooring material-related parts, base isolation/damping parts, shutters, gutters, clean water/waste water-related parts (lifeline-related parts), parking garages, gas/electrical-related parts (lifeline-related parts), civil engineering-related parts, traffic signals, road signs, pylons, center poles, guard rails (guard wires), and equipment for construction work;
medical supplies such as mouthpieces, medical devices, and pharmaceutical containers;
clothing-related items such as shoes; and
agriculture-, forestry-, and fishery-related products such as agricultural machines, agricultural tools, flower pots (planters), fishing tools, aquaculture tools, and forestry tools.
The modifier of the present invention is a polyethylene modifier in which the resin to be modified is a polyethylene (PE1). By blending the modifier of the present invention, it is possible to realize modification of improving the impact resistance of the polyethylene (PE1). In particular, also when a plant-derived polyethylene (plant-derived PE) having a bio-based carbon content rate of 80% or more according to ISO 16620-2 is selected as the polyethylene (PE1), an excellent impact resistance-imparting effect can be obtained.
The modifier of the present invention contains a polyethylene (PE2), a polyamide, and a compatibilizer. Among these components, the compatibilizer is a modified elastomer having a reactive group that reacts with the polyamide.
Furthermore, the polyethylene (PE2) has a bio-based carbon content rate of 80% or more according to ISO 16620-2. That is, it is a plant-derived polyethylene (plant-derived PE).
Furthermore, the polyamide has a bio-based carbon content rate of 80% or more according to ISO 16620-2. That is, it is a plant-derived polyamide (plant-derived PA).
<1> Polyethylene PE2
The polyethylene PE2 is basically the same as the plant-derived PE described above in the description about the thermoplastic resin composition, and the “plant-derived PE” in the thermoplastic resin composition can be read as “polyethylene PE2” (hereinafter, the polyethylene is also simply referred to as “plant-derived PE2”).
The plant-derived PE2 is a polymer having a structure (methylene chain) in which methylene groups (—CH2—) are linked as a main skeleton. The methylene chain is a constitutional unit derived particularly from ethylene.
Also, the plant-derived PE2 includes a homopolymer of ethylene and a copolymer of ethylene and another olefin. These may be used singly, or two or more thereof may be used in combination. When the plant-derived PE2 is a copolymer, a non-ethylene-derived unit (another olefin-derived unit) preferably occupies 50% or less (further 30% or less, and further 10% or less) of the total number of constitutional units. This is because the lower the proportion of the non-ethylene-derived unit, the higher the bio-based carbon content rate. That is, the plant-derived PE2 is preferably a substantial ethylene homopolymer having a low proportion of the non-ethylene-derived unit (for example, 10% or less).
As another olefin as described above, similar examples indicated with respect to the plant-derived PE described above in the description about the thermoplastic resin composition can be directly applied.
Various properties of the plant-derived PE2 are not limited, but a high density polyethylene having a density of 0.942 g/cm3 or more is preferred. Furthermore, the MFR (230° C./2.16 kg) of the plant-derived PE2 is preferably 35 g/10 min or less. The MFR of the plant-derived PE2 is 35 g/10 min or less (usually, 1 g/10 min or more), so that the resulting modifier can have excellent modification performance. Further, the MFR is preferably 20 g/10 min or less, and more preferably 15 g/10 min or less. A lower limit is not limited, but is preferably 2 g/10 min or more, and more preferably 3 g/10 min or more, from the viewpoint of ease of melt-kneading.
In the present invention, the MFR (230° C./2.16 kg) of the polyethylene is a value as measured according to the standard ISO 1133 or ASTM D1238. Values according to these standards are usually substantially the same.
As described above, the density of the plant-derived PE2 is preferably 0.942 g/cm3 or more, and, further, more preferably 0.950 g/cm3 or more. An upper limit of the density is not limited, but is preferably 0.954 g/cm3 or less.
Achievement of both the MFR and the density described above can be adjusted by linearity, a branching amount, a molecular weight, and the like of the polyethylene.
In the present invention, the density of the polyethylene is a value as measured according to the standard ISO 1183 or ASTM D792. Values according to these standards are usually substantially the same.
Furthermore, the MFR (230° C./2.16 kg) of the plant-derived PE2 is preferably small. Specifically, the MFR is preferably closer to an MFR (230° C./2.16 kg) of a melt-kneaded product obtained from a plant-derived PA and a compatibilizer, which will be described later. That is, it is considered that, as for kneading of the plant-derived PA and the compatibilizer can be promoted by a reaction between them, and the kneading of them is hardly affected by a difference in MFR. On the other hand, in kneading of the plant-derived PE2 and the melt-kneaded product (the melt-kneaded product of the plant-derived PA and the compatibilizer), they are not reacted. Thus, it is considered that the kneading of them is easily affected by a difference in MFR therebetween. Therefore, it is considered that kneadability is improved by bringing the MFR of the plant-derived PE2 and the MFR of the melt-kneaded product close to each other, and that the impact resistance can be improved accordingly.
Specifically, when the MFR (230° C./2.16 kg) of the plant-derived PE2 is MPE2 (g/10 min) and the MFR (230° C./2.16 kg) of the melt-kneaded product of the plant-derived PA and the compatibilizer is MPX (g/10 min), a ratio between them, MPE2/PX (=MPE2/MPX), is preferably 0.5≤MPE2/PX≤20, more preferably 1≤MPE2/PX≤17, even more preferably 2≤MPE2/PX≤13, and particularly preferably 5≤MPE2/PX≤10.
Although a range of MPX is not limited, for example, 0.1≤MPX (g/10 min)≤10 can be set, further 0.5≤MPX (g/10 min)≤5 can be set, and further 1≤MPX (g/10 min)≤3 can be set.
