Resin composition

Abstract

To provide a resin composition which contains an olefinic polymer and thermoplastic polyester and is excellent in dyeability.SOLUTION: A resin composition contains an olefinic polymer A, a polymer B-1 and a polymer B-2. The polymer B-1 is a poly(3-hydroxyalkanoate)-based polymer having a melting point of 150-220°C, and the polymer B-2 is aromatic polyester having a melting point of 180-220°C. With respect to 100 pts.mass of the total of the polymer A, the polymer B-1 and the polymer B-2, a content of the polymer A is 70-95 pts.mass, a content of the polymer B-1 is 1-15 pts.mass, and a content of the polymer B-2 is 1-25 pts.mass.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition.

Background Art

[0002] Among thermoplastic resins, olefin polymers are inexpensive, lightweight, and excellent in properties such as moldability, mechanical properties, heat resistance, and long-term heat deterioration resistance. For this reason, olefin polymers are used in various containers such as bottles, food packaging materials, caps for containers, stationery, daily sundries, fibers for carpets and sofas, interior and exterior automotive materials, electrical and electronic equipment parts, and building materials such as interior materials for buildings and houses. In recent years, there have been many demands for improving airtightness, paintability, dyeability, etc. for these articles.

[0003] Therefore, as a means to meet these demands, as described in Patent Document 1, a method of blending a thermoplastic polyester typified by polyethylene terephthalate and polybutylene terephthalate, which is more excellent in airtightness, paintability, and dyeability than olefin polymers, with olefin polymers can be considered.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, olefin polymers and thermoplastic polyesters have poor compatibility. Therefore, even when a composition containing a sufficiently melt-kneaded olefin polymer and thermoplastic polyester is dyed with a disperse dye, there has been a problem that it is difficult to efficiently dye the composition due to phase separation between the olefin polymer and the thermoplastic polyester.

[0006] The present invention has been made in view of the above problems, and an object thereof is to provide a resin composition containing an olefin-based polymer and a thermoplastic polyester and having excellent dyeability.

Means for Solving the Problems

[0007] One aspect of the present invention is a resin composition containing an olefin-based polymer A, a polymer B-1, and a polymer B-2, wherein the polymer B-1 is a poly(3-hydroxyalkanoate)-based polymer having a melting point of 150°C to 220°C, the polymer B-2 is an aromatic polyester having a melting point of 180 to 220°C, with respect to a total of 100 parts by mass of the polymer A, the polymer B-1, and the polymer B-2, the content of the polymer A is 70 to 95 parts by mass, the content of the polymer B-1 is 1 to 15 parts by mass, and the content of the polymer B-2 is 1 to 25 parts by mass.

[0008] In the above resin composition, with respect to a total of 100 parts by mass of the polymer A, the polymer B-1, and the polymer B-2, the content of the polymer A can be 80 to 90 parts by mass, the content of the polymer B-1 can be 1 to 10 parts by mass, and the content of the polymer B-2 can be 1 to 20 parts by mass.

[0009] The polymer A can be a propylene homopolymer.

Effects of the Invention

[0010] According to the present invention, there is provided a resin composition containing an olefin-based polymer and a thermoplastic polyester and having excellent dyeability.

Modes for Carrying Out the Invention

[0011] Hereinafter, some embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

[0012] The resin composition according to the present invention contains an olefin polymer A, a polymer B-1, and a polymer B-2.

[0013] <Olefin polymer A> The olefin polymer A is a polymer containing 50% by mass or more of structural units derived from olefins having 2 to 10 carbon atoms (wherein the total amount of the olefin polymer is 100% by mass). Examples of olefins having 2 to 10 carbon atoms are ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and 1-decene.

[0014] The olefin polymer A may contain structural units derived from monomers other than olefins having 2 to 10 carbon atoms. Examples of monomers other than olefins having 2 to 10 carbon atoms are 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.

[0015] 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 thereof.

[0016] An ethylene copolymer is a polymer containing 50% by mass or more of structural units derived from ethylene, and examples thereof are ethylene homopolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, and ethylene-1-butene-1-hexene copolymer. The ethylene copolymer may be a combination of two or more ethylene copolymers.

[0017] A propylene-based copolymer is a polymer containing 50% by mass or more of structural units derived from propylene. Examples thereof include a propylene homopolymer, a propylene-ethylene copolymer, a propylene-1-butene copolymer, a propylene-1-hexene copolymer, a propylene-1-octene copolymer, a propylene-ethylene-1-butene copolymer, a propylene-ethylene-1-hexene copolymer, and a propylene-ethylene-1-octene copolymer. The propylene-based copolymer may be a combination of two or more propylene-based copolymers. It is preferable that the olefin polymer A is a propylene-based copolymer.

