composition

Abstract

To provide a composition comprising an aliphatic polyester polymer, yet capable of reducing odor emissions post-molding.SOLUTION: This composition includes an olefin polymer A, an aliphatic polyester polymer B, and an inorganic powder C. The pH of the inorganic powder C, evaluated in accordance with JIS M 8016-1991, is 6.5-11.5.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a composition. [Background technology]

[0002] Aliphatic polyester polymers are resins with low environmental impact that can be synthesized from renewable resources without using fossil resources, and are also resins with excellent moldability and mechanical properties. Therefore, the environmental impact can be reduced by adding aliphatic polyester polymers to various packaging materials, various containers such as bottles, food packaging materials, container caps, stationery, daily necessities, fibers for carpets and sofas, interior and exterior materials for automobiles, electrical and electronic equipment parts, building and residential interior materials, and other construction materials.

[0003] As compositions containing such an aliphatic polyester polymer, those described in Patent Documents 1 to 3 are known. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2008-239858 A [Patent Document 2] JP 2006-241445 A [Patent Document 3] JP 2019-178206 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, in the case of a conventional composition containing an aliphatic polyester polymer, there have been cases where an odor is generated from a molded article after molding.

[0006] The present invention has been made in view of the above problems, and has an object to provide a composition which contains an aliphatic polyester polymer and yet is capable of reducing the generation of odor after molding. [Means for solving the problem]

[0007] [1] A composition comprising an olefin polymer A, an aliphatic polyester polymer B, and an inorganic powder C, wherein the inorganic powder C has a pH of 6.5 to 11.5 as evaluated according to JIS M 8016-1991.

[0008] [2] The composition described in [1], wherein the inorganic powder C does not contain a fatty acid metal salt.

[0009] [3] The composition according to [2], wherein the aliphatic polyester polymer B is a poly(3-hydroxyalkanoate) polymer having a melting point of 150° C. or higher.

[0010] [4] The composition according to any one of [1] to [3], wherein the inorganic powder C has a pH of 8.5 to 9.5 as evaluated according to JIS M 8016-1991.

[0011] [5] The composition according to any one of [1] to [4], wherein the inorganic powder C has a median diameter D50 of 0.05 to 30 μm in a weight-based particle size distribution measured by a laser diffraction method.

[0012] [6] The composition according to any one of [1] to [5], wherein the content of the olefin polymer A is 51 to 99.9 parts by mass and the content of the aliphatic polyester polymer B is 0.1 to 49 parts by mass, relative to 100 parts by mass in total of the olefin polymer A and the aliphatic polyester polymer B.

[0013] [7] The composition according to any one of [1] to [6], wherein the content of the inorganic powder C is 0.1 to 40 parts by mass based on 100 parts by mass of the total of the polymer A and the polymer B.

[0014] [8] The composition according to any one of [1] to [7], wherein the content of the aliphatic polyester polymer B is 0.1 to 20 parts by mass.

[0015] [9] The composition according to any one of [1] to [8], wherein the olefin-based polymer A is a propylene-based copolymer.

[0016]

[10] The melt mass flow rate of the aliphatic polyester polymer B measured under conditions of a temperature of 210° C. and a load of 2.16 kgf is defined as MFR(B); The composition according to any one of [1] to [9], wherein, when a mixture X containing 0.5 parts by mass of the inorganic powder C per 100 parts by mass of the total of the aliphatic polyester polymer B and the inorganic powder C is defined as a melt mass flow rate measured at a temperature of 210°C under a load of 2.16 kgf, MFR(X) / MFR(B) is 1.0 or less. Effect of the Invention

[0017] According to the present invention, there is provided a composition which contains an aliphatic polyester polymer and yet is capable of reducing odor generation after molding. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] Hereinafter, several embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

[0019] (composition) The composition according to an embodiment of the present invention contains an olefin polymer A, an aliphatic polyester polymer B, and an inorganic powder C.

[0020] <Olefin Polymer A> The olefin polymer A is a polymer containing 50% by mass or more of structural units derived from an olefin having from 2 to 10 carbon atoms (wherein the total amount of the olefin polymer is taken as 100% by mass). Examples of the olefin having from 2 to 10 carbon atoms include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and 1-decene.

[0021] The olefin polymer A may contain a structural unit derived from a monomer other than an olefin having from 2 to 10 carbon atoms. Examples of the monomer other than an olefin having from 2 to 10 carbon atoms include aromatic vinyl monomers such as styrene, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, and ethyl methacrylate, vinyl ester compounds such as vinyl acetate, conjugated dienes such as 1,3-butadiene and 2-methyl-1,3-butadiene (isoprene), and non-conjugated dienes such as dicyclopentadiene and 5-ethylidene-2-norbornene.

[0022] The olefin polymer A can be at least one selected from the group consisting of ethylene polymers, propylene polymers, and butene polymers, and may be any combination of two or more of these.

[0023] An ethylene-based copolymer is a polymer containing 50% by mass or more of structural units derived from ethylene, and examples thereof include ethylene homopolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, and ethylene-1-butene-1-hexene copolymer. The ethylene-based copolymer may be a combination of two or more ethylene-based copolymers.

[0024] The propylene copolymer is a polymer containing 50% by mass or more of structural units derived from propylene, and examples thereof include propylene homopolymer, propylene-ethylene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, and propylene-ethylene-1-octene copolymer. The propylene copolymer may be a combination of two or more kinds of propylene copolymers. It is preferable that the olefin polymer A is a propylene copolymer.