<2> Polyamide
The polyamide used in the modifier is basically the same as the plant-derived PA described above in the description about the thermoplastic resin composition, and is the same as the plant-derived PA described above with respect to the bio-based carbon content rate. Furthermore, the polyamide is the same as the plant-derived PA described above in that it is a polymer having a structure in which hydrocarbon groups are linked via amide bonds as a main skeleton, and similar compounds are exemplified as the monomer. Furthermore, the polyamide is the same as the plant-derived PA described above in that it can be obtained by copolymerization of a diamine and a dicarboxylic acid, and similar compounds can be exemplified as the monomer in this case. Among them, from the viewpoint of a high bio-based carbon content rate, it preferably contains a large amount of plant-derived 1,10-diaminodecane and/or 1,5-diaminopentane as the diamine. Further, from the viewpoint of a high bio-based carbon content rate, it preferably contains a large amount of plant-derived sebacic acid, furandicarboxylic acid, and/or glutaric acid as the dicarboxylic acid. Examples of the plant-derived PA are similar to those in a case of the plant-derived PA described above, and these polyamides may be used singly, or two or more thereof may be used in combination. Further, when two or more of these copolymers are used, both pellets made of a mixed resin and a pellet mixture are included.
In addition, regardless of whether the plant-derived PA is a homopolymer of an amino acid or alactam or a copolymer of a diamine and a dicarboxylic acid, the plant-derived PA becomes plant-derived due to the fact that a monomer that forms these polymers is derived from a plant raw material. A total amount of the monomer may be a plant-derived monomer, or only apart thereof may be a plant-derived monomer (that is, a fossil-derived monomer may be contained in the other part). That is, as a result, the plant-derived PA has only to have a bio-based carbon content rate of 80% or more.
Although various properties of the plant-derived PA are not limited, it is preferable that the plant-derived PA is a polyamide having a density of 1.15 g/cm3 or less and have an MFR (230° C./2.16 kg) of 50 g/10 min or less. The MFR of the plant-derived PA is 50 g/10 min or less (usually, 1 g/10 min or more), so that the resulting modifier can have excellent modification performance. The MFR is even more preferably 40 g/10 min or less, and more preferably 35 g/10 min or less. A lower limit is not limited, but is preferably 3 g/10 min or more, and more preferably 5 g/10 min or more, from the viewpoint of ease of melt-kneading.
In the present invention, the MFR (230° C./2.16 kg) of the plant-derived PA is a value as measured according to the standard ISO 1133 or ASTM D1238. Values according to these standards are usually substantially the same.
As described above, the density of the plant-derived PA is preferably 1.15 g/cm3 or less, and, further, more preferably 1.08 g/cm3 or less. A lower limit of the density is not limited, but is preferably 0.98 g/cm3 or more.
Achievement of both the MFR and the density can be adjusted by linearity, a branching amount, a molecular weight, and the like of the plant-derived PA.
In the present invention, the density of the plant-derived PA is a value as measured according to the standard ISO 1183 or ASTM D792. Values according to these standards are usually substantially the same.
<3> Compatibilizer
The compatibilizer used in the modifier is basically the same as the compatibilization described above in the description about the thermoplastic resin composition, but is preferably a component having affinity for the plant-derived PE2. In this case, the compatibilizer is a component having a compatibilizing effect on the plant-derived PE2 and the plant-derived PA. That is, the compatibilizer is preferably a compatibilizer for the plant-derived PE2 and the plant-derived PA.
In the present modifier, the compatibilizer may be reacted entirely with the plant-derived PA, or may be reacted only partially therewith.
Furthermore, the reactive group of the modified elastomer is similar to that of the compatibilization described above in the description about the thermoplastic resin composition, the modification amount of the modified elastomer by the reactive group is also similar to that of the compatibilization described above, and examples of the reactive group of the modified elastomer are also similar. Furthermore, the modification amount of the modified elastomer by the reactive group is also similar. Similarly, examples of the modified elastomer include polymers using various monomers capable of introducing a reactive group, oxidative decomposition products of various polymers, and graft polymers of organic acids to various polymers. Examples of the monomer capable of introducing a reactive group are also similar. Furthermore, the same type of skeleton resin of the modified elastomer is employed.
Although various properties of the compatibilizer are not limited, it is preferable that the compatibilizer is a modified elastomer having a density of 0.90 g/cm3 or less and have an MFR (230° C./2.16 kg) of 10 g/10 min or less. The MFR of the compatibilizer is 10 g/10 min or less (usually, 0.5 g/10 min or more), so that the resulting modifier can have excellent modification performance. Further, the MFR is preferably 7 g/10 min or less, and more preferably 5 g/10 min or less. An upper limit is not limited, but is preferably 0.5 g/10 min or more, and more preferably 1.0 g/10 min or more, from the viewpoint of ease of melt-kneading.
In the present invention, the MFR (230° C./2.16 kg) of the compatibilizer is a value as measured according to the standard ISO 1133 or ASTM D1238. Values according to these standards are usually substantially the same.
As described above, the density of the compatibilizer is preferably 0.90 g/cm3 or less, and, further, more preferably 0.89 g/cm3 or less. A lower limit of the density is not limited, but is preferably 0.85 g/cm3 or more.
Achievement of both the MFR and the density can be adjusted by linearity, a branching amount, a molecular weight, a modification amount, and the like of the compatibilizer.
In the present invention, the density of the compatibilizer is a value as measured according to the standard ISO 1183 or ASTM D792. Values according to these standards are usually substantially the same.
The molecular weight of the modified elastomer is not particularly limited, but a 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 a GPC method (in terms of standard polystyrene).
<4> Blending of Each Component
Furthermore, when the total mass proportion of the plant-derived PE2, the plant-derived PA, and the compatibilizer constituting the modifier of the present invention is 100 mass %, a mass proportion of the plant-derived PE2 is RPE2 mass %, a mass proportion of the plant-derived PA is RPA mass %, and a mass proportion of the compatibilizer is RCB mass %.
