composition

Abstract

The composition of the present application is a composition comprising an olefin-based polymer A and a polymer B, wherein the polymer B is a poly(3-hydroxyalkanoate)-based polymer having a melting point of 150°C or higher, and the content of the polymer A is 51 to 99.9 parts by mass and the content of the polymer B is 0.1 to 49 parts by mass, with respect to 100 parts by mass in total of the polymer A and the polymer B.

Description

Technical Field

[0001] This invention relates to compositions. Background Technology

[0002] Among thermoplastic resins, olefin polymers are inexpensive, lightweight, and possess excellent properties such as molding processability, mechanical properties, heat resistance, and resistance to long-term heat degradation. Therefore, olefin polymers are used in various containers such as bottles, food packaging materials, container lids, stationery, daily necessities, carpet or sofa fibers, automotive interior and exterior parts, electrical and electronic equipment components, and building materials such as interior decoration materials for buildings or residences. In recent years, there has been a growing demand for improvements in airtightness, paintability, and dyeability in these products.

[0003] Therefore, as a way to address these requirements, as described in Patent Document 1, it is conceivable to incorporate thermoplastic polyesters, such as polyethylene terephthalate and polybutylene terephthalate, which have better airtightness, coatability and dyeability than olefin polymers, into olefin polymers.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 6-73264 Summary of the Invention

[0007] The problem that the invention aims to solve

[0008] However, olefin polymers have poor compatibility with thermoplastic polyesters. Therefore, the following problem exists: even when a melt-blended composition containing olefin polymers and thermoplastic polyesters is introduced into the cavity of a mold with a fine-structured pattern, and the mold is then cooled to solidify the composition, the phase separation of the olefin polymers and thermoplastic polyesters makes it difficult for the mold cavity to seal tightly with the composition, resulting in poor transfer of the fine-structured pattern onto the molded article.

[0009] The present invention was made in view of the above-mentioned problems, and its object is to provide a composition in which the transferability of microstructure patterns is excellent even when thermoplastic polyester is incorporated therein.

[0010] means for solving problems

[0011] One aspect of the present invention is a composition comprising an olefin polymer A and a polymer B, wherein,

[0012] The polymer B is a poly(3-hydroxyalkanoate) polymer with a melting point above 150°C, and

[0013] Relative to a total of 100 parts by mass of polymer A and polymer B, the content of polymer A is 51 to 99.9 parts by mass, and the content of polymer B is 0.1 to 49 parts by mass.

[0014] Here, relative to a total of 100 parts by mass of polymer A and polymer B, the content of polymer A can be 60.1 parts by mass to 99.9 parts by mass, and the content of polymer B can be 0.1 parts by mass to 39.9 parts by mass.

[0015] In addition, polymer A can be a propylene polymer.

[0016] Invention Effects

[0017] According to the present invention, a composition is provided that exhibits excellent transferability of microstructure patterns while incorporating thermoplastic polyester as the main component. Detailed Implementation

[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] The composition of the present invention comprises olefin polymer A and polymer B.

[0020] <Olefin Polymer A>

[0021] Olefin polymer A refers to a polymer containing more than 50% by mass of structural units derived from olefins having 2 or more but less than 10 carbon atoms (wherein, the total amount of olefin polymers is set to 100% by mass). Examples of olefins having 2 or more but less than 10 carbon atoms are ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and 1-decene.

[0022] Olefin polymer A may contain structural units derived from monomers other than olefins having 2 or more but less than 10 carbon atoms. Examples of monomers other than olefins having 2 or more but less than 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-ethimide-2-norbornene.

[0023] Olefin polymer A can be at least one selected from the group consisting of ethylene polymers, propylene polymers and butene polymers, or any combination of two or more of them.

[0024] Ethylene polymers are polymers containing 50% or more structural units derived from ethylene. Examples include ethylene homopolymers, ethylene-1-butene copolymers, ethylene-1-hexene copolymers, ethylene-1-octene copolymers, and ethylene-1-butene-1-hexene copolymers. Ethylene polymers can be combinations of two or more ethylene polymers.

[0025] Propylene polymers refer to polymers containing 50% by mass or more structural units derived from propylene. Examples include: propylene homopolymers, propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-1-hexene copolymers, propylene-1-octene copolymers, propylene-ethylene-1-butene copolymers, propylene-ethylene-1-hexene copolymers, and propylene-ethylene-1-octene copolymers. Propylene polymers can be combinations of two or more propylene polymers. Olefin polymer A is preferably a propylene polymer.