[0025] The butene copolymer is a polymer containing 50% by mass or more of structural units derived from 1-butene, and examples thereof include 1-butene homopolymer, 1-butene-ethylene copolymer, 1-butene-propylene copolymer, 1-butene-1-hexene copolymer, 1-butene-1-octene copolymer, 1-butene-ethylene-propylene copolymer, 1-butene-ethylene-1-hexene copolymer, 1-butene-ethylene-1-octene copolymer, 1-butene-propylene-1-hexene copolymer, and 1-butene-propylene-1-octene copolymer. The butene copolymer may be a combination of two or more butene copolymers.

[0026] The above olefin polymer A can be produced by a known polymerization method using a known polymerization catalyst.

[0027] The melt mass flow rate (MFR) of the olefin polymer A measured according to JIS K7210-2014 at a temperature of 230° C. or 190° C. and a load of 2.16 kgf is preferably 0.1 g / 10 min or more and 200 g / 10 min or less.

[0028] <Aliphatic polyester polymer B>

[0029] The aliphatic polyester polymer has a structure of a polycondensation product of an aliphatic polycarboxylic acid component and an aliphatic polyhydric alcohol component, or a polycondensation product of an aliphatic hydroxycarboxylic acid, and the main chain of the repeating unit does not contain an aromatic hydrocarbon structure.

[0030] Examples of the aliphatic polyester polymer include a polymer of a hydroxycarboxylic acid or lactone, a polycondensation product of a diol and a dicarboxylic acid, and a copolymer thereof. When the polymer B is a copolymer, the arrangement of the copolymer may be any of a random copolymer, an alternating copolymer, a block copolymer, a graft copolymer, and the like.

[0031] At least a part of these may be crosslinked with a crosslinking agent such as a polyisocyanate such as xylylene diisocyanate, 2,4-tolylene diisocyanate, etc., or a polysaccharide such as cellulose, acetyl cellulose, ethyl cellulose, etc. Furthermore, at least a part of these may have any structure such as a linear, cyclic, branched, star-shaped, or three-dimensional network structure, without any limitation, and may be a copolymer with a polyolefin resin or a graft polymer with a polyolefin resin.

[0032] Moreover, the aliphatic polyester polymer B can be used alone or in combination.

[0033] Examples of the hydroxycarboxylic acid include hydroxycarboxylic acids having 2 to 18 carbon atoms, preferably 6 or less carbon atoms, and most preferably 4 carbon atoms. Specific examples include glycolic acid, L-lactic acid, D-lactic acid, D,L-lactic acid, 3-hydroxybutyrate, 3-hydroxyvalerate, 3-hydroxypropionate, 4-hydroxybutyrate, 4-hydroxyvalerate, 5-hydroxyvalerate, 3-hydroxypentenoate, 3-hydroxyhexanoate, 3-hydroxyheptanoate, 3-hydroxyoctanoate, 3-hydroxynonanoate, and 3-hydroxydecanoate.

[0034] Examples of lactones include propiolactone, butyrolactone, valerolactone, caprolactone, and laurolactone.

[0035] The diol is preferably a diol having 2 to 10 carbon atoms. Among them, an aliphatic diol having 2 to 4 carbon atoms or an alicyclic diol having 5 or 6 carbon atoms is more preferable. Specific examples thereof include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethylol, and 1,4-cyclohexanedimethylol.

[0036] The dicarboxylic acid is preferably an aliphatic dicarboxylic acid having 2 to 12 carbon atoms. Among them, an aliphatic dicarboxylic acid having 2 to 6 carbon atoms or an alicyclic dicarboxylic acid having 5 to 6 carbon atoms is more preferable. Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecadicarboxylic acid, dodecadicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, dimer acid and its hydrogenated products, hexahydrophthalic acid, hexahydroisophthalic acid, and hexahydroterephthalic acid. These dicarboxylic acids may also be derivatives such as alkyl esters and acid anhydrides having 1 to 4 carbon atoms.

[0037] Of the above aliphatic polyester polymers, it is preferable to use polylactic acid, polybutylene succinate, poly(butylene succinate-co-butylene adipate), polycaprolactone, poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), and polyglycolic acid.

[0038] When polylactic acid is used as the aliphatic polyester polymer B, the polylactic acid preferably has an L-form ratio of 94 mol % or more in the lactic acid components constituting the polylactic acid. By setting the L-form ratio in this range, it is possible to prevent a decrease in the melting point.

[0039] (Poly(3-hydroxyalkanoate) polymer) Polymer B may be a poly(3-hydroxyalkanoate)-based polymer having a melting point of 150° C. or higher.

[0040] The poly(3-hydroxyalkanoate) polymer is a polyhydroxyalkanoate, i.e., a polycondensate (polyester) of hydroxyalkanoic acid, and necessarily contains a repeating unit of 3-hydroxyalkanoate represented by formula (1). In formula (1), R is a hydrogen atom, a halogen atom, an alkyl group having 1 to 15 carbon atoms, a cyano group, an amino group having 1 to 11 carbon atoms, an alkoxy group (alkyloxy group) having 1 to 11 carbon atoms, an amide group having 2 to 20 carbon atoms, an aryl group having 6 to 12 carbon atoms, or a monovalent heterocyclic group having 1 to 9 carbon atoms. These groups may have a substituent. In particular, from the viewpoint of compatibility with components other than polymer B contained in the composition (for example, polymer A), R is preferably an alkyl group having 1 to 8 carbon atoms, an amide group having 1 to 20 carbon atoms, or an aryl group having 6 to 8 carbon atoms.

[0041] [-O-CHR-CH2-CO-]…(1)

[0042] Examples of halogen atoms are F, Cl, Br, and I.

[0043] The alkyl group having 1 to 15 carbon atoms may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 8, and more preferably 1 to 4. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a 2-methylbutyl group, a 1-methylbutyl group, a hexyl group, an isohexyl group, a 3-methylpentyl group, a 2-methylpentyl group, a 1-methylpentyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a 3,7-dimethyloctyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tetradecyl group, and a pentadecyl group.