In this case, the mass proportion RCB (mass %) of the compatibilizer is preferably 1 to 70 mass %, more preferably 2 to 60 mass %, even more preferably 2 to 50 mass %, still even more preferably 3 to 40 mass %, still even more preferably 3 to 35 mass %, and still even more preferably 4 to 30 mass %.
In addition, a ratio (RPE2/RPA) of the mass proportion RPE2 of the plant-derived PE2 to the mass proportion RPA of the plant-derived PA is preferably 0.3 to 3.5. Further, the ratio (RPE2/RPA) can be 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, in a case where the resin to be modified by the modifier of the present invention is the polyethylene PE1, the modification effect tends to be remarkably improved when RPE2≥RPA. More specifically, the ratio (RPE2/RPA) is preferably 1 to 3.5, more preferably 1.0 to 3.3, even more preferably 1.2 to 3.0, still even more preferably 1.5 to 2.5, and still even more preferably 1.8 to 2.3. This ratio (RPE/RPA) is particularly effective when the mass proportion RCB of the compatibilizer is 30 mass % or less.
In addition, the mass proportion RPE2 (mass %) of the plant-derived PE2 is preferably 10 to 90 mass %, more preferably 13 to 85 mass %, even more preferably 17 to 80 mass %, still even more preferably 20 to 75 mass %, still even more preferably 23 to 70 mass %, and still even more preferably 25 to 65 mass %.
Furthermore, the total proportion RPA+CB (mass %) of the plant-derived PA and the compatibilizer is preferably 10 to 90 mass %, more preferably 15 to 87 mass %, even more preferably 20 to 83 mass %, still even more preferably 25 to 80 mass %, still even more preferably 30 to 77 mass %, and still even more preferably 35 to 75 mass %.
In addition, the mass proportion RPA (mass %) of the plant-derived PA is preferably 1 to 80 mass %, more preferably 3 to 75 mass %, even more preferably 5 to 70 mass %, still even more preferably 10 to 75 mass %, still even more preferably 15 to 70 mass %, and still even more preferably 20 to 65 mass %.
Further, when the total mass proportion of the plant-derived PA and the compatibilizer is 100 mass %, a mass proportion of the compatibilizer is preferably 3 to 70 mass %, more preferably 4 to 65 mass %, even more preferably 5 to 60 mass %, still even more preferably 6 to 55 mass %, still even more preferably 7 to 45 mass %, and still even more preferably 8 to 40 mass %.
In particular, in a case of obtaining a modifier capable of exerting a high impact resistance-imparting effect in a range in which the mass proportion RPA of the plant-derived PA is lower than the mass proportion RPE2 of the plant-derived PE2 (that is, RPA<RPE2), RPE2:RPA:RCB is preferably 50 to 80 mass %:20 to 45 mass %:1 to 25 mass %, more preferably 52 to 70 mass %:24 to 40 mass %:3 to 18 mass %, and particularly preferably 55 to 65 mass %:27 to 35 mass %:6 to 14 mass %. In the above ranges, the Charpy impact strength of the polyethylene PE1 can be improved 3 times or more by the modification.
Although the fluidity of the modifier of the present invention is not limited, the density is 0.93 to 1.00 g/cm3, and the MFR (230° C./2.16 kg) can be set to 3 g/10 min or more (usually, 30 g/10 min or less). The MFR can be further set to 6 g/10 min or more, further set to 12 g/10 min or more, and further set to 17 g/10 min or more. An upper limit value is not limited, but can be 27 g/10 min or less. In particular, the MFR can be set to 3 to 30 g/10 min, further to 3 to 27 g/10 min, further to 3 to 17 g/10 min, and further to 3 to 12 g/10 min.
In the present invention, the MFR (230° C./2.16 kg) of the compatibilizer is a value as measured according to the standard ISO 1133 or ASTM D1238. Values according to these standards are usually substantially the same.
The phase structure of the modifier of the present invention is not limited, and may similarly have any of the specific phase structures (1) to (3) described above in the description about the thermoplastic resin composition (provided that the “plant-derived PE” is read as “plant-derived PE2”). Similarly, in particular, when the phase structures (1) and (2) described above are exhibited, excellent impact resistance properties can be obtained by the phase structure having the finely dispersed phase (B2). Similarly, in a case where the thermoplastic resin composition has the co-continuous structure (3), excellent impact resistance properties can be obtained.
In a case where the modifier has any of the phase structures described above, the size of the dispersed phase contained in the continuous phase is not limited, and the above description in the description about the thermoplastic resin composition can be applied as it is.
When the modifier has the dispersed phase in the dispersed phase, the size of the finely dispersed phase contained in the dispersed phase is not limited, and the above description in the description about the thermoplastic resin composition can be applied as it is.
<5> Other Components
The thermoplastic resin composition of the present invention can contain any other component, in addition to the plant-derived PE2, the plant-derived PA, and the compatibilizer described above.
When the other component is a thermoplastic polymer which can act similarly to the plant-derived PE2, the plant-derived PA, and the compatibilizer (provided that components functioning as filling materials, fillers, and the like are excluded), an amount of the thermoplastic polymer as the other component is preferably 20 parts by mass or less when the total amount of the plant-derived PE2, the plant-derived PA, and the compatibilizer is 100 parts by mass. A lower limit value of the amount of the other component, when contained in the thermoplastic resin composition, is not limited, but can be, for example, 1 part by mass.
The other component that is a thermoplastic polymer include fossil-derived polyolefins having a bio-based carbon content rate of less than 80% according to ISO 16620-2 (polyolefins not included in the plant-derived PE2 described above). The fossil-derived polyolefins include homopolymers of olefins and/or copolymers of olefins.