[0026] Butene polymers refer to polymers containing more than 50% by mass of structural units derived from 1-butene. Examples include: 1-butene homopolymers, 1-butene-ethylene copolymers, 1-butene-propylene copolymers, 1-butene-1-hexene copolymers, 1-butene-1-octene copolymers, 1-butene-ethylene-propylene copolymers, 1-butene-ethylene-1-hexene copolymers, 1-butene-ethylene-1-octene copolymers, 1-butene-propylene-1-hexene copolymers, and 1-butene-propylene-1-octene copolymers. Butene polymers can be combinations of two or more butene polymers.

[0027] The aforementioned olefin polymer A can be manufactured using a known polymerization method employing a known polymerization catalyst.

[0028] The melt mass flow rate (MFR) of olefin polymer A, as determined 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.

[0029] <Polymer B>

[0030] Polymer B is a poly(3-hydroxyalkanoate) polymer with a melting point above 150°C.

[0031] Poly(3-hydroxyalkanoate) polymers refer to polyesters of polyhydroxyalkanoates, i.e., hydroxyalkanoic acids, and must contain repeating units of 3-hydroxyalkanoates represented by formula (1). In formula (1), R is a hydrogen atom, a halogen atom, an alkyl group with 1 to 15 carbon atoms, a cyano group, an amino group with 1 to 11 carbon atoms, an alkoxy group with 1 to 11 carbon atoms (alkyloxy group), an amide group with 2 to 20 carbon atoms, an aryl group with 6 to 12 carbon atoms, or a monovalent heterocyclic group with 1 to 9 carbon atoms. These groups may have substituents. In particular, from the viewpoint of compatibility with components other than polymer B contained in the composition (e.g., polymer A), R is preferably an alkyl group with 1 to 8 carbon atoms, an amide group with 2 to 20 carbon atoms, or an aryl group with 6 to 8 carbon atoms.

[0032] [-O-CHR-CH2-CO-]……(1)

[0033] Examples of halogen atoms are F, Cl, Br and I.

[0034] Alkyl groups having 1 to 15 carbon atoms can be straight-chain or branched. The preferred number of carbon atoms in an alkyl group is 1 to 8, more preferably 1 to 4. Examples of alkyl groups include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, 2-methylbutyl, 1-methylbutyl, hexyl, isohexyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, heptyl, octyl, isooctyl, 2-ethylhexyl, 3,7-dimethyloctyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, and pentadecyl.

[0035] Examples of amino groups with 1 to 11 carbon atoms include: amino, alkylamino, dialkylamino, arylamino, alkylarylamino, benzylamino, and dibenzylamino.

[0036] Examples of alkylamino groups include: methylamino, ethylamino, propylamino, butylamino, pentylamino, hexylamino, heptaylamino, octylamino, nonylamino, decylamino, dodecylamino, isopropylamino, isobutylamino, isopentylamino, sec-butylamino, tert-butylamino, sec-pentylamino, tert-pentylamino, tert-octylamino, neopentylamino, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cycloheptylamino, cyclooctylamino, 1-adamantylamino, and 2-adamantylamino.

[0037] Examples of dialkylamino compounds include: dimethylamino, diethylamino, dipropylamino, dibutylamino, dipentylamino, diisopropylamino, diisobutylamino, diisopentylamino, methylethylamino, methylpropylamino, methylbutylamino, methylisobutylamino, dicyclopropylamino, pyrrolyl, piperidinyl, and piperazine.

[0038] Examples of aryl amino groups include: aniline, 1-naphthylamino, 2-naphthylamino, o-toluidine, m-toluidine, p-toluidine, 1-fluorenamino, 2-fluorenamino, 2-thiazolamino, and p-terphenylamino.

[0039] The alkylaryl amino groups are N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline, N-isopropylaniline, and N-pentylaniline.

[0040] Examples of alkoxy groups with 1 to 11 carbon atoms include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, cyclopropoxy, cyclobutoxy, and cyclopentoxy.