[0044] Examples of the amino group having 1 to 18 carbon atoms include an amino group, an alkylamino group, a dialkylamino group, an arylamino group, an alkylarylamino group, a benzylamino group, and a dibenzylamino group.

[0045] Examples of the alkylamino group include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, a heptylamino group, an octylamino group, a nonylamino group, a decylamino group, a dodecylamino group, an isopropylamino group, an isobutylamino group, an isopentylamino group, a sec-butylamino group, a tert-butylamino group, a sec-pentylamino group, a tert-pentylamino group, a tert-octylamino group, a neopentylamino group, a cyclopropylamino group, a cyclobutylamino group, a cyclopentylamino group, a cyclohexylamino group, a cycloheptylamino group, a cyclooctylamino group, a 1-adamantamino group, and a 2-adamantamino group.

[0046] Examples of dialkylamino groups include a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a dipentylamino group, a diisopropylamino group, a diisobutylamino group, a diisopentylamino group, a methylethylamino group, a methylpropylamino group, a methylbutylamino group, a methylisobutylamino group, a dicyclopropylamino group, a pyrrolidino group, a piperidino group, and a piperazino group.

[0047] Examples of the arylamino group include an anilino group, a 1-naphthylamino group, a 2-naphthylamino group, an o-toluidino group, a m-toluidino group, a p-toluidino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, and a p-terphenylamino group.

[0048] The alkylarylamino group includes an N-methylanilino group, an N-ethylanilino group, an N-propylanilino group, an N-butylanilino group, an N-isopropylanilino group, and an N-pentylanilino group.

[0049] Examples of the alkoxy group having 1 to 11 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a cyclopropoxy group, a cyclobutoxy group, and a cyclopentoxy group.

[0050] The term "amide group" refers to a group in which one hydrogen atom bonded to a nitrogen atom has been removed from a carboxylic acid amide. Examples of the amide group having 1 to 20 carbon atoms include -NH-C(=O)-R groups such as formamide, acetamide, propionamide, butylamide, benzamide, trifluoroacetamide, and pentafluorobenzamide. A (wherein R A is a hydrogen atom or a monovalent organic group), and -N(-C(=O)-R such as a diformamide group, a diacetamide group, a dipropionamide group, a dibutyroamide group, a dibenzamide group, a ditrifluoroacetamide group, and a dipentafluorobenzamide group. A )(-C(=O)-R B ) (wherein R A 、 R B are each independently a hydrogen atom or a monovalent organic group. The organic group may be an alkyl group, an alkoxy group, or an aryl group, which may be substituted with a halogen atom. Among these, the amide group is preferably a formamide group, an acetamide group, a propionamide group, a butyroamide group, or a benzamide group.

[0051] Examples of the aryl group having 6 to 12 carbon atoms are a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenyl group, and among these, a phenyl group, a tolyl group, and a xylyl group are more preferred.

[0052] Examples of heteroatoms in the monovalent heterocyclic group having 1 to 9 carbon atoms are N, O, and S, and the group may be saturated or unsaturated, may have a single or multiple heteroatoms, or may have different types of heteroatoms. Examples of such heterocyclic groups include a thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, a piperidinyl group, a quinolinyl group, an isoquinolinyl group, a pyrimidinyl group, a triazinyl group, and a thiazolyl group.

[0053] The repeating units of the aliphatic polyester polymer B may consist solely of one or more types of 3-hydroxyalkanoates represented by formula (1), or may have one or more types of 3-hydroxyalkanoates represented by formula (1) and one or more types of other hydroxyalkanoates.

[0054] Aliphatic polyester polymer B preferably contains 3-hydroxyalkanoate repeating units represented by formula (1) in an amount of 50 mol % or more, more preferably 70 mol % or more, based on the total repeating units of hydroxyalkanoate (100 mol %).

[0055] Examples of 3-hydroxyalkanoates represented by formula (1) are those in which R is a hydrogen atom or C n H 2n+1 where n is an integer of 1 to 15, examples of the alkyl group include 3-hydroxybutyrate (hereinafter, may be referred to as 3HB) where n=1, 3-hydroxyvalerate (hereinafter, may be referred to as 3HV) where n=2, 3-hydroxyhexanoate (hereinafter, may be referred to as 3HH) where n=3, 3-hydroxyoctanate where n=5, 3-hydroxyoctadecanate where n=15, and 3-hydroxypropionate where R is a hydrogen atom.

[0056] An example of the polymer B having only one type of repeating unit represented by formula (1) is poly(3-hydroxybutyrate) (hereinafter, sometimes referred to as P3HB).

[0057] Examples of polymer B having only multiple types of repeating units represented by formula (1) are poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (hereinafter, sometimes referred to as P3HB3HH), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (hereinafter, sometimes referred to as P3HB3HV), and poly(3-hydroxybutyrate-co-3-hydroxypropionate) (hereinafter, sometimes referred to as P3HB3HP).

[0058] Examples of hydroxyalkanoates other than the 3-hydroxyalkanoate represented by formula (1) include the repeating unit represented by formula (2) (wherein R 1 is a hydrogen atom or C n H 2n+1 where n is an integer of 1 or more and 15 or less, and m is an integer of 2 to 10.

[0059] [-O-CHR 1 -C m H 2m+1 -CO-]…(2)

[0060] An example of polymer B containing repeating units of formulae (1) and (2) is poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (for example, formula (P3HB4HB) below).

[0061] From the viewpoint of increasing the melting point, it is preferable that the repeating unit of the aliphatic polyester polymer B contains at least 3-hydroxybutyrate among the 3-hydroxyalkanoates represented by the formula (1).