[0018] A butene-based copolymer is a polymer containing 50% by mass or more of structural units derived from 1-butene. Examples thereof include a 1-butene homopolymer, a 1-butene-ethylene copolymer, a 1-butene-propylene copolymer, a 1-butene-1-hexene copolymer, a 1-butene-1-octene copolymer, a 1-butene-ethylene-propylene copolymer, a 1-butene-ethylene-1-hexene copolymer, a 1-butene-ethylene-1-octene copolymer, a 1-butene-propylene-1-hexene copolymer, and a 1-butene-propylene-1-octene copolymer. The butene-based copolymer may be a combination of two or more butene-based copolymers.

[0019] The olefin polymer may be one kind of polymer or a mixture of two or more kinds of polymers.

[0020] The melt mass flow rate (MFR) of the olefin polymer A measured according to JIS K7210-2014 under the conditions of 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.

[0021] The melting point of the olefin polymer A can be 110 to 180 °C.

[0022] The above olefin polymer A can be produced by using a known polymerization method with a known polymerization catalyst.

[0023] The olefin polymer A is preferably a propylene homopolymer. A propylene homopolymer is a polymer composed only of structural units derived from propylene.

[0024] From the perspective of processability, the melt mass flow rate of the propylene homopolymer measured under the conditions of a temperature of 230°C and a load of 2.16 kgf can be 0.1 g / 10 min or more, 1 g / 10 min or more, 3 g / 10 min or more, 5 g / 10 min or more. This melt mass flow rate can be 80 g / 10 min or less, 60 g / 10 min or less, 50 g / 10 min or less, 30 g / 10 min or less, 20 g / 10 min or less. The melt mass flow rate of the propylene homopolymer is determined according to JIS K 7210-2014.

[0025] The propylene homopolymer can be a propylene homopolymer having an isotactic structure. Having an isotactic structure means that the isotactic pentad fraction (hereinafter also referred to as [mmmm]) measured using 13C-NMR is 0.85 or more. This [mmmm] is preferably 0.90 or more, and can be 0.95 or more, 0.96 or more, and 0.97 or more. [mmmm] may be 0.99 or less.

[0026] Here, the isotactic pentad fraction indicates the existence ratio of isotactic chains in the pentad units in the molecular chain measured using 13C-NMR, and is the fraction of the structural unit derived from propylene at the center of the chain in which 5 consecutive structural units derived from propylene are meso-bonded. Specifically, it is a value calculated as the fraction of the [mmmm] peak in the total absorption peak in the methyl carbon region observed in the 13C-NMR spectrum. Here, the [mmmm] peak is the peak derived from propylene at the center of the chain in which 5 consecutive structural units are meso-bonded.

[0027] Incidentally, this [mmmm] can be determined according to the method described in the report by A. Zambelli et al. (Macromolecules, 1973, No. 6).

[0028] The propylene homopolymer can be produced by a known polymerization method using a catalyst system formed by contacting a known solid titanium catalyst component, an organometallic compound catalyst component, and, if necessary, an electron donor; a catalyst system formed by contacting a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring and an alkylaluminoxane; a catalyst system formed by contacting a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring, a compound that reacts with the transition metal compound to form an ionic complex, and an organoaluminum compound, etc.

[0029] <Polymer B-1> Polymer B-1 is a poly(3-hydroxyalkanoate)-based polymer having a melting point of 150 to 220°C.

[0030] The poly(3-hydroxyalkanoate)-based polymer is a polyester of polyhydroxyalkanoate, i.e., hydroxyalkanoic acid, and necessarily contains a structural 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 substituents. In particular, from the viewpoint of compatibility with components other than Polymer B-1 contained in the composition (for example, olefin-based polymer A), R is preferably an alkyl group having 1 to 8 carbon atoms, an amide group having 2 to 20 carbon atoms, or an aryl group having 6 to 8 carbon atoms.

[0031] [-O-CHR-CH2-CO-]…(1)

[0032] Examples of the halogen atom are F, Cl, Br, and I.

[0033] The alkyl group having 1 to 15 carbon atoms may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 8, more preferably 1 to 4. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl group, hexyl group, isohexyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group.

[0034] Examples of the amino group having 1 to 11 carbon atoms include amino group, alkylamino group, dialkylamino group, arylamino group, alkylarylamino group, benzylamino group, dibenzylamino group.

[0035] Examples of the alkylamino group include methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentylamino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, 1-adamantamino group, 2-adamantamino group.

[0036] Examples of the dialkylamino group 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.

[0037] Examples of the arylamino group include an anilino group, a 1-naphthylamino group, a 2-naphthylamino group, an o-toluidino group, an m-toluidino group, a p-toluidino group, a 1-fluorenamino group, a 2-fluorenamino group, a 2-thiazolamino group, and a p-terphenylamino group.