[0041] An "amide group" refers to the group remaining after removing one hydrogen atom bonded to a nitrogen atom from a carboxylic amide. Examples of amide groups with 2 to 20 carbon atoms include: formamido, acetamido, propionamido, butyramido, benzamide, trifluoroacetamido, pentafluorobenzamide, etc., derived from -NH-C(=O)-R. A The group represented (where R) A (A hydrogen atom or a monovalent organic group); and like diformamido, diacetamido, dipropionamido, dibutamido, dibenzoamide, di(trifluoroacetyl)amine, and di(pentafluorobenzoyl)amine, it is composed of -N(-C(=O)-R A (-C(=O)-R) B The group represented by ) (where R A R B Each group can be an independent hydrogen atom or a monovalent organic group. The organic group can be an alkyl group that can be substituted with a halogen atom, an alkoxy group that can be substituted with a halogen atom, or an aryl group that can be substituted with a halogen atom. Among them, the amide group is preferably formamido, acetamido, propionamido, butyamido, or benzamide.

[0042] Examples of aryl groups having 6 to 12 carbon atoms include phenyl, tolyl, xylyl, naphthyl, and biphenyl, with phenyl, tolyl, and xylyl being more preferred.

[0043] Examples of heteroatoms in monovalent heterocyclic groups with 1 to 9 carbon atoms include N, O, and S. These groups can be saturated or unsaturated, and can contain one or more heteroatoms of different types. Examples of such heterocyclic groups include: thiophene, pyrrole, furanyl, pyridinyl, piperidinyl, quinolinyl, isoquinolinyl, pyrimidinyl, triazine, and thiazolyl.

[0044] The repeating unit of polymer B may contain only one or more 3-hydroxyalkanoates represented by formula (1), or it may have one or more 3-hydroxyalkanoates represented by formula (1) and one or more other hydroxyalkanoates.

[0045] Relative to all repeating units (100 mol%) of the hydroxyalkanoate, polymer B preferably contains more than 50 mol% of repeating units of the 3-hydroxyalkanoate represented by formula (1), and more preferably contains more than 70 mol% of repeating units of the 3-hydroxyalkanoate represented by formula (1).

[0046] Examples of 3-hydroxyalkanoates represented by formula (1) are: R is a hydrogen atom or is composed of C n H 2n+1 The alkyl group represents the 3-hydroxybutyrate (hereinafter sometimes referred to as 3HB) where n is an integer from 1 to 15, n=1, n=2, n=2, n=3, n=3, n=3, n=5, n=15, and R is a hydrogen atom in the 3-hydroxypropionate.

[0047] An example of polymer B having only one repeating unit represented by formula (1) is poly(3-hydroxybutyrate) (hereinafter sometimes referred to as P3HB).

[0048] Examples of polymers B that have only multiple 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).

[0049] Examples of other hydroxyalkanoates besides the 3-hydroxyalkanoate represented by formula (1) are repeating units represented by formula (2) (in formula (2), R 1 It is a hydrogen atom or composed of C n H 2n+1 The alkyl group is represented by n, which is an integer from 1 to 15, and m is an integer from 2 to 10.

[0050] [-O-CHR 1 -C m H 2m+1 -CO-]……(2)

[0051] Examples of polymers B containing repeating units of formula (1) and formula (2) are poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (e.g., formula (P3HB4HB)).

[0052] From the viewpoint of increasing the melting point, in the 3-hydroxyalkanoate represented by formula (1), the repeating unit of polymer B preferably contains at least 3-hydroxybutyrate.

[0053] Relative to all repeating units (100 mol%) of hydroxyalkanoate, polymer B preferably contains more than 50 mol% of repeating units of 3-hydroxybutyrate, more preferably more than 70 mol% of repeating units of 3-hydroxybutyrate.

[0054] Polymer B may have two or more repeating units of esters, for example, it may be a binary polymer with two repeating units, a ternary copolymer with three repeating units, or a quaternary copolymer with four repeating units as described above.

[0055] For example, an example of a terpolymer is poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate) (hereinafter, sometimes referred to as (P3HB3HV3HH)).

[0056] As described above, in the repeating unit of the 3-hydroxyalkanoate represented by formula (1), polymer B preferably contains 3-hydroxybutyrate. The ratio XX of the repeating unit of 3-hydroxybutyrate relative to 100 mol% of the ester repeating unit of all hydroxyalkanoates is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 98.0 mol% or more.