[0062] The aliphatic polyester polymer B preferably contains 3-hydroxybutyrate repeating units in an amount of 50 mol % or more, more preferably 70 mol % or more, based on the total repeating units of hydroxyalkanoate (100 mol %).

[0063] The aliphatic polyester polymer B may have two or more types of ester repeating units, and may be, for example, a di-polymer having two types of repeating units, a tri-copolymer having three types of repeating units, or a tetra-copolymer having four types of repeating units, as described above.

[0064] For example, an example of a tri-copolymer is poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate) (hereinafter, sometimes referred to as (P3HB3HV3HH)).

[0065] As described above, the aliphatic polyester polymer B preferably contains 3-hydroxybutyrate among the repeating units of 3-hydroxyalkanoate represented by formula (1). The proportion XX of the repeating units of 3-hydroxybutyrate relative to 100 moles of all the repeating units of hydroxyalkanoate ester is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 98.0 mol% or more.

[0066] The proportion XX is usually 100 mol % or less, preferably 99.9 mol % or less, and more preferably 99.8 mol % or less.

[0067] The arrangement of the copolymer may be any of a random copolymer, an alternating copolymer, a block copolymer, a graft copolymer, and the like.

[0068] The aliphatic polyester polymer B may have other ester repeating units than those of the formulae (1) and (2), but the main chain of the other ester repeating units does not contain an aromatic hydrocarbon structure. That is, the aliphatic polyester polymer B is an aliphatic polyester. However, it is possible that a group having an aromatic hydrocarbon group is bonded to a carbon of the main chain of the other ester repeating units.

[0069] The constituent ratio of the repeating units in the aliphatic polyester polymer B can be calculated from the results of NMR measurements such as 1H-NMR and 13C-NMR, as described in L. Tripathi., MCFactories, 11, 44 (2012).

[0070] Furthermore, the aliphatic polyester polymer B may be a mixture of two or more kinds of poly(3-hydroxyalkanoate) polymers.

[0071] The weight average molecular weight (Mw) of the aliphatic polyester polymer B can be 10,000 to 1,000,000, preferably 20,000 to 800,000, and more preferably 30,000 to 600,000. By making the weight average molecular weight (Mw) 10,000 or more, it is possible to obtain a molded product excellent in impact strength and tensile elongation. In addition, by making the weight average molecular weight 500,000 or less, the dispersibility in the olefin polymer A becomes good. The weight average molecular weight may be 400,000 or less, 300,000 or less, 200,000 or less, or 100,000 or less. In this specification, the weight average molecular weight (Mw) is measured by GPC using standard polystyrene as a molecular weight standard substance.

[0072] The aliphatic polyester polymer B is a thermoplastic resin, and is preferably crystalline.

[0073] The melt mass flow rate (MFR(B)) of the aliphatic polyester polymer B measured according to JIS K7210-2014 at a temperature of 190°C or 170°C and a load of 2.16 kgf is preferably 0.1 g / 10 min or more and 200 g / 10 min or less. MFR(B) may be 1 g / 10 min or more, 3 g / 10 min or more, 5 g / 10 min or more, 7 g / 10 min or more, 8 g / 10 min or more, 10 g / 10 min or more, or 20 g / 10 min or more. MFR(B) may be 150 g / 10 min or less, or 100 g / 10 min or less.

[0074] The melting point (Tm) of the aliphatic polyester polymer B is preferably 150° C. or higher, and may be 155° C. or higher, 160° C. or higher, 165° C. or higher, 170° C. or higher, or 175° C. or higher. The melting point (Tm) of the polymer B may be 220° C. or lower, may be 200° C. or lower, or may be 190° C. or lower.

[0075] The melting point (Tm) of the aliphatic polyester polymer B is measured from the position of the main peak due to the melting of crystals as determined by differential scanning calorimetry (DSC) in accordance with JIS K7121.

[0076] Poly(3-hydroxyalkanoate) polymers may be produced by microorganisms or may be derived from compounds (eg, cyclic lactones) derived from petroleum or plant sources.

[0077] The poly(3-hydroxyalkanoate) polymer may be one in which each repeating unit of hydroxyalkanoate is composed only of the D-form (R-form), such as in one produced from a microorganism, or may be one in which the repeating unit of hydroxyalkanoate contains both the D-form (R-form) and the L-form (S-form), such as in one derived from a mixture of the D-form (R-form) and the L-form (S-form).

[0078] In the poly(3-hydroxyalkanoate) polymer produced from a microorganism, the repeating unit of formula (1) can be expressed as follows: (BI-1) In formula (BI-1), n ​​represents the degree of polymerization. [ka]

[0079] For example, poly-(3-hydroxybutyrate) produced from a microorganism has the following structure: (BI-2) where n represents the degree of polymerization. [ka]

[0080] Also, poly-(3-hydroxybutyrate-co-3-hydroxyhexanoate) produced from a microorganism has the following structure: (BI-3) where m and n represent the degree of polymerization. [ka]

[0081] Furthermore, poly-(3-hydroxybutyrate-co-4-hydroxybutyrate) produced from microorganisms has the following structure: (BI-4) where m and n represent the degree of polymerization. [ka]

[0082] The aliphatic polyester polymer B can be biodegradable.

[0083] For example, poly(3-hydroxyalkanoate) polymers can be produced by microorganisms such as Alcaligenes eutrophus AC32 strain, which is an Alcaligenes eutrophus strain into which a PHA synthase gene derived from Aeromonas caviae has been introduced (international deposit under the Budapest Treaty, international depository authority: National Institute of Advanced Industrial Science and Technology Patent Organism Depositary Center (6-1-1 Central, Higashi 1-chome, Tsukuba City, Ibaraki Prefecture, Japan), original deposit date: August 12, 1996, transferred on August 7, 1997, accession number FERMBP-6038 (transferred from original deposit FERMP-15786)) (J. Bacteriol., 179, 4821 (1997)).