[0038] Examples of the alkylarylamino group include 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.

[0039] 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.

[0040] The "amide group" means a group obtained by removing one hydrogen atom bonded to a nitrogen atom from a carboxylic acid amide. Examples of the amide group having 2 to 20 carbon atoms include groups represented by -NH-C(=O)-R such as a formamide group, an acetamide group, a propionamide group, a butylamide group, a benzamide group, a trifluoroacetamide group, and a pentafluorobenzamide group (where R is a hydrogen atom or a monovalent organic group), and groups such as a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group, a ditrifluoroacetamide group, and a dipentafluorobenzamide group represented by -N(-C(=O)-R)(-C(=O)-R). A where R A is a hydrogen atom or a monovalent organic group), and A -N(-C(=O)-R)(-C(=O)-R BA group represented by (where R A , R B are each independently a hydrogen atom or a monovalent organic group). The organic group can be an alkyl group, an alkoxy group, or an aryl group, which may be substituted with a halogen atom. Among them, the amide group is preferably a formamide group, an acetamide group, a propionamide group, a butyramide group, or a benzamide group.

[0041] 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. Among them, a phenyl group, a tolyl group, and a xylyl group are preferred.

[0042] Examples of the heteroatom of the monovalent heterocyclic group having 1 to 9 carbon atoms are N, O, and S, which may be saturated or unsaturated, and may have a single heteroatom, a plurality of heteroatoms, or different heteroatoms. Examples of such a heterocyclic group 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.

[0043] The structural unit of polymer B-1 may consist only of one or more 3-hydroxyalkanoates represented by formula (1), or may have one or more 3-hydroxyalkanoates represented by formula (1) and one or more other hydroxyalkanoates.

[0044] Polymer B-1 preferably contains 50 mol% or more, more preferably 70 mol% or more, of the structural unit of 3-hydroxylcanoate represented by formula (1) with respect to all the structural units (100 mol%) of hydroxyalkanoate.

[0045] When R is a hydrogen atom or C n H 2n+1An alkyl group represented by, where n is an integer from 1 to 15. Examples of 3-hydroxyalkanoates represented by formula (1) include 3-hydroxybutyrate where n = 1 (hereinafter sometimes referred to as 3HB), 3-hydroxyvalerate where n = 2 (hereinafter sometimes referred to as 3HV), 3-hydroxyhexanoate where n = 3 (hereinafter sometimes referred to as 3HH), 3-hydroxyoctanoate where n = 5, 3-hydroxyoctadecanoate where n = 15, and 3-hydroxypropionate where R is a hydrogen atom.

[0046] An example of polymer B-1 having only one kind of structural unit represented by formula (1) is poly(3-hydroxybutyrate) (hereinafter sometimes referred to as P3HB).

[0047] Examples of polymer B-1 having only a plurality of kinds of structural 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).

[0048] Examples of hydroxyalkanoates other than 3-hydroxyalkanoates represented by formula (1) are structural units represented by formula (2) (wherein R 1 is a hydrogen atom or an alkyl group represented by C n H 2n+1 and n is an integer of 1 or more and 15 or less, and m is an integer of 2 to 10).

[0049] [-O-CHR 1 -C m H 2m+1 -CO-]…(2)

[0050] Examples of polymer B-1 containing the structural units of formula (1) and formula (2) include poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (for example, the following formula (P3HB4HB)).

[0051] From the viewpoint of increasing the melting point, it is preferable that the structural unit of polymer B-1 contains at least 3-hydroxybutyrate among the 3-hydroxyalkanoates represented by formula (1).

[0052] Polymer B-1 preferably contains 50 mol% or more, more preferably 70 mol% or more of the structural unit of 3-hydroxybutyrate based on all the structural units (100 mol%) of hydroxyalkanoate.

[0053] Polymer B-1 may have structural units of two or more esters. For example, it may be a di-polymer having two structural units as described above, a tri-copolymer having three structural units, or a tetra-copolymer having four structural units.

[0054] For example, an example of a tri-copolymer is poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate) (hereinafter sometimes referred to as (P3HB3HV3HH)).

[0055] As described above, it is preferable that polymer B-1 contains 3-hydroxybutyrate among the structural units of the 3-hydroxyalkanoate represented by formula (1). The ratio XX of the structural unit of 3-hydroxybutyrate is preferably 90 mol% or more, more preferably 95 mol% or more, and still more preferably 98.0 mol% or more based on 100 mol of the ester structural units of all hydroxyalkanoates.

[0056] The ratio XX is usually 100 mol% or less, preferably 99.9 mol% or less, and preferably 99.8 mol% or less.