[0057] The ratio XX is typically 100 mol% or less, preferably 99.9 mol% or less, and more preferably 99.8 mol% or less.

[0058] The arrangement of copolymers can be any of the following: random copolymers, alternating copolymers, block copolymers, graft copolymers, etc.

[0059] Polymer B may have other ester repeating units besides those in formulas (1) and (2), but the main chain of such other ester repeating units does not contain an aromatic hydrocarbon structure. That is, polymer B is an aliphatic polyester. However, groups with aromatic hydrocarbon groups may be bonded to the carbon atoms of the main chain of such other ester repeating units.

[0060] As described in L. Tripathi., MC Factories, 11, 44 (2012), the composition ratio of repeating units in polymer B can be calculated from NMR measurements such as 1H-NMR and 13C-NMR.

[0061] In addition, polymer B can be a blend of two or more poly(3-hydroxyalkanoate) polymers.

[0062] The weight-average molecular weight (Mw) of polymer B 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, molded articles with excellent impact strength and tensile elongation can be obtained. Furthermore, by setting the weight-average molecular weight to 500,000 or less, polymer B exhibits good dispersibility in olefin polymer A. The weight-average molecular weight can be 400,000 or less, 300,000 or less, 200,000 or less, or 100,000 or less. It should be noted that in this specification, the weight-average molecular weight (Mw) is determined by GPC using standard polystyrene as the molecular weight standard.

[0063] Polymer B is a thermoplastic resin, preferably crystalline.

[0064] The melt mass flow rate (MFR(B)) of polymer B, as determined 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) can 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) can be 150 g / 10 min or less, or 100 g / 10 min or less.

[0065] The melting point (Tm) of polymer B is above 150°C, and can be above 155°C, 160°C, 165°C, 170°C, or 175°C. The melting point (Tm) of polymer B can be below 220°C, and can be below 200°C or below 190°C.

[0066] The melting point (Tm) of polymer B was determined by measuring the position of the main peak of crystal melting using a differential scanning calorimeter (DSC) according to JIS K7121.

[0067] Poly(3-hydroxyalkanoates) polymers can be produced by microorganisms or derived from compounds derived from petroleum or plant feedstocks (such as cyclic lactones).

[0068] Poly(3-hydroxyalkanoate) polymers can be like polymers produced by microorganisms, where each repeating unit of the hydroxyalkanoate contains only D-type (R-type), or like polymers derived from a mixture of D-type (R-type) and L-type (S-type), where the repeating units of the hydroxyalkanoate contain both D-type (R-type) and L-type (S-type).

[0069] In poly(3-hydroxyalkanoate) polymers produced by microorganisms, the repeating unit of formula (1) can be as shown in the following formula. In formula (BI-1), n ​​represents the degree of polymerization.

[0070]

[0071] Furthermore, poly-(3-hydroxybutyrate), for example, produced by microorganisms, has the structure shown below. In formula (BI-2), n represents the degree of polymerization.

[0072]

[0073] Furthermore, the poly-(3-hydroxybutyrate-co-3-hydroxyhexanoate) produced by microorganisms has the structure shown below. In formula (BI-3), m and n represent the degree of polymerization.

[0074]

[0075] Furthermore, the poly-(3-hydroxybutyrate-co-4-hydroxybutyrate) produced by microorganisms has the structure shown below. In formula (BI-4), m and n represent the degree of polymerization.

[0076]

[0077] Polymer B is biodegradable.

[0078] For example, poly(3-hydroxyalkanoate) polymers can be produced by introducing the PHA synthase gene from Aeromonascaviae into Alcaligenes eutrophus, resulting in Alcaligenes eutrophus strain AC32 (international deposit based on the Budapest Treaty, international depositary institution: National Institute of Advanced Industrial Science and Technology (IAIST) Patent Biological Collection Center (1-1 Higashi, Tsukuba City, Ibaraki Prefecture, Japan, Central No. 6), original deposit date: August 12, 2008, transferred on August 7, 2009, depositary number FERMBP-6038 (transferred from the original deposit FERMBP-15786)) (J. Bacteriol., 179, 4821 (1997)).

[0079] <Composition of the Composition>

[0080] In the composition, relative to a total of 100 parts by mass of olefin polymer A and polymer B, the content of olefin polymer A is 51 parts by mass to 99.9 parts by mass, and the content of polymer B is 0.1 parts by mass to 49 parts by mass.