[0084] (Inorganic powder C) Inorganic powder refers to powder of an inorganic material. Examples of inorganic materials include simple metals or metalloids, alloys of two or more elements selected from the group consisting of metals and metalloids, and compounds such as oxides, sulfides, nitrides, hydroxides, and salts (sulfates, phosphates, etc.) that contain one element or two or more elements selected from the group consisting of metals and metalloids. Examples of metals constituting the inorganic material are Al, Li, Ti, Fe, Mg, K, Na, Ca, Zn, Pb, Cu, Cr, Ba, Rb, Cs, Mn, V, Be, Ni, and Co. Examples of metalloids are Si and B. In this specification, the inorganic material may also be carbon. The inorganic material may be a natural mineral or an artificially synthesized material. The powder of the inorganic material may be surface-modified.

[0085] The pH of inorganic powder C evaluated according to JIS M 8016-1991 is 6.5 to 11.5. The pH of inorganic powder C evaluated according to JIS M 8016-1991 may be 8.5 or more and 9.5 or less.

[0086] The pH of the above-mentioned inorganic powder C is obtained by adding 20 g of inorganic powder C to 80 mL of pure water, stirring the mixture, and measuring the pH of the liquid.

[0087] The pH of the inorganic powder C is determined by the surface state of the inorganic powder, i.e., the surface functional groups. Therefore, the pH of the inorganic powder such as talc exemplified in this embodiment does not necessarily fall within the range of 6.5 to 11.5, and the pH of the inorganic powder varies depending on the manufacturing method of the inorganic powder, the presence or absence of surface treatment, the type of treatment agent, etc.

[0088] The inorganic powder C may be a powder of a single element or compound that exhibits a pH of 6.5 to 11.5, or may be a mixture of powders of two or more materials selected from the group consisting of elements and compounds that exhibit a pH of 6.5 to 11.5.

[0089] Examples of the inorganic powder C include at least one selected from the group consisting of glass beads, glass balloons, glass flakes, asbestos, mica, calcium-based compounds, talc, silica, calcium silicate, hydrotalcite, titanium oxide, kaolinite, wollastonite, diatomaceous earth, graphite, pumice, and barium sulfate.

[0090] In particular, the inorganic powder C preferably contains at least one selected from the group consisting of mica, calcium-based compounds, talc, silica, hydrotalcite, and wollastonite, more preferably contains at least one selected from the group consisting of mica, calcium-based compounds, talc, silica, and hydrotalcite, and even more preferably contains at least one selected from the group consisting of mica, calcium-based compounds, and talc.

[0091] Examples of micas are muscovite, aluminoceladonite, ferroaluminoceladonite, celadonite, ferroceladonites, Roscoe mica, chromphyllite, boromuscovite, sodalite, nanpingite, tobe mica, iron mica, phlogopite, siderophyllite, eastonite, muscovite, Hendricksite, Montdorite, yangzhuming mica, tainiolite, polylithiomica, trilithiomica, masuomi mica, norrishite, tetra-ferri-annite, tetra-ferriphlogopite, sodalite, preiswerkite, ephesite, nacre mica, chernykhite, clintonite, bityite, anandite, kinoshi mica, fluorkinoshi mica, illite, glauconite, brammallite, wonesite, biotite, lepidolite, and zinwaldite. Examples of muscovite are Yamaguchi Mica muscovite (A-11, A-21S, AB-25S, J-31M, SYA-21R).

[0092] Examples of calcium-based compounds are calcium ascorbate, calcium sulfite, calcium bisulfite, calcium monophosphate, Egyptian blue, calcium chloride, calcium chloride hydroxide, calcium chlorate, calcium peroxide, casein phosphopeptide, kalimate, calcium superphosphate, calcium cyanamide, calcium formate, calcium gluconate, calcium glutamate, calcium chromate, chrome tin pink, calcium silicate, anhydrite, calcium acetate, calcium oxide, calcium hypochlorite, calcium cyanide, calcium bromide, calcium triple superphosphate, calcium oxalate, calcium bromate, calcium tartrate, calcium nitrate, calcium hydroxide, calcium hydride, gypsum, calcium carbide, calcium carbonate, calcium bicarbonate, calcium titanate, calcium lactate, tricalcium diphosphate, calcium fluoride, POs-Ca, calcium polycarbophil, calcium iodide, calcium iodate, lysole rubin BK, calcium sulfide, calcium sulfate, calcium phosphide, calcium monohydrogen phosphate, calcium phosphate, tricalcium phosphate, and calcium dihydrogen phosphate. Examples of calcium carbonate include Hayashi Kasei's FP#300, KS#500, KS#800, KS#1000, KS#1200, ACE#25, SST#40, Kansui-seki 3-minute, Escalon#200, Escalon#1500, Escalon#2000, and Escalon#2300.

[0093] Examples of talc include the Talcan Powder series, Micron White series, GH series, and KHP series manufactured by Hayashi Kasei, and the Nano Ace series and ultrafine powder talc series manufactured by Nippon Talc.

[0094] (Components that inorganic powder C preferably does not contain) An example of a component that is preferably not contained in the inorganic powder C is a fatty acid metal salt such as a long-chain fatty acid metal salt. A long-chain fatty acid refers to a fatty acid having 13 or more carbon atoms. Examples of fatty acids are stearic acid, lauric acid, and palmitic acid. Examples of metal salts are magnesium salts, calcium salts, zinc salts, lithium salts, and barium salts. In particular, it is preferable that the surface of the inorganic powder does not have a long-chain fatty acid metal salt.