The olefins constituting the fossil-derived polyolefins are not particularly limited, and examples thereof include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, and 1-octene. These may be used singly, or two or more thereof may be used in combination.
That is, the fossil-derived polyolefins include polyethylene, polypropylene, poly(1-butene), poly(1-hexene), and poly(4-methyl-1-pentene). These polymers may be used singly, or two or more thereof may be used in combination. Further, when two or more of these copolymers are used, both pellets made of a mixed resin and a pellet mixture are included.
Examples of the polyethylene include an ethylene homopolymer and a copolymer of ethylene and another olefin. Examples of the latter include an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, an ethylene-1-octene copolymer, and an ethylene-4-methyl-1-pentene copolymer. In addition, in the copolymer of ethylene and another olefin, 50% or more of the total number of constitutional units is derived from ethylene.
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.
Further, the copolymer of propylene and another olefin may be a random copolymer or a block copolymer. Of them, a block copolymer can be used from the viewpoint of excellent impact resistance. In particular, a propylene-ethylene block copolymer in which another olefin is ethylene can be used. The propylene-ethylene block copolymer is a block copolymerized polypropylene having an ethylene block as a dispersed phase. That is, it is a polypropylene resin in which homopolypropylene is used as a continuous phase and a dispersed phase containing a polyethylene is present in the continuous phase. Such a block copolymerized 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 copolymerized polypropylene is preferred from the viewpoint of excellent impact resistance.
In addition, in the copolymer of propylene and another olefin, 50% or more of the total number of constitutional units is derived from propylene.
The other component that is a thermoplastic polymer include fossil-derived polyamides having a bio-based carbon content rate of less than 80% according to ISO 16620-2 (polyamides not included in the plant-derived PA described above). Examples of the fossil-derived polyamide 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, and polyamide 9T/2M-8T. These polyamides may be used singly, or two or more thereof may be used in combination. Further, when two or more of these copolymers are used, both pellets made of a mixed resin and a pellet mixture are included.
<6> Production of Modifier
The modifier of the present invention may be produced in any way, and can be obtained by melt-kneading a melt-kneaded product of the plant-derived PA and the modified elastomer with the plant-derived PE2. 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 product of the plant-derived PA and the compatibilizer with the plant-derived PE2.
The melt-kneaded product of the plant-derived PA and the compatibilizer may be a composition in a molten state or a composition in a softened state, or may be solidified by pelletization or the like.
Also, in this melt-kneading step, any melt-kneading apparatus may be used. For example, it is possible to use an extruder (single screw extruder, twin screw kneading extruder, etc.), a kneader, a mixer (high speed flow mixer, paddle mixer, ribbon mixer, etc.) and the like. These apparatuses may be used singly, or may be used in combination of two or more thereof. In addition, when two or more types of apparatuses are used, they may be operated continuously or batchwise. Furthermore, the raw materials may be mixed all at once, or may be mixed by adding and charging in plural separate parts (multistage compounding).
A 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.
In the above method, a melt-kneaded product is used. When this melt-kneaded product is obtained, kneading is performed when the plant-derived PA reacts with the compatibilizer. Therefore, it is considered that a reactive group is added to a surface of the plant-derived PA due to the compatibilizer having the reactive group, so that the plant-derived PA in which the compatibilizer is bonded to the surface is formed. The plant-derived PA in which the compatibilizer is bonded to the surface is sheared by further kneading, so that an unreacted surface of the plant-derived PA appears. Then, it is considered that an unreacted compatibilizer reacts further with the unreacted surface. It is considered that the plant-derived PA to which the compatibilizer is bound is sheared in this way, an unreacted surface of the plant-derived PA appears, and a reaction of the unreacted compatibilizer with the unreacted surface is repeated, whereby a smaller reaction product of the plant-derived PA and the compatibilizer can be stably formed without relying on a high shear.
It is considered that, when the amount of the compatibilizer that can be supplied in the above-described process is small, the plant-derived PA to which the compatibilizer is bound is difficult to be reduced in size, and that, when the amount of the compatibilizer that can be supplied is sufficiently large, the plant-derived PA to which the compatibilizer is bound is easily reduced in size.
<7> Resin to be Modified (Polyethylene PE1)
The resin to be modified by the modifier of the present invention is the polyethylene PE1. The polyethylene PE1 can be used regardless of raw material from which it is derived. That is, it may be a fossil-derived polyethylene, a plant-derived polyethylene, or a polyethylene derived from both of them, but, among them, a plant-derived polyethylene is preferred. A plant-derived polyethylene is used as the polyethylene PE1, thereby making it possible to obtain a polyethylene-based molded body raw material and a polyethylene-based molded body each having excellent mechanical properties while improving the bio-based carbon content rate.
When the polyethylene PE1 is a plant-derived polyethylene (that is, plant-derived PE1), the bio-based carbon content rate thereof is not limited, but, as is the case with the plant-derived PE2, the bio-based carbon content rate as measured according to the standard ISO 16620-2 is preferably 80% or more (may be 100%). The bio-based carbon content rate of the plant-derived PE1 may further be 85% or more, or 90% or more.
As is the case with the plant-derived PE2, the bio-based carbon content rate of the plant-derived PE1 can be a value as measured according to the standard ASTM D6866, in addition to ISO 16620-2. Usually, values according to these standards are substantially the same.
The polyethylene PE1 is a polymer having a structure (methylene chain) in which methylene groups (—CH2—) are linked as a main skeleton. The methylene chain is a constitutional unit derived particularly from ethylene.