[0057] The pattern of the copolymer array may be any pattern such as a random copolymer, an alternating copolymer, a block copolymer, a graft copolymer, etc.

[0058] Polymer B-1 may have other ester structural units other than those of formula (1) and formula (2), but the main chain of the other ester structural units does not contain an aromatic hydrocarbon structure. That is, polymer B-1 is an aliphatic polyester. However, it is possible that a group having an aromatic hydrocarbon group is bonded to the carbon of the main chain of the other ester structural unit.

[0059] The composition ratio of the structural units in polymer B-1 can be determined by calculating from the NMR measurement results such as 1H-NMR and 13C-NMR as described in L. Tripathi., M.C. Factories, 11, 44 (2012).

[0060] Also, polymer B-1 may be a blend of two or more poly(3-hydroxyalkanoate) polymers.

[0061] The weight average molecular weight (Mw) of polymer B-1 can be from 10,000 to 1,000,000, preferably from 20,000 to 800,000, and more preferably from 30,000 to 600,000. By setting the weight average molecular weight (Mw) to 10,000 or more, it becomes possible to obtain a molded article excellent in impact strength and tensile elongation. Also, by setting the weight average molecular weight to 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, or 200,000 or less. In this specification, the weight average molecular weight (Mw) is measured by GPC using standard polystyrene as the molecular weight standard substance.

[0062] Polymer B-1 is preferably a thermoplastic resin and is crystalline.

[0063] According to JIS K7210-2014, the melt mass flow rate (MFR(B-1)) of Polymer B-1 measured under the conditions of a temperature of 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. MFR(B-1) may be 1 g / 10 min or more, 3 g / 10 min or more, or 5 g / 10 min or more.

[0064] The melting point (Tm) of Polymer B-1 is 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 Polymer B-1 is 220 °C or lower, and may be 210 °C or lower, 200 °C or lower, or 190 °C or lower.

[0065] The melting point (Tm) of each polymer in this specification is measured based on the position of the main peak due to the melting of crystals determined by differential scanning calorimetry (DSC) measurement in accordance with JIS K7121.

[0066] The poly(3-hydroxyalkanoate) - based polymer may be produced by microorganisms or may be derived from compounds (such as cyclic lactones) derived from petroleum or plant raw materials.

[0067] In the poly(3-hydroxyalkanoate) - based polymer produced from microorganisms, each structural unit of hydroxyalkanoate may consist only of the D form (R form), but may also contain both the D form (R form) and the L form (S form) like those derived from a mixture of the D form (R form) and the L form (S form).

[0068] In the poly(3-hydroxyalkanoate) - based polymer produced from microorganisms, the structural unit of formula (1) can be represented as follows. In formula (BI-1), n represents the degree of polymerization.

[0069] [Chemical formula]

[0070] And, for example, poly-(3-hydroxybutyrate) produced from microorganisms has the following structure. (BI-2) In the formula, n represents the degree of polymerization.

[0071]

Chemical formula

[0072] Also, poly-(3-hydroxybutyrate-co-3-hydroxyhexanoate) produced from microorganisms has the following structure. (BI-3) In the formula, m and n represent the degree of polymerization.

[0073]

Chemical formula

[0074] Also, poly-(3-hydroxybutyrate-co-4-hydroxybutyrate) produced from microorganisms has the following structure. (BI-4) In the formula, m and n represent the degree of polymerization.

[0075]

Chemical formula

[0076] Polymer B-1 can have biodegradability.

[0077] For example, poly(3-hydroxyalkanoate)-based polymers can be produced by microorganisms such as Alcaligenes eutrophus AC32 strain (international deposit based on the Budapest Treaty, international deposit authority: Patent Biological Deposit Center, National Institute of Advanced Industrial Science and Technology (1-1-1 Higashi, Tsukuba, Ibaraki, Japan, Central 6), original deposit date: August 12, 1996, transferred on August 7, 1997, deposit number FERMBP-6038 (transferred from the original deposit FERM P-15786)) (J. Bacteriol., 179, 4821 (1997)), which was obtained by introducing a PHA synthase gene derived from Aeromonas caviae into Alcaligenes eutrophus.

[0078] <Polymer B-2> The polymer B-2 of the present embodiment is an aromatic polyester having a melting point of 180 to 220°C. An aromatic polyester is a polymer having an aromatic hydrocarbon structure (aromatic ring) and an ester bond in the main chain.

[0079] Polymer B-2 can be a polycondensate of a polycarboxylic acid and a polyol (polyhydroxy compound). A polycarboxylic acid refers to an organic compound having a plurality of carboxyl groups or a derivative thereof (for example, an acid anhydride, an ester). A polyol (polyhydroxy compound) refers to an organic compound having a plurality of hydroxyl groups.