[0095] Specific examples of long-chain fatty acid metal salts include metal salts of stearic acid such as magnesium stearate, calcium stearate, and zinc stearate, magnesium laurate, and calcium palmitate. When a fatty acid metal salt such as a long-chain fatty acid metal salt is present on the surface of inorganic powder C, the pH tends to decrease and fall outside the range of 6.5 to 11.5.

[0096] (Components that the composition preferably does not contain) The composition suitably does not contain inorganic powders having a pH of less than 6.5 or more than 11.5 as evaluated by JIS M 8016-1991.

[0097] (Particle size of inorganic powder C: Median diameter D50 measured by laser diffraction method) From the viewpoint of improving mechanical strength such as bending modulus, the median diameter D50 of the inorganic powder C may be 30 μm or less, 25 μm or less, or 20 μm or less. If D50 is too large, mechanical strength such as bending modulus is likely to decrease. From the viewpoint of improving mechanical strength such as bending elastic modulus, the median diameter D50 of the inorganic powder C may be 0.05 μm or more, 0.5 μm or more, 1 μm or more, or 5 μm or more.

[0098] The median diameter D50 can be determined by measuring the particle size distribution based on weight using a laser diffraction particle size distribution analyzer in accordance with JIS R 1629, and reading the particle size value at a cumulative amount of 50% by weight from the obtained particle size cumulative distribution curve. An example of a laser diffraction particle size distribution analyzer is the MT-3300EX-II manufactured by Nikkiso Co., Ltd.

[0099] (MFR(X) / MFR(B)) The melt mass flow rate of aliphatic polyester polymer B measured under conditions of a temperature of 210°C and a load of 2.16 kgf is defined as MFR(B), When a mixture X containing 0.5 parts by mass of inorganic powder C per 100 parts by mass of aliphatic polyester polymer B and inorganic powder C has a melt mass flow rate measured at a temperature of 210°C under a load of 2.16 kgf, MFR(X) is preferably 1.0 or less.

[0100] When the addition of inorganic powder C causes deterioration of aliphatic polyester polymer B, MFR(X) becomes larger than MFR(B). When the addition of inorganic powder C suppresses the deterioration of aliphatic polyester polymer B, MFR(X) becomes smaller than MFR(B). In other words, MFR(X) / MFR(B) being 1.0 or less means that inorganic powder C is a compound that is unlikely to cause significant deterioration of aliphatic polyester polymer B due to heating.

[0101] (Additives) The composition may contain additives as necessary, which may be at least one selected from the group consisting of stabilizers, antibacterial agents, antifungal agents, dispersants, plasticizers, flame retardants, tackifiers, colorants, metal powders, organic powders, inorganic fibers, organic fibers, organic and inorganic composite fibers, inorganic whiskers, and fillers.

[0102] Examples of the stabilizer include at least one selected from the group consisting of lubricants, antioxidants, heat stabilizers, light resistance agents, weather resistance agents, metal deactivators, ultraviolet absorbers, light stabilizers, and copper damage inhibitors. Examples of the light resistance agent include hindered amine-based light resistance agents.

[0103] An example of the colorant is at least one selected from the group consisting of titanium oxide, carbon black, and organic pigments. An example of the metal powder is ferrite.

[0104] An example of an organic powder is a protein. Examples of inorganic fibers are glass fibers and metal fibers. Examples of organic fibers are carbon fibers and aramid fibers. An example of an inorganic whisker is potassium titanate whisker.

[0105] An example of the filler is at least one selected from the group consisting of ebonized powder, cotton flock, cork powder, cellulose powder, and wood powder.

[0106] The composition may contain only one of the above additives or a combination of two or more of them.

[0107] (Composition of the composition) There is no particular limitation on the contents of the olefin polymer A and the aliphatic polyester polymer B relative to 100 parts by mass in total of the olefin polymer A and the aliphatic polyester polymer B, but from the viewpoint of increasing mechanical strength such as flexural modulus, the content of the olefin polymer A may be 51 to 99.9 parts by mass, and the content of the aliphatic polyester polymer B may be 0.1 to 49 parts by mass. The content of the olefin polymer A may be 60 parts by mass or more, 70 parts by mass or more, 80 parts by mass or more, or 90 parts by mass or more, relative to 100 parts by mass in total of the olefin polymer A and the aliphatic polyester polymer B.

[0108] The content of inorganic powder C is not particularly limited, but is preferably 0.01 to 40 parts by mass, relative to 100 parts by mass of the total of olefin polymer A and aliphatic polyester polymer B. The content of inorganic powder C may be 0.1 parts by mass or more, 1 part by mass or more, or 20 parts by mass or less.

[0109] The total proportion of the olefin polymer A, the aliphatic polyester polymer B, and the inorganic powder C in the entire composition may be 20 mass% or more, 30 mass% or more, 40 mass% or more, 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, or 90 mass% or more.

[0110] The olefin polymer A can account for more than 50% by mass of the composition, and can account for 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more.

[0111] The aliphatic polyester polymer B may account for 0.1 to 20 parts by mass of the composition.

[0112] (effect) According to the composition of the present embodiment, the generation of odor is suppressed by containing the inorganic powder C having a specific pH. The reason for this is not clear, but it is thought that, for example, it is due to the suppression of thermal decomposition of the aliphatic polyester polymer B. Furthermore, when the composition ratio of the olefin polymer A and the aliphatic polyester polymer B is within a specific range and the median diameter D50 of the inorganic powder C is within the above-mentioned specific range, the mechanical strength of the molded product, such as the flexural modulus (FM), is further increased. Although the reason for this is unclear, it is believed to be due to the fact that the inorganic powder C can suppress the thermal decomposition of not only the aliphatic polyester polymer B but also the olefin polymer A during molding (melt-kneading).

[0113] (Production method of the composition) The composition can be obtained by melt-kneading the respective raw material components.