[0081] The content of olefin polymer A can be 60.1 parts by mass to 99.9 parts by mass and the content of polymer B can be 0.1 parts by mass to 39.9 parts by mass; the content of olefin polymer A can be 70 parts by mass to 99.9 parts by mass and the content of polymer B can be 0.1 parts by mass to 30 parts by mass; the content of olefin polymer A can be 75 parts by mass to 99.9 parts by mass and the content of polymer B can be 0.1 parts by mass to 25 parts by mass. When the content of polymer B is too high, sometimes the transferability of the mold's surface and the demolding properties from the mold's surface decrease.

[0082] Furthermore, from the viewpoint of forming a eutectic of polymer A and polymer B and exhibiting a crystallization delay effect of the composition, the content of olefin polymer A can be 60 parts by mass to 99.9 parts by mass and the content of polymer B can be 0.1 parts by mass to 40 parts by mass; the content of olefin polymer A can be 70 parts by mass to 99.9 parts by mass and the content of polymer B can be 0.1 parts by mass to 30 parts by mass; and the content of olefin polymer A can be 80 parts by mass to 99.9 parts by mass and the content of polymer B can be 0.1 parts by mass to 20 parts by mass.

[0083] The content of olefin polymer A can be 80 parts by mass to 99.9 parts by mass and the content of polymer B can be 0.1 parts by mass to 20 parts by mass; the content of olefin polymer A can be 85 parts by mass to 99.9 parts by mass and the content of polymer B can be 0.1 parts by mass to 15 parts by mass; the content of olefin polymer A can be 90 parts by mass to 99.9 parts by mass and the content of polymer B can be 0.1 parts by mass to 10 parts by mass.

[0084] The total percentage of olefin polymer A and polymer B in the overall composition can be 50% by mass or more, preferably 60% by mass or more, and more preferably 70% by mass or more.

[0085] In the composition, polymer B may or may not form a dispersed phase. When polymer B forms a dispersed phase, it means the composition has an island structure, where olefin polymer A is the continuous phase (sea) and polymer B is the dispersed phase (island). The average equivalent circle diameter of the dispersed phase (island) can range from 10 nm to 400 μm.

[0086] (additive)

[0087] The composition may include additives as needed. As additives, they may be at least one selected from the group consisting of stabilizers, antibacterial agents, antifungal agents, dispersants, plasticizers, flame retardants, thickeners, colorants, metal powders, organic powders, inorganic fibers, organic fibers, organic and inorganic composite fibers, inorganic whiskers, and fillers.

[0088] Examples of stabilizers are at least one selected from the group consisting of lubricants, anti-aging agents, heat stabilizers, light stabilizers, weather stabilizers, metal passivators, ultraviolet absorbers, light stabilizers, and copper inhibitors. Examples of light stabilizers are hindered amine light stabilizers.

[0089] Examples of colorants are at least one selected from the group consisting of titanium dioxide, carbon black, and organic pigments. Examples of metal powders are ferrite.

[0090] Examples of organic powders include proteins. Examples of inorganic fibers include glass fibers, metal fibers, and carbon fibers. An example of an organic fiber is aramid fiber. An example of inorganic whiskers is potassium titanate whiskers.

[0091] Examples of fillers include at least one from the group consisting of glass beads, hollow glass microspheres, flake glass, asbestos, mica, calcium carbonate, talc, silica, calcium silicate, hydrotalcite, kaolin, diatomaceous earth, graphite, pumice, hard adhesive powder, cotton scraps, cork powder, barium sulfate, fluorinated resin, cellulose powder, and wood flour.

[0092] The composition may contain only one of the above-mentioned additives, or it may contain a combination of two or more of them.

[0093] In the composition, the additive can be included in either olefin polymer A or polymer B. The additive can form a dispersed phase different from polymer B in the continuous phase of olefin polymer A.

[0094] The curve of the loss modulus E” of the composition relative to temperature obtained by dynamic mechanical analysis (DMA) can have multiple peaks (e.g., bimodal), but preferably one peak (single peak).

[0095] The DMA method can be performed as follows: For a test sample cut into strips with a thickness of 0.3 mm, in tensile testing mode at a testing frequency of 5 Hz, the temperature is gradually increased from the testing temperature of -150 °C at a rate of 2 °C / min until the sample melts and cannot be measured. This is performed within a strain range of less than 0.1%.