Also, the polyethylene PE1 includes a homopolymer of ethylene and a copolymer of ethylene and another olefin. These may be used singly, or two or more thereof may be used in combination. When the polyethylene PE1 is a copolymer, anon-ethylene-derived unit (another olefin-derived unit) preferably occupies 50% or less (further 30% or less, and further 10% or less) of the total number of constitutional units. This is because the lower the proportion of the non-ethylene-derived unit, the higher the bio-based carbon content rate. That is, the polyethylene PE1 is preferably a substantial ethylene homopolymer having a low proportion of the non-ethylene-derived unit (for example, 10% or less).
Examples of another olefin as described above include an olefin having 3 carbon atoms (propylene), an olefin having 4 carbon atoms (e.g., 1-butene), an olefin having 5 carbon atoms (3-methyl-1 butene, 1-pentene, etc.), an olefin having 6 carbon atoms (3-methyl-1 pentene, 4-methyl-1 pentene, 1-hexene, etc.), and an olefin having 8 carbon atoms (e.g., 1-octene). These may be used singly, or two or more thereof may be used in combination.
Various properties of the polyethylene PE1 are not limited, but a high density polyethylene having a density of 0.942 g/cm3 or more is preferred. Furthermore, the MFR (230° C./2.16 kg) of the polyethylene PE1 is preferably 35 g/10 min or less. The MFR of the polyethylene PE1 is 35 g/10 min or less (usually, 1 g/10 min or more), so that the molded body can obtain more excellent impact resistance properties. Further, the MFR is preferably 20 g/10 min or less, and more preferably 15 g/10 min or less. A lower limit is not limited, but is preferably 2 g/10 min or more, and more preferably 3 g/10 min or more, from the viewpoint of ease of melt-kneading.
In the present invention, the MFR (230° C./2.16 kg) of the polyethylene is a value as measured according to the standard ISO 1133 or ASTM D1238. Values according to these standards are usually substantially the same.
As described above, the density of the polyethylene PE1 is preferably 0.942 g/cm3 or more, and, further, more preferably 0.950 g/cm3 or more. An upper limit of the density is not limited, but is preferably 0.954 g/cm3 or less.
Achievement of both the MFR and the density described above can be adjusted by linearity, a branching amount, a molecular weight, and the like of the polyethylene.
In the present invention, the density of the polyethylene is a value as measured according to the standard ISO 1183 or ASTM D792. Values according to these standards are usually substantially the same.
Furthermore, the MFR (230° C./2.16 kg) of the polyethylene PE1 is preferably small. Specifically, MFR is preferably closer to the MFR (230° C./2.16 kg) of the modifier. It is considered that kneadability is improved by bringing the MFR of the polyethylene PE1 and the MFR of the modifier close to each other, and that the impact resistance can be improved accordingly.
The polyethylene PE1 and the plant-derived PE2 may be different polyethylenes, but are preferably the same polyethylenes. This makes it possible to improve the bio-based carbon content rate of the entire molded body obtained. When the polyethylene PE1 and the plant-derived PE2 are the same polyethylenes, the polyethylene PE1 is the plant-derived PE1. Both plant-derived PE1 and plant-derived PE2 are high density polyethylenes and have substantially the same bio-based carbon content rate, MFR (230° C./2.16 kg) and density (g/cm3).
<8> Use of Modifier as Carrier for Additive
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 added to the obtained molded body simultaneously with the improvement (modification) in impact resistance.
In this case, the modifier of the present invention can be rephrased as a carrier for adding an additive to a resin to be added which is a polyethylene (PE1),
the carrier containing an additive, a polyethylene (PE2), a polyamide, and a compatibilizer,
wherein the compatibilizer is a modified elastomer having a reactive group that reacts with the polyamide, and
wherein the polyethylene (PE2) and the polyamide have a bio-based carbon content rate of 80% or more according to ISO 16620-2.
The type of additive is not limited, and examples thereof include a flame retardant, a flame retardant aid, a filling material, a colorant, an antibacterial agent, and an antistatic agent. These may be used singly, or two or more thereof may be used in combination.
When the modifier of the present invention is used as a carrier for an additive, for example, 500 parts by mass or less of the additive can be blended when the total amount of the plant-derived PE2, the plant-derived PA, and the compatibilizer is 100 parts by mass. A lower limit value of an amount of the additive contained in the carrier, but can be, for example, 1 part by mass.
The method for producing a molded body of the present invention is characterized by including a molding step of molding a raw material obtained by dry-blending a resin to be modified with the modifier of the present invention described above. That is, the present method for producing a molded body can be rephrased as a modification method.
In this modification, dry blending can be utilized. Specifically, a modified molded body (for example, shaped body) can be obtained by mixing the modifier with raw material particles (pellets, granular materials, etc.) of the polyethylene PE1, which is a resin to be modified, by dry blending, and then molding the mixed particles. In general, at the time of modification, a modified molded body (for example, shaped body) is obtained by pelletizing a melt-kneaded product obtained by melt-kneading them and molding the obtained modified pellet. However, the present method can provide an excellent modification effect through dry blending, without requiring the melt-kneading. That is, according to the present method, it is possible to easily obtain a polyethylene-based molded body having excellent impact resistance while realizing a reduction in environmental load through a small number of steps without undergoing a preliminary kneading step.
An amount of the modifier used in the present method is not limited, but the modifier can be used so as to constitute 30 to 70 mass % when a total amount of the resin to be modified and the modifier is 100 mass %. Furthermore, the modifier is preferably used so as to constitute 35 to 65 mass %, and more preferably used so as to constitute 40 to 60 mass %.