[0114] The kneading temperature (the set temperature of the kneader) is preferably 150 to 300° C., and more preferably 170 to 280° C. It is also possible to process at 210° C. or higher.

[0115] The composition can be produced by melt-kneading all of the olefin polymer A, the aliphatic polyester polymer B, the inorganic powder C, and additives that are added as required at once.

[0116] The composition may be produced by a first step of melt-kneading a part of the olefin polymer A, all of the aliphatic polyester polymer B, some or all of the inorganic powder C, and some or all of the additives added as needed to produce a preliminary composition, and then a second step of melt-kneading the preliminary composition with the remainder of the olefin polymer A, the remainder of the inorganic powder C, and the remainder of the additives added as needed. It is not necessary to add any olefin polymer in the first step.

[0117] It is preferable to add the inorganic powder C in the first step.

[0118] (Method for producing molded article of composition) A molded article having a desired shape can be obtained from the above composition using a known resin molding method such as injection molding, extrusion molding, vacuum molding, pressure molding, press molding, foam molding, blow molding, or rotational molding.

[0119] The above composition can also be laminated with other materials such as other resins, metals, paper, leather, etc. to obtain a multi-layer structure.

[0120] The surface of the article molded from the composition of the present invention may be subjected to a surface treatment such as embossing, corona discharge treatment, flame treatment, plasma treatment, ozone treatment, etc.

[0121] The above composition can be widely used as a resin material.

[0122] Applications of the resin composition of the present invention include textile materials, exterior construction materials, furniture and interior decoration materials, house materials, toy materials, gardening materials, automotive parts, and packaging materials. Examples of the textile materials include fabric materials for clothing, fabric materials for interior use, and textile materials for industrial use. Examples of the exterior materials include carport materials, fence materials, gate materials, gatepost materials, post materials, cycle port materials, deck materials, sunroom materials, roof materials, terrace materials, handrail materials, shade materials, and awning materials. Examples of the furniture and interior decoration materials include sofa materials, table materials, chair materials, bed materials, chest materials, cab net materials, and dresser materials. Examples of the home appliance materials include clock materials, mobile phone materials, and white goods home appliance materials. Examples of the toy materials include plastic model materials, diorama materials, and video game main body materials. Examples of the gardening materials include planter materials, flower vase materials, and flower pot materials. Examples of the automobile materials include bumper materials, instrument panel materials, and airbag cover materials. Examples of the packaging materials include food packaging materials, fiber packaging materials, and miscellaneous packaging materials. Further, other applications include, for example, monitor parts, office automation (OA) equipment parts, medical parts, drainage pans, toiletry parts, bottles, containers, snow removal equipment parts, and various construction parts. EXAMPLES

[0123] The present invention will be described below with reference to examples and comparative examples. The olefin polymer A, aliphatic polyester polymer B and inorganic powder C used in the examples and comparative examples are shown below.

[0124] (1) Olefin Polymer A (A-1) Propylene homopolymer MFR (230℃, 2.16kg load): 7g / 10min Melting point (Tm): 163℃

[0125] (2) Aliphatic polyester polymer B (B-1) Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) Structural formula: (BI-3) formula Comonomer (3HH) component content (mol%): 0.4 mol% Weight average molecular weight (Mw): 397800 MFR (190℃, 2.16kg load): 8g / 10min MFR (B-1) (210℃, 2.16kg load): 171g / 10 minutes Melting point (Tm): 175℃

[0126] (3) Inorganic powder C (C-1) Talc Product name: Nippon Talc Nano Ace D-600 pH:9.0 Particle size D50: 0.6μm (C-2) Talc Product name: Nippon Talc Nano Ace FG-15 pH:8.7 Particle size D50: 1.5μm (C-3) Talc Product name: Hayashi Kasei Micron White TT-H pH:8.7 Particle size: 4.8μm (C-4) Wollastonite Product name: Hayashi Kasei Wollastonite VN-8N pH:9.9 Particle size: 11.0μm (C-5) Kaolinite Product name: Hayashi Kasei PoleStar450 pH: 5.9 Particle size: 1.5μm (C-6) Kaolinite Product name: Hayashi Kasei GlomaxLL pH: 6.2 Particle size: 1.5μm

[0127] The physical properties of each polymer, inorganic powder, and composition were measured according to the methods shown below.

[0128] (1) Melt mass flow rate (MFR, unit: g / 10 min) Measurement was performed according to the method specified in JIS K7210-2014. The measurement temperature was 230°C, 210°C, or 190°C, and the load was 2.16 kg. The cylinder in which the resin was melted and kneaded was made of metal, and no light was irradiated onto the resin. The above MFR(X) is a melt mass flow rate of a mixture X containing 0.5 part by mass of any one of the inorganic powders C-1 to C-5 per 100 parts by mass of the total of the polymer B-1 and any one of the inorganic powders C-1 to C-5, measured at a temperature of 210°C and a load of 2.16 kgf. MFR(B-1) is the melt mass flow rate of polymer B-1 measured under conditions of a temperature of 210° C. and a load of 2.16 kgf.

[0129] (2) Weight average molecular weight (Mw) The weight average molecular weight (Mw) was calculated based on the results of gel permeation chromatography (GPC). In the GPC measurement, a Waters GPC-150C was used as the measuring device, an orthodichlorobenzene solution with a polymer concentration of 0.05% by weight was used, and a mixed polystyrene gel column (Tosoh PSKgelGMH6-HT) was used as the column, and the measurement temperature was 135°C.

[0130] (3) Melting point of polymer (Tm) The measurement was performed according to the method specified in JIS K7121. The measurement temperature was −50° C. to 200° C. or −50° C. to 250° C., and the temperature rise rate was 10° C. / min.