[0080] In polymer B-2, the main chain of the structural unit derived from the polycarboxylic acid may have an aromatic ring, the main chain of the structural unit derived from the polyol may have an aromatic ring, or both the main chains of the structural unit derived from the polycarboxylic acid and the structural unit derived from the polyol may have an aromatic ring.

[0081] From the viewpoint of lowering the melting point, it is preferable that the structural unit derived from the polycarboxylic acid has an aromatic ring in the main chain and the structural unit derived from the polyol does not have an aromatic ring in the main chain. It is more preferable that the structural unit derived from the polyol is aliphatic. Aliphatic includes those containing an oxygen atom.

[0082] Examples of polycarboxylic acids in the case where the main chain of the structural unit derived from a polycarboxylic acid has an aromatic ring include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl ether 4,4'-dicarboxylic acid, trimellitic acid, trimethacrylic acid, and derivatives thereof. The polycarboxylic acid may contain one type of polycarboxylic acid, or may contain a plurality of types of polycarboxylic acids.

[0083] Among them, it is preferable that the polycarboxylic acid contains terephthalic acid. The ratio of the number of moles of the structural unit derived from a polycarboxylic acid other than terephthalic acid to the number of moles of the structural unit derived from all acid components can be 10 mol% or less, 5 mol% or less, 1 mol% or less, or 0.5 mol% or less.

[0084] When the polycarboxylic acid contains terephthalic acid, the polycarboxylic acid may contain other polycarboxylic acid components in addition to terephthalic acid.

[0085] Examples of other polycarboxylic acid components include the above aromatic polycarboxylic acids other than terephthalic acid, and aliphatic polycarboxylic acids such as adipic acid, sebacic acid, succinic acid, dimer acid, 1,4-cyclohexanedicarboxylic acid, and derivatives thereof.

[0086] Examples of polyols in the case where the structural unit derived from a polyol is aliphatic include aliphatic polyols such as ethylene glycol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, diethylene glycol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol.

[0087] Any one of the polyols may be added alone, or two or more of them may be added in any ratio.

[0088] Among aliphatic polyols, from the viewpoint of lowering the melting point, a mixture of ethylene glycol and an aliphatic polyol having a longer chain length than ethylene glycol is preferred. Examples of polyols having a longer chain length than ethylene glycol are aliphatic polyols such as 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and the like.

[0089] The chain length is the length of the atomic chain existing between OH groups. The aliphatic polyol having a longer chain length than ethylene glycol may be only one kind or a mixture of a plurality of kinds.

[0090] The amount of the structural unit derived from ethylene glycol is preferably 10 mol% or more based on the total amount of the structural units derived from polyol. The amount of the structural unit derived from ethylene glycol may be 20 mol% or more, 30 mol% or more, 40 mol% or more, 45 mol% or more based on the total amount of the structural units derived from polyol. The amount of the structural unit derived from a polyol having a longer chain length than ethylene glycol is preferably 27 mol% or more based on the total amount of the structural units derived from polyol. By including a polyol component having a longer chain length than ethylene glycol, the melting point of polymer B-2 can be lowered. The amount of the structural unit derived from a polyol having a longer chain length than ethylene glycol may be 30 mol% or more, 35 mol% or more, 40 mol% or more, and may be 55 mol% or less, 52 mol% or less, 50 mol% or less, 45 mol% or less based on the total amount of the structural units derived from polyol.

[0091] Among them, polymer B-2 preferably contains structural units derived from ethylene glycol and 2,2-dimethyl-1,3-propanediol (neopentyl glycol) as the structural units derived from aliphatic polyols.

[0092] The content rate of the structural unit derived from neopentyl glycol is preferably 27 mol% or more, more preferably 30 mol% or more, still more preferably 35 mol% or more, and even more preferably 40 mol% or more, based on the total amount of the structural units derived from the polyol. If it is 25 mol% or less, the molding temperature of the composition will exceed 200°C. The content rate of the structural unit derived from neopentyl glycol is preferably 55 mol% or less, more preferably 52 mol% or less, still more preferably 50 mol% or less, and even more preferably 45 mol% or less, based on the total amount of the structural units derived from the polyol component. If it exceeds 55 mol%, sufficient mechanical properties may not be obtained.

[0093] In the aromatic polyester, when the structural unit derived from the polycarboxylic acid has an aromatic ring in the main chain and the structural unit derived from the polyhydroxy compound also has an aromatic ring in the main chain, examples of the polyhydroxy compound having an aromatic ring in the main chain are hydroquinone, 4,4'-dihydroxybiphenyl, and bisphenol A.