[0096] When there is only one peak in the curve, the temperature of that peak corresponds to the glass transition temperature Tg. The glass transition temperature Tg of the composition can be -70℃ to 150℃.

[0097] The composition can have a eutectic of olefin polymer A and polymer B. The presence or absence of the eutectic can be confirmed by the presence or absence of peaks in X-ray diffraction results that differ from the peaks of the single crystals of the constituent components. For example, in the case of a mixture of polypropylene and poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (P3HB3HH), the peaks of the single crystal of polypropylene appear at 2θ = about 14°, about 17°, and about 18.5°, the peaks of P3HB3HH appear at 2θ = about 13.5° and about 17°, and the peak of the eutectic appears at about 16°. For the single crystal peaks of polypropylene, refer to J. Polymer Sci. B. Polymer Physics Vol. 24, 461-491 (1986).

[0098] The eutectic ratio (the volume fraction of eutectic structure in the entire structure) in the composition can be 0.1% or higher. The eutectic ratio can be calculated as the ratio of the total area of ​​the peaks of the single crystal and the eutectic peaks relative to the total area of ​​the eutectic peaks of the olefin polymer A.

[0099] For example, for a mixture of polypropylene and P3HB3HH, the eutectic rate can be calculated as follows. First, the two-dimensional X-ray diffraction pattern of the composition is evaluated, and the resulting two-dimensional X-ray diffraction pattern is transformed into a diffraction angle-intensity distribution by circumferential averaging relative to all omnidirectional angles. Then, the eutectic rate can be calculated based on the ratio of the area of ​​the peak at 2θ = 16° to the total area of ​​the peaks attributed to the single crystals of polypropylene and the peaks at 2θ = 16°.

[0100] When the composition has a eutectic structure, the crystallization rate of the composition is delayed. Compositions with a slow crystallization rate are useful in aspects such as the transferability of fine-structure patterns.

[0101] (Method for manufacturing the composition)

[0102] The above composition can be obtained by melt-blending olefin polymer A, polymer B, and additives as needed. The blending temperature (set temperature of the mixer) is preferably set to 150°C to 300°C, more preferably to 170°C to 280°C. Alternatively, a portion of each of olefin polymer A and polymer B can be melt-blended to obtain a premix, and then the remaining portions of olefin polymer A and polymer B can be added to the premix and further melt-blended to obtain the composition.

[0103] (Method for manufacturing the molded part of the composition)

[0104] Molded bodies of the above-mentioned compositions having the desired shape can be obtained using known resin molding methods such as injection molding, extrusion molding, vacuum molding, compressed air molding, compression molding, foam molding, blow molding, and rotational molding.

[0105] In addition, the above composition can be bonded with other materials such as resins, metals, paper, and leather to obtain a multilayer structure.

[0106] Surface treatment can be applied to the surface of the molded article of the composition of the present invention. Examples of surface treatment methods include: embossing, corona discharge, flame treatment, plasma treatment, ozone treatment, etc.

[0107] The above composition can be widely used as a resin material.

[0108] Examples of uses for the compositions of this invention include: external structural components, furniture and interior decoration components, house components, toy components, gardening components, automotive components, and packaging materials. Examples of external structural components include: carport components, fence components, door components, gatepost components, pillar components, bicycle garage components, deck components, sunroom components, roof components, balcony components, handrail components, sun visor components, awning components, etc.; examples of furniture and interior decoration components include: sofa components, table components, chair components, bed components, wardrobe components, cabinet components, dressing table components, etc.; examples of household appliance components include: watch components, mobile phone components, white goods components, etc.; examples of toy components include: plastic model components, see-through mirror components, main body components of video game consoles, etc.; examples of gardening components include: seeding mechanism components, vase components, flowerpot components, etc.; examples of automotive components include: bumper materials, dashboard materials, airbag cover materials, etc.; examples of packaging materials include: food packaging materials, fiber packaging materials, grocery packaging materials, etc. In addition, other uses include, for example: components for monitors, components for office automation (OA) equipment, medical components, drain trays, components for toiletries, bottles, containers, components for snow removal products, and various building components.