[0131] (4) Content of comonomer component in aliphatic polyester polymer B The content of the comonomer component refers to the molar ratio of repeating units other than 3-hydroxybutyrate (3-hydroxyhexanoate (3HH) or 4-hydroxybutyrate (4HB)) to the total number of ester repeating units of hydroxyalkanoate in the aliphatic polyester polymer B.

[0132] The content of the comonomer component was determined by the method using 1H-NMR spectrum described in L. Tripathi., MCFactories, 11, 44 (2012). [Measurement conditions] Model: Bruker AVANCE600 Probe: 10mm cryoprobe Measurement temperature: 135℃ Pulse repetition time: 1 second Pulse width: 45° Number of times: 700 Magnetic field strength: 600MHz

[0133] (5) Flexural modulus (FM) Using a Toyo Machinery & Metals SI30III injection molding machine, injection molding was performed at a molding temperature of 220°C and a mold temperature of 50°C to obtain bending test pieces with a thickness of 4 mm, width of 10 mm, and length of 80 mm. The measurement conditions were in accordance with JIS-K-7171, and the bending modulus (unit: MPa) at 23°C was measured.

[0134] (6) Detection amount Using a Toyo Machinery Metal SI30III injection molding machine, injection molding was performed at a molding temperature of 220°C and a mold temperature of 50°C to obtain bending test pieces with a thickness of 4 mm, width of 10 mm, and length of 80 mm. 50 g of the bending test pieces obtained were weighed and cut to a width of 4 mm. The cut test pieces were placed in a polyethylene bag, sealed, and heated in an oven at 40°C for 2 hours. A Gastec gas detector (GV-100) equipped with a Gastec gas detector tube (81 L: acetic acid) was inserted into the polyethylene bag containing the heated sample, and the detection amount (unit: ppm) was evaluated. The higher the detection amount, the stronger the odor of the test piece.

[0135] (7) pH of inorganic powder The pH of the inorganic powder was evaluated according to JIS M 8016-1991 by adding 20 g of inorganic powder to 80 mL of pure water and stirring, and then using LAQUAtwin manufactured by Horiba Advanced Techno Co., Ltd. to evaluate the pH of the liquid.

[0136] Example 1 5.0% by mass of polymer (B-1), 85% by mass of polymer (A-1), and 10.0% by mass of inorganic powder (C-1) were mixed and melt-kneaded using a 15 mm twin-screw extruder KZW15-45MG (manufactured by Technobel) under conditions of cylinder set temperature: 210°C, screw rotation speed: 500 rpm, and extrusion rate: approximately 4 kg / hour to obtain a resin composition (Q-1).

[0137] Example 2 A resin composition (Q-1) was obtained in the same manner as in Example 1, except that the inorganic powder (C-2) was used.

[0138] Example 3 A resin composition (Q-1) was obtained in the same manner as in Example 1, except that the inorganic powder (C-3) was used.

[0139] Example 4 A resin composition (Q-1) was obtained in the same manner as in Example 1, except that the inorganic powder (C-4) was used.

[0140] Comparative Example 1 A resin composition (Q-1) was obtained in the same manner as in Example 1, except that the inorganic powder (C-5) was used.

[0141] Comparative Example 2 A resin composition (Q-1) was obtained in the same manner as in Example 1, except that the inorganic powder (C-6) was used. The results are shown in Table 1.

[0142] [Table 1]

[0143] In Examples 1 to 4, in which inorganic powders C1 to C4 having a pH in the range of 6.5 to 11.5 were used, the amount of detection was smaller than in Comparative Examples 1 and 2. In particular, in Examples 1 to 3, in which the pH was 9.5 or less, the amount of detection was particularly small.

Claims

1. A composition comprising an olefin polymer A, an aliphatic polyester polymer B, and an inorganic powder C, wherein the inorganic powder C has a pH of 6.5 to 11.5 as evaluated according to JIS M 8016-1991.

2. The composition according to claim 1 , wherein the inorganic powder C does not contain a fatty acid metal salt.

3. 3. The composition according to claim 2, wherein the aliphatic polyester polymer B is a poly(3-hydroxyalkanoate) polymer having a melting point of 150° C. or higher.

4. The composition according to claim 1 or 2, wherein the inorganic powder C has a pH of 8.5 to 9.5 as evaluated by JIS M 8016-1991.

5. 3. The composition according to claim 1, wherein the inorganic powder C has a median diameter D50 of 0.05 to 30 μm in a weight-based particle size distribution measured by a laser diffraction method.

6. The composition according to claim 1 or 2, wherein the content of the olefin polymer A is 51 to 99.9 parts by mass, and the content of the aliphatic polyester polymer B is 0.1 to 49 parts by mass, relative to 100 parts by mass in total of the olefin polymer A and the aliphatic polyester polymer B.

7. 3. The composition according to claim 1, wherein the content of the inorganic powder C is 0.1 to 40 parts by mass with respect to 100 parts by mass of the total of the olefin polymer A and the aliphatic polyester polymer B.

8. The composition according to claim 1 or 2, wherein the content of the aliphatic polyester polymer B is 0.1 to 20 parts by mass.

9. 3. The composition according to claim 1, wherein the olefin polymer A is a propylene copolymer.

10. The melt mass flow rate of the aliphatic polyester polymer B measured under conditions of a temperature of 210° C. and a load of 2.16 kgf is defined as MFR(B), 3. The composition according to claim 1, wherein, when a mixture X containing 0.5 parts by mass of the inorganic powder C per 100 parts by mass of the total of the aliphatic polyester-based polymer B and the inorganic powder C is determined to have a melt mass-flow rate measured at a temperature of 210°C under a load of 2.16 kgf, MFR(X) / MFR(B) is 1.0 or less.