In particular, in the method for producing a molded body of the present invention, a molded body to which a high modification effect is imparted can be obtained by using the plant-derived PE1 as the resin to be modified and using a modifier satisfying RPE2≥RPA. Furthermore, in a range in which the mass proportion RCB of the compatibilizer is 30 mass % or less, a modifier having a ratio (RPE2/RPA) of 1 to 3.5, further 1.0 to 3.3, further 1.2 to 3.0, further 1.5 to 2.5, or further 1.8 to 2.3 is used, so that a molded body to which an especially high modification effect is imparted can be obtained. In this case, as described above, when the total amount of the resin to be modified and the modifier is 100 mass %, the modifier is used so as to constitute 30 to 70 mass %, whereby a molded body to which a particularly high modification effect is imparted can be obtained. Furthermore, as described above, the modifier is preferably used so as to constitute 35 to 65 mass %, and more preferably used so as to constitute 40 to 60 mass %.
At the time of molding, any known molding method can be used. Specifically, examples of molding methods 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 may be used singly, or two or more thereof may be used in combination.
In addition, the shape, size, thickness, and the like of the molded body are not particularly limited, and the application thereof is not particularly limited. The above description in the description about the molded body can be applied as it is.
Hereinafter, the present invention will be specifically described by way of examples.
As the plant-derived PE, the following two polyethylenes were prepared.
PE-1: HDPE (product name “SHA7260” manufactured by Braskem S.A.), density: 0.955 g/cm3, MFR (230° C./2.16 kg): 32 g/10 min, bio-based carbon content rate: 94% or more
PE-2: HDPE (product name “SHC7260” manufactured by Braskem S.A.), density: 0.953 g/cm3, MFR (230° C./2.16 kg): 12 g/10 min, bio-based carbon content rate: 94% or more
As the plant-derived PA, the following polyamide was prepared.
PA: PA11 (product name “Rilsan BMN O” manufactured by Arkema S.A.), density: 1.03 g/cm3, MFR (230° C./2.16 kg): 32 g/10 min, bio-based carbon content rate: 99% or more
As the compatibilizer, the following ethylene-1-butene copolymer was prepared.
Compatibilizer: maleic anhydride-modified EBR (product name “TAFMER MH7020” manufactured by Mitsui Chemicals, Inc.), density: 0.866 g/cm3, MFR (230° C./2.16 kg): 1.5 g/10 min
The plant-derived PA and the compatibilizer were dry-blended, and the resultant mixture was then charged into a twin-screw melt-kneading extruder (manufactured by Plastic Engineering Laboratory Co., Ltd., screw diameter: 30 mm, L/D=42), and melt-kneaded under conditions: a kneading temperature of 210° C., an extrusion speed of 3.0 kg/hr, and a screw rotation speed of 200 rpm, whereby a pellet of a melt-kneaded product was obtained through a pelletizer. The MFR (230° C./2.16 kg) of the obtained melt-kneaded product was 1.5 g/10 min.
The melt mixture obtained in the above [2] and the plant-derived PE were dry-blended, and the resultant mixture was then charged into a twin-screw melt-kneading extruder (manufactured by Plastic Engineering Laboratory Co., Ltd., screw diameter: 30 mm, L/D=42), and mixed under conditions: a kneading temperature of 210° C., an extrusion speed of 3.0 kg/hr, and a screw rotation speed of 200 rpm, whereby pellets of Experimental Examples 1-1 to 1-8 were obtained through a pelletizer.
Each of the thermoplastic resin compositions of Experimental Examples 1-1 to 1-8 obtained in the above [3] was charged into a hopper of an injection molding machine (100 ton injection molding machine), and a molded body for physical property measurement was injection molded under injection conditions: a set temperature of 210° C. and a mold temperature of 60° C.
)
The densities of each of the thermoplastic resin compositions of Experimental Examples 1-1 to 1-8 obtained in the above [4] and each of the raw material components were measured in accordance with ISO 1183. The results are shown in Table 1 and [1].
Test temperature: 23° C.
Drying conditions: vacuum drying 80° C.×8 hours or more
The MFRs of each of the thermoplastic resin compositions of Experimental Examples 1-1 to 1-8 obtained in the above [4] and each of the raw material components (230° C./2.16 kg) were measured in accordance with ISO 1133. The results are shown in Table 1 and [1].
Test apparatus: Melt indexer (model “F-F01” manufactured by Toyo Seiki Seisaku-sho, Ltd.)
Test temperature: 230° C.
Test load: 2.16 kgf
Drying conditions: vacuum drying 80° C.×8 hours or more
Charpy impact strength (test temperature: 23° C.) was measured according to ISO 179 by using each of the molded bodies for evaluation of Experimental Examples 1-1 to 1-8 obtained in the above [4]. The results are shown in Table 1.
In the measurement of the Charpy impact strength, a test piece having a notch (type A) was used, and the impact was measured by the edgewise test method at a temperature of 23° C.
Each of the molded bodies for evaluation of Experimental Examples 1-1 to 1-8 obtained in the above [4] was used to perform a tensile test in accordance with ISO 527-1. As a result, the obtained yield stress, elongation at break, and elastic modulus are shown in Table 1.
Test apparatus: Autograph 50 kN (model “AGS-X” manufactured by Shimadzu Corporation)
Test temperature: 23° C.
Test piece shape: ISO multipurpose test piece
Tensile rate (elastic modulus measurement): 1 mm/min
Tensile rate (strength and elongation measurement): 50 mm/min
Drying conditions: vacuum drying 23° C.×24 hours or more
The phase structure of each thermoplastic resin composition was observed using each of test pieces of Experimental Example 1-6 (see
Among the obtained SEM images, an image obtained by magnifying the surface of Experimental Example 1-6 5,000 times is shown in
From the results in Table 1, Experimental Examples 1-1 to 1-8 can each give a thermoplastic resin composition having a density reduced to 1.00 g/cm3 and excellent impact resistance of a Charpy impact strength of 20 to 84 kJ/m2 while using a polyethylene and a polyamide having a bio-based carbon content rate of 80% or more in an amount of 75 mass % or more based on 100 mass % of the total thermoplastic resin composition. Furthermore, the MFR of the thermoplastic resin composition can be controlled in a wide range of 1.86 to 22.83 g/10 min, and, in particular, a thermoplastic resin composition having high fluidity of 10 g/10 min or more can be obtained. That is, there can be obtained a thermoplastic resin composition capable of achieving both high impact resistance and high fluidity using three components, i.e., a polyolefin, a polyamide, and a compatibilizer, while realizing a reduction in environmental load, a method for producing the same, and a molded body using the thermoplastic resin composition.