[0109] Example

[0110] The present invention will now be described using examples and comparative examples. The olefin polymer (A) and thermoplastic ester polymer (B) used in the examples and comparative examples are shown below.

[0111] (1) Olefin polymer A

[0112] (A-1) Propylene homopolymer

[0113] MFR (230℃, 2.16kgf load): 7g / 10 minutes

[0114] Melting point (Tm): 163℃

[0115] (A-2) Ethylene homopolymer (high-density polyethylene)

[0116] (Product Name) KEIYO polyethylene G2500: Manufactured by KEIYO Polyethylene Co., Ltd.

[0117] MFR (190℃, 2.16kgf load): 5.4g / 10min

[0118] Melting point (Tm): 131℃

[0119] (2) Polymer B

[0120] (B-1) Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)

[0121] Structural formula: Formula (BI-3)

[0122] Comonomer (3HH) content (mol%): 1.1 mol%.

[0123] Weight-average molecular weight (Mw): 79,000

[0124] MFR (190℃, 2.16kgf load): 38g / 10 minutes

[0125] Melting point (Tm): 175℃

[0126] (B-2) Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)

[0127] Structural formula: Formula (BI-3)

[0128] Comonomer (3HH) content (mol%): 0.2 mol%.

[0129] Weight-average molecular weight (Mw): 104,000

[0130] MFR (190℃, 2.16kgf load): 7.8g / 10min

[0131] Melting point (Tm): 175℃

[0132] (B-3) Poly(3-hydroxybutyrate-co-4-hydroxybutyrate)

[0133] Structural formula: Formula (BI-4)

[0134] (Product Name) M4300: Manufactured by CJ Daiichi Seisakusho Co., Ltd. Content (mol%) of comonomer (3HH): 45 mol%.

[0135] Weight-average molecular weight (Mw): 216,000

[0136] MFR (190℃, 2.16kgf load): 4.0g / 10min

[0137] Melting point (Tm): 48.7℃

[0138] (B-4) Polyethylene terephthalate (trade name) Bellpet EFG70: Manufactured by Bell Polyester Products. Intrinsic viscosity: 0.75 dl / g

[0139] Melting point (Tm): 255℃

[0140] (B-5) Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)

[0141] Structural formula: Formula (BI-3)

[0142] Comonomer (3HH) content (mol%): 20 mol%.

[0143] MFR (170℃, 2.16kgf load): 38g / 10 minutes

[0144] Melting point (Tm): 74℃

[0145] (B-6) Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)

[0146] Structural formula: Formula (BI-3)

[0147] Comonomer (3HH) content (mol%): 12 mol%.

[0148] Weight-average molecular weight (Mw): 850,000

[0149] MFR (190℃, 2.16kgf load): 3.5g / 10min

[0150] Melting point (Tm): 129℃

[0151] (B-7) Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)

[0152] Structural formula: Formula (BI-3)

[0153] Comonomer (3HH) content (mol%): 8.5 mol%.

[0154] Weight-average molecular weight (Mw): 850,000

[0155] MFR (190℃, 2.16kgf load): 3.7g / 10min

[0156] Melting point (Tm): 148℃

[0157] The physical properties of each polymer and composition were determined according to the methods shown below.

[0158] (1) Melt mass flow rate (MFR, unit: g / 10 min)

[0159] The determination was performed according to the method specified in JIS K7210-2014. The measurement temperature was set to 230°C or 190°C, and the load was set to 2.16 kgf.

[0160] (2) Weight-average molecular weight (Mw)

[0161] The weight-average molecular weight (Mw) was calculated based on the results of gel permeation chromatography (GPC). In the GPC determination, a Waters GPC-150C was used as the measuring apparatus, a 0.05% by weight o-dichlorobenzene solution was used, a mixed polystyrene gel column (PSKgelGMH6-HT manufactured by Tosoh Corporation) was used, and the measurement temperature was set to 135°C.

[0162] (3) Melting point (Tm) of the polymer

[0163] The determination shall be performed according to the method specified in JIS K7121. The determination shall be performed at a temperature of -50℃ to 200℃ or -50℃ to 250℃ and a heating rate of 10℃ / min.

[0164] (4) Content of comonomer components in polymer B

[0165] The content of the comonomer component is the molar ratio of the number of repeating units other than 3-hydroxybutyrate (3-hydroxyhexanoate (3HH) or 4-hydroxybutyrate (4HB)) to the total number of repeating ester units of the hydroxyalkanoate of polymer B.