[0094] Also, Polymer B-2 may be a polycondensate of monomers that do not contain polycarboxylic acid. For example, Polymer B-2 may be a polycondensate of an aromatic hydroxycarboxylic acid in which two Hs of the aromatic ring are substituted with a hydroxy group and a carboxyl group. Examples of the aromatic hydroxycarboxylic acid are parahydroxybenzoic acid and 6-hydroxy-2-naphthalenecarboxylic acid.

[0095] Also, Polymer B-2 may be a polycondensate of a mixture of an aromatic hydroxycarboxylic acid and at least one of a polyol and a polycarboxylic acid. In this case, the polyol and the polycarboxylic acid may each independently be aliphatic or aromatic having an aromatic ring in the main chain.

[0096] The melting point of Polymer B-2 is 180 to 220°C, preferably 180 to 210°C, and more preferably 180 to 200°C.

[0097] According to JIS K7210-2014, the melt mass flow rate of polymer B-2 (MFR(B-2)) measured under the conditions of a temperature of 230 °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-2) 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-2) may be 150 g / 10 min or more, 100 g / 10 min or more, or 70 g / 10 min or less.

[0098] <Composition of the resin composition> The resin composition contains 70 to 95 parts by mass of olefin polymer A, 1 to 15 parts by mass of polymer B-1, and 1 to 25 parts by mass of polymer B-2 with respect to a total of 100 parts by mass of olefin polymer A, polymer B-1, and polymer B-2. The resin composition can contain 80 to 90 parts by mass of olefin polymer A, 1 to 10 parts by mass of polymer B-1, and 1 to 20 parts by mass of polymer B-2. Polymer B-2 may be 2 parts by mass or more, 4 parts by mass or more, 18 parts by mass or less, or 16 parts by mass or less.

[0099] The total proportion of olefin polymer A, polymer B-1, and polymer B-2 in the entire resin composition can be 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more.

[0100] That polymer B-1 forms a dispersed phase means that the resin composition has a sea-island structure in which olefin polymer A is the continuous phase (sea part) and polymer B is the dispersed phase (island part). The average equivalent circle diameter of the dispersed phase (island part) can be 10 nm to 400 μm.

[0101] (Additive) The resin composition may contain additives as necessary. The additives can 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 stabilizers are at least one selected from the group consisting of lubricants, antioxidants, heat stabilizers, light-resistant agents, weather-resistant agents, metal deactivators, ultraviolet absorbers, light stabilizers, and copper corrosion inhibitors. An example of a light-resistant agent is a hindered amine light stabilizer.

[0103] Examples of colorants are at least one selected from the group consisting of dyes such as organic dyes, or titanium oxide, carbon black, and organic pigments. An example of a metal powder is ferrite.

[0104] Examples of organic powders are proteins. Examples of inorganic fibers are glass fibers and metal fibers. Examples of organic fibers are carbon fibers and aramid fibers. An example of inorganic whiskers is potassium titanate whiskers.

[0105] Examples of fillers are at least one selected from the group consisting of glass beads, glass balloons, glass flakes, asbestos, mica, calcium carbonate, talc, silica, calcium silicate, hydrotalcite, kaolin, diatomaceous earth, graphite, pumice, EVA powder, cotton flock, cork powder, barium sulfate, fluororesin, cellulose powder, and wood powder.

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

[0107] In the resin composition, the additives may be contained in any of polymers A, B-1, and B-2. The additives may form a separate dispersed phase in the continuous phase of the olefin-based polymer A, distinct from polymers B-1 and B-2.

[0108] (Method for producing the resin composition) The above resin composition can be obtained by melt-kneading an olefin-based polymer A, a polymer B-1, a polymer B-2, and an additive added as required. The kneading temperature (set temperature of the kneader) is preferably 150 to 300 °C, more preferably 170 °C to 280 °C. Further, a part of the olefin-based polymer A and the polymers B-1 and B-2 can be melt-kneaded to obtain a preliminary kneaded product, and then the remaining olefin-based polymer A and polymers B-1 and B-2 can be added to the preliminary kneaded product and further melt-kneaded to obtain the resin composition.

[0109] (Method for manufacturing a molded article of the resin composition) Using a known resin molding method such as an injection molding method, an extrusion molding method, a spinning molding method, a vacuum molding method, a pressure air molding method, a press molding method, a foam molding method, a blow molding method, a rotational molding method, etc., a molded article of the above propylene-based composition having a required shape can be obtained.

[0110] In addition, the above resin composition can be bonded to other materials such as other resins, fibers, metals, papers, and leathers to obtain a multilayer structure.

[0111] The surface of the molded article of the resin composition of the present invention may be subjected to a surface treatment. Examples of the surface treatment method include embossing treatment, corona discharge treatment, flame treatment, plasma treatment, ozone treatment, etc.

[0112] The above resin composition can be widely used as a resin material.