From the results in
As the plant-derived PE2, the same HDPE as PE-2 in <<Example 1>> was prepared.
As the plant-derived PA, the same PA11 as PA in <<Example 1>> was prepared.
As the compatibilizer, the compatibilizer of <<Example 1>> and the maleic anhydride-modified EBR were prepared.
As the resin to be modified, the following non-plant-derived PP and the following plant-derived PE were prepared.
Non-plant-derived PP: block polypropylene (product name “J817U” manufactured by Prime Polymer Co., Ltd.), density: 0.90 g/cm3, MFR (230° C./2.16 kg): 31 g/10 min, bio-based carbon content rate: 0%
Plant-derived PE1: the same HDPE as PE-1 in <<Example 1>> was prepared.
The plant-derived PA and the compatibilizer were dry-blended at a blending ratio (on a mass basis) of 6:1 or 3:1, and the resultant mixture was then charged into a twin-screw melt-kneading extruder (manufactured by Plastic Engineering Laboratory Co., Ltd., screw diameter: 30 mm, L/D=42), and melt-kneaded under conditions: a kneading temperature of 210° C., an extrusion speed of 3.0 kg/hr, and a screw rotation speed of 200 rpm, whereby a pellet of a melt-kneaded product was obtained through a pelletizer. As for the MFR of the obtained melt-kneaded product (230° C./2.16 kg), the MFR of the melt kneaded product A having a blending ratio of the plant-derived PA to the compatibilizer ratio of 6:1 was 5.9 g/10 min, and the MFR of the melt kneaded product B having a blending ratio of the plant-derived PA to the compatibilizer of 3:1 was 0.98 g/10 min.
The melt mixture A obtained in the above [2] and the plant-derived PE2 were dry-blended (on a mass basis) at a blending ratio of 7:3, and the resultant mixture was then charged into a twin-screw melt-kneading extruder (manufactured by Plastic Engineering Laboratory Co., Ltd., screw diameter: 30 mm, L/D=42), and mixed under conditions: a kneading temperature of 210° C., an extrusion speed of 3.0 kg/hr, and a screw rotation speed of 200 rpm, whereby modifiers (pellets) of Experimental Example 1 and Experimental Example 2-9 were obtained through a pelletizer. The obtained modifier had a density of 0.99 g/cm3 and an MFR (230° C./2.16 kg) of 22.8 g/10 min.
The melt mixture B obtained in the above [2] and the plant-derived PE2 were dry-blended (on a mass basis) at a blending ratio of 4:6, and the resultant mixture was then charged into a twin-screw melt-kneading extruder (manufactured by Plastic Engineering Laboratory Co., Ltd., screw diameter: 30 mm, L/D=42), and mixed under conditions: a kneading temperature of 210° C., an extrusion speed of 3.0 kg/hr, and a screw rotation speed of 200 rpm, whereby modifiers (pellets) of Experimental Example 2-5 and Experimental Example 2-13 were obtained through a pelletizer. The obtained modifier had a density of 0.94 g/cm3 and an MFR (230° C./2.16 kg) of 4.9 g/10 min.
The modifier of Experimental Example 2-1 obtained in the above [3] and the plant-derived PE1 as the resin to be modified were dry-blended at a blending ratio of 1:1 (Experimental Example 2-2) and a blending ratio of 1:4 (Experimental Example 2-3), and then the obtained dry blend raw material was charged into a hopper of an injection molding machine (100 ton injection molding machine), and injection-molded under injection conditions: a set temperature of 210° C. and a mold temperature of 60° C. to obtain molded bodies (molded bodies for evaluation) of Experimental Examples 2-2 and 2-3.
The modifier of Experimental Example 2-5 obtained in the above [3] and the plant-derived PE1 as the resin to be modified were dry-blended at a blending ratio of 1:1 (Experimental Example 2-6) and a blending ratio of 1:4 (Experimental Example 2-7), and then the obtained dry blend raw material was charged into a hopper of an injection molding machine (100 ton injection molding machine), and injection-molded under injection conditions: a set temperature of 210° C. and a mold temperature of 60° C. to obtain molded bodies (molded bodies for evaluation) of Experimental Examples 2-6 and 2-7.
The modifiers of Experimental Example 2-1 and Experimental Example 2-5 obtained in the above [3] were charged into a hopper of an injection molding machine (100 ton injection molding machine) and injection-molded under injection conditions: a set temperature of 210° C. and a mold temperature of 60° C. to obtain molded bodies (molded bodies for evaluation) of Experimental Example 2-1 and Experimental Example 2-5. The molded bodies of Experimental Example 2-1 and Experimental Example 2-9 are the same. Furthermore, the molded bodies of Experimental Example 2-5 and Experimental Example 2-13 are the same.
The plant-derived PE1 (high density polyethylene) prepared in the above [1] (4) was charged into a hopper of an injection molding machine (100 ton injection molding machine) and injection-molded under injection conditions: a set temperature of 210° C. and a mold temperature of 60° C. to mold molded bodies (molded bodies for evaluation) of Experimental Example 2-4 and Experimental Example 2-8. The molded bodies of Experimental Example 2-4 and Experimental Example 2-8 are the same.
Further, the modifier of Experimental Example 2-9 obtained in the above [3] and the non-plant-derived PP as the resin to be modified were dry-blended at a blending ratio of 1:1 (Experimental Example 2-10) and a blending ratio of 1:4 (Experimental Example 2-11), and then the obtained dry blend raw material was charged into a hopper of an injection molding machine (100 ton injection molding machine), and injection-molded under injection conditions: a set temperature of 210° C. and a mold temperature of 60° C. to obtain molded bodies (molded bodies for evaluation) of Experimental Examples 2-10 and 2-11.
Also, the modifier of Experimental Example 2-13 obtained in the above [3] and the non-plant-derived PP as the resin to be modified were dry-blended at a blending ratio of 1:1 (Experimental Example 2-14) and a blending ratio of 1:4 (Experimental Example 2-15), and then the obtained dry blend raw material was charged into a hopper of an injection molding machine (100 ton injection molding machine), and injection-molded under injection conditions: a set temperature of 210° C. and a mold temperature of 60° C. to obtain molded bodies (molded bodies for evaluation) of Experimental Examples 2-14 and 2-15.
The modifiers of Experimental Example 2-9 and Experimental Example 2-13 obtained in the above [3] were charged into a hopper of an injection molding machine (100 ton injection molding machine) and injection-molded under injection conditions: a set temperature of 210° C. and a mold temperature of 60° C. to obtain molded bodies (molded bodies for evaluation) of Experimental Example 2-9 and Experimental Example 2-13. The molded bodies of Experimental Example 2-9 and Experimental Example 2-1 are the same. Furthermore, the molded bodies of Experimental Example 2-13 and Experimental Example 2-5 are the same.
The plant-derived PE prepared in the above [1] (4) was charged into a hopper of an injection molding machine (100 ton injection molding machine) and injection-molded under injection conditions: a set temperature of 210° C. and a mold temperature of 60° C. to mold molded bodies (molded bodies for evaluation) of Experimental Example 2-12 and Experimental Example 2-16. The molded bodies of Experimental Example 2-12 and Experimental Example 2-16 are the same.
The density was measured according to ISO 1183.
Test temperature: 23° C.
Drying conditions: vacuum drying 80° C.×8 hours or more
The MFR (230° C./2.16 kg) was measured according to ISO 1133.
Test apparatus: Melt indexer (model “F-F01” manufactured by Toyo Seiki Seisaku-sho, Ltd.)
Test temperature: 230° C.
Test load: 2.16 kgf
Drying conditions: vacuum drying 80° C.×8 hours or more
Charpy impact strength (test temperature: 23° C.) was measured according to ISO 179 by using each of the molded bodies for evaluation of Experimental Examples 2-1 to 2-16 obtained in the above [4]. The results are shown in Tables 2 and 3. In the measurement of the Charpy impact strength, a test piece having a notch (type A) was used, and the impact was measured by the edgewise test method at a temperature of 23° C.
The impact resistance factors in Tables 2 and 3 indicate factors of Charpy impact strength in the corresponding experimental examples when the Charpy impact strength of the resin to be modified (plant-derived PE or non-plant-derived PP) is 1.0.
The total polyolefin amount indicates a total amount of polyolefins (plant-derived PE, plant-derived PE2, and non-plant-derived PP) contained in each of the experimental examples.
The phase structure was observed using each of the test pieces of Experimental Example 2-1 and Experimental Example 2-5. Of these test pieces, the test piece of Experimental Example 2-1 is the same as the test piece of Experimental Example 1-6 in [6] of <<Example 1>>. The test piece of Experimental Example 2-5 is the same as the test piece of Experimental Example 1-8 in [6] of <<Example 1>>. The results are as described in [6] of <<Example 1>>, and the effects are as described in [7] of <<Example 1>>.
From the results in Table 2, it can be seen, from the results of Experimental Example 2-3 and Experimental Example 2-7, that it is difficult to obtain a sufficient modification effect when the modifier is blended with the polyethylene PE1 at a blending ratio (on a mass basis) of 4:1, but it can be seen, from the results of Experimental Example 2-2 and Experimental Example 2-6, that a high modification effect is obtained when the modifier is blended with the polyethylene PE1 at a blending ratio (on a mass basis) of 1:1.
From the results of Experimental Example 2-2 and Experimental Example 2-6, the total polyolefin amount of Experimental Example 2-2 having a Charpy impact strength of 13 kJ/m2 is 65 mass %, whereas the total polyolefin amount of Experimental Example 2-6 having a Charpy impact strength of 23 kJ/m2 reaches 80 mass %. It can be seen that, while the impact resistance of Experimental Example 2-2 is 2.2 times that of Experimental Example 2-4, the impact resistance of Experimental Example 2-6 reaches 3.8 times that of Experimental Example 2-8. Therefore, it can be seen that a modifier having a higher blending proportion of the plant-derived PE2 has more excellent modification performance as the modifier.
On the other hand, the results in Table 2 do not show that a modifier having a higher blending proportion of the plant-derived PE2 has more excellent modification performance, and suggests that the use of the plant-derived PE1 acts specifically.
The present invention is not limited to the above-described specific examples, and can be variously modified within the scope of the present invention depending on the purpose and intended use.
The above-mentioned examples are for illustrative purposes only and are not to be construed as limiting the present invention. While the present invention has been described by way of examples of typical embodiments, it is understood that the language used in the description and illustration of the present invention is to be regarded as explanatory and illustrative and not restrictive. Modifications within the scope of the appended claims are possible without departing from the scope or spirit of the present invention in its form as detailed herein. Although reference has been made herein to specific structures, materials and examples in the detailed description of the present invention, it is not intended to limit the present invention to the disclosure set forth herein, but rather, to cover all functionally equivalent structures, methods, and uses within the scope of appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-123260 | Jul 2020 | JP | national |
| 2021-010579 | Jan 2021 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2021/026629 | 7/15/2021 | WO |