[0113] Examples of the uses of the resin composition of the present invention include fiber materials, exterior members, furniture and interior decoration members, household members, toy members, gardening members, automobile members, and packaging materials. Examples of fiber materials include clothing fabric members, interior fabric members, industrial fiber members, etc. Examples of exterior members include carport members, fence members, door members, gatepost members, post members, cycle port members, deck members, sunroom members, roof members, terrace members, handrail members, shade members, awning members, etc. Examples of furniture and interior decoration members include sofa members, table members, chair members, bed members, chest of drawers members, cabinet members, dresser members, etc. Examples of household electrical appliance members include watch members, mobile phone members, white goods household electrical appliance members, etc. Examples of toy members include plastic model members, diorama members, video game console members, etc. Examples of gardening members include planter members, vase members, flowerpot members, etc. Examples of automobile members include bumper materials, instrument panel materials, airbag cover materials, etc. Examples of packaging materials include food packaging materials, fiber packaging materials, miscellaneous goods packaging materials, etc. Further, examples of other uses include monitor members, office automation (OA) equipment members, medical members, drain pans, toiletries members, bottles, containers, snow removal supplies members, various building members, etc.

Examples

[0114] Hereinafter, the present invention will be described using examples and comparative examples. The olefin-based polymer A, polymer B-1, and polymer B-2 used in the examples and comparative examples are shown below.

[0115] (1) Olefin-based polymer A (A-1) Propylene homopolymer MFR (230 °C, 2.16 kg load): 7 g / 10 min Melting point (Tm): 163 °C

[0116] (2) Polymer B-1 (B-1-1) Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) Structural formula: Formula (BI-3) Content of comonomer (3HH) component (mol%): 0.2 mol% Weight-average molecular weight (Mw): 104,000 MFR (190 °C, 2.16 kg load): 7.8 g / 10 min Melting point (Tm): 177 °C

[0117] (B-1-2) Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) Structural formula: Formula (BI-4) (Trade name) M4300: Manufactured by CJ CheilJedang Corporation Content of comonomer (4HB) component (mol%): 45 mol% Weight-average molecular weight (Mw): 216,000 MFR (190 °C, 2.16 kg load): 4.0 g / 10 min Melting point (Tm): 48.7 °C

[0118] (3) Polymer B-2 (B-2-1) Aromatic polyester Polycarboxylic acid: terephthalic acid (100 mol%) Polyol: ethylene glycol (67 mol%) Polyol: neopentyl glycol (33 mol%) MFR (230 °C, 2.16 kg load): 48 g / 10 min Melting point (Tm): 198 °C

[0119] (B-2-2) Aromatic polyester (Trade name) Bellpet EFG70: Manufactured by Bell Polyester Products Polycarboxylic acid: terephthalic acid Polyol: ethylene glycol Intrinsic viscosity: 0.75 dl / g Melting point (Tm): 255 °C

[0120] The physical properties of each polymer and composition were measured according to the methods shown below.

[0121] (1) Melt mass flow rate (MFR, unit: g / 10 min) It was measured according to the method specified in JIS K7210-2014. The measurement temperature was 230 °C or 190 °C, and the load was 2.16 kg.

[0122] (2) Weight-average molecular weight (Mw) The weight-average molecular weight (Mw) was calculated based on the measurement results of gel permeation chromatography (GPC). In the GPC measurement, Waters GPC-150C manufactured by Waters was used as the measurement device, an orthodichlorobenzene solution with a polymer concentration of 0.05% by weight was used, a mixed polystyrene gel column (PSKgel GMH6-HT manufactured by Tosoh Corporation) was used as the column, and the measurement temperature was 135 °C.

[0123] (3) Content of the comonomer component of polymer B-1 The content of the comonomer component is the molar ratio of other structural units (3-hydroxyhexanoate (3HH) or 4-hydroxybutyrate (4HB)) other than 3-hydroxybutyrate to the total number of ester structural units of the hydroxyalkanoate of polymer B-1.

[0124] The content of the comonomer component was determined by the method using the 1H-NMR spectrum described in L. Tripathi., M.C. Factories, 11, 44 (2012). 〔Measurement conditions〕 Model: Bruker AVANCE600 Probe: 10 mm cryoprobe Measurement temperature: 135 °C Pulse repetition time: 1 second Pulse width: 45° Number of integrations: 700 times Magnetic field strength: 600 MHz

[0125] (4) Melting point (Tm) of the polymer It was measured 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 heating rate was 10 °C / min.

[0126] (5) Dyeing degree Using a Shindo Metal Industry Co., Ltd. compression molding machine (P-37), the resin was preheated at 210°C for 5 minutes, and then compressed at 210°C under a pressure of 10 MPa for 5 minutes to obtain a molded product shaped to a width of 23 mm, length of 43 mm, and thickness of 50 μm. The absorption spectrum of the obtained molded product was obtained using a spectrophotometer (UV3150 manufactured by Shimadzu Corporation), and then the integral value (1) of the absorption spectrum in the wavelength range of 450 to 650 nm was calculated. Next, 500 mL of water, 15 g of organic dye (Mecikron rubine spw manufactured by Jiangsu Dewang), 0.5 g of polyethylene glycol monooleate, 0.5 g of glycerol monostearate, and 0.5 mL of acetic acid were mixed to prepare a dye solution, which was then placed in a sealed reactor together with the molded body described above, sealed, and the molded body was dyed at 110°C for 40 minutes while stirring with a magnetic stirrer. Next, 300 mL of water, 0.9 g of sodium sulfate, 1.2 g of sodium hydroxide, and 0.3 g of polyethylene glycol 4000 were mixed to prepare a soaping solution, which was then placed in a sealed reactor together with the dyed molded body described above, sealed, and soaped at 70°C for 20 minutes while stirring with a magnetic stirrer. The soaped molded product was subjected to an absorption spectrum measurement using a spectrophotometer (Shimadzu Corporation UV3150), and the integral value (2) of the absorption spectrum in the wavelength range of 450 to 650 nm was then calculated. The dyeing degree was calculated from the following formula (3) using the integral value (1) of the obtained absorption spectrum, the integral value (2) of the obtained absorption spectrum, and the thickness of the molded article. Dyeing degree = {[Integral value from 450 to 650 nm in the absorption spectrum of the molded body after soaping (2)] - [Integral value from 450 to 650 nm in the absorption spectrum of the molded body (1)]} / Thickness of molded body (μm) ... (3) The larger the value, the better the dyeability.

[0127] (6) Density (g / cm 3 ) The density of the resin composition was determined according to Method A in the method specified in JIS K7112-1999.

[0128] (Example 1) 85% by mass of polymer (A-1), 5% by mass of polymer (B-1-1), and 10% by mass of polymer (B-2-1) were uniformly mixed in a powder state and then supplied to a small kneader (Xplore; manufactured by DSM) for kneading under the conditions of a resin temperature of 190 °C, a kneading time of 4 minutes, and a screw rotation speed of 100 rpm to obtain a resin composition. The degree of staining and density of the resin composition were evaluated.

[0129] (Example 2) The same procedure as in Example 1 was carried out except that 82% by mass of polymer (A-1), 8% by mass of polymer (B-1-1), and 10% by mass of polymer (B-2-1) were used.

[0130] (Example 3) The same procedure as in Example 1 was carried out except that 70% by mass of polymer (A-1), 5% by mass of polymer (B-1-1), and 25% by mass of polymer (B-2-1) were used.

[0131] (Comparative Example 1) The same procedure as in Example 1 was carried out except that 100% by mass of polymer (A-1) was used alone.

[0132] (Comparative Example 2) The same procedure as in Example 1 was carried out except that 85% by mass of polymer (A-1) and 15% by mass of polymer (B-1-1) were used.

[0133] (Comparative Example 3) The same procedure as in Example 1 was carried out except that 85% by mass of polymer (A-1) and 15% by mass of polymer (B-2-1) were used.

[0134] (Comparative Example 4) The same procedure as in Example 1 was carried out except that 85% by mass of polymer (A-1), 5% by mass of polymer (B-1-2), and 10% by mass of polymer (B-2-1) were used.

[0135] (Comparative Example 5) The same procedure as in Example 1 was carried out, except that 85% by mass of polymer (A-1), 5% by mass of polymer (B-1-1), and 10% by mass of polymer (B-2-2) were used, and the resin temperature during kneading was 230°C.

[0136] The conditions and results are shown in Table 1.

Table 1

Claims

1. A composition comprising an olefin polymer A, a polymer B-1, and a polymer B-2, The polymer B-1 is a poly(3-hydroxyalkanoate) polymer having a melting point of 150 to 220°C, The polymer B-2 is an aromatic polyester having a melting point of 180 to 220°C, Based on a total of 100 parts by mass of the polymer A, the polymer B-1, and the polymer B-2, the content of the polymer A is 70 to 95 parts by mass, the content of the polymer B-1 is 1 to 15 parts by mass, and the content of the polymer B-2 is 1 to 25 parts by mass. A resin composition.

2. Based on a total of 100 parts by mass of the polymer A, the polymer B-1, and the polymer B-2, the content of the polymer A is 80 to 90 parts by mass, the content of the polymer B-1 is 1 to 10 parts by mass, and the content of the polymer B-2 is 1 to 20 parts by mass. The resin composition according to claim 1.

3. The resin composition according to claim 1 or 2, wherein the polymer A is a propylene homopolymer.

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