[0166] The content of the comonomer component was determined by the method using 1H-NMR spectroscopy described in L. Tripathi., MC Factories, 11, 44 (2012).

[0167] [Measurement Conditions]

[0168] Model: Bruker AVANCE600

[0169] Probe: 10mm cryoprobe

[0170] Measurement temperature: 135℃

[0171] Pulse repetition time: 1 second

[0172] Pulse width: 45°

[0173] Total number of times: 700

[0174] Magnetic field strength: 600MHz

[0175] (5) Determination of the Tg of the composition

[0176] Temperature-storage modulus curves of the composition were obtained using a viscoelastic apparatus (SII Nanotechnology; DMS200), and the number of peaks was counted.

[0177] (6) Transferability of microstructure patterns

[0178] Using a compression molding machine (P-37) from Shindo Metal Industries, resin was preheated at 200°C for 5 minutes on an embossing plate with a fine-structured pattern and a surface roughness (Ra) of 60 μm. The resin was then pressed onto the embossing plate at 200°C and a pressure of 1 MPa for 30 seconds to obtain a shaped molded body. The surface roughness of the shaped molded body was evaluated. A surface roughness closer to 60 μm indicates higher transferability of the fine-structured pattern.

[0179] (7) Surface roughness (Ra)

[0180] The surface roughness was measured using a Surfcoder SE-30K three-dimensional surface roughness measuring instrument (manufactured by Kosaka Labs Co., Ltd.). The roughness was measured along the X direction at a speed of 0.5 mm / s, covering an area of ​​2 mm in the X direction and 0.99 mm in the Y direction (with a spacing of 2 μm in the Y direction). The arithmetic mean surface roughness (Ra) was calculated based on the measurement results.

[0181] (8) Demolding properties

[0182] Using a compression molding machine (P-37) from Shindo Metal Industries, resin was preheated at 200°C for 5 minutes on an embossed plate with a fine-structured pattern and a surface roughness (Ra) of 60 μm. The resin was then pressed onto the embossed plate at 200°C and a pressure of 1 MPa for 30 seconds to obtain a shaped molded body. When the shaped molded body was peeled off the embossed plate at a 45° angle, a rating of × was given if the molded body broke, and a rating of ○ was given if the molded body did not break.

[0183] (9) Eutectic

[0184] The two-dimensional X-ray diffraction pattern of the composition was evaluated by circumferentially averaging the obtained two-dimensional X-ray diffraction pattern relative to all omnidirectional angles to transform it into a diffraction angle-intensity distribution. The presence or absence of peaks corresponding to the diffraction based on the eutectic (2θ = 16°) confirmed the presence of a eutectic. Furthermore, the eutectic ratio was calculated based on the area of ​​the eutectic peaks and the peaks of the polypropylene single crystal. Specifically, the eutectic ratio was calculated by peak fitting of the two-dimensional X-ray diffraction pattern, calculating the area values, and then calculating the eutectic ratio according to the following formula.

[0185] Eutectic ratio = 16° peak area / (14° peak area + 17° peak area + 18.5° peak area + 16° peak area)

[0186] (10) Crystallization rate

[0187] The composition was rapidly cooled from 190°C to 125°C, and then differential scanning calorimetry was performed while maintaining the temperature, and the crystallization rate (half-crystallization time t1 / 2) was determined.

[0188] The properties of polymer A and polymer B are shown in Table 1 and Table 2, respectively.

[0189] [Table 1]

[0190]

[0191] [Table 2]

[0192]

[0193] (Example 1)

[0194] 95.8% by weight of polymer (A-1) and 4.2% by weight of polymer (B-1) were uniformly mixed in powder form and then fed into a small mixer (Xplore; manufactured by DSM) and mixed at a resin temperature of 190°C, a mixing time of 4 minutes, and a screw rotation speed of 100 rpm to obtain a resin composition. The microstructure pattern transferability of the resin composition was evaluated.

[0195] (Example 2)

[0196] The procedure was carried out in the same manner as in Example 1, except that 95% by mass of polymer (A-1) and 5% by mass of polymer (B-2) were used.

[0197] (Example 3)

[0198] The procedure was carried out in the same manner as in Example 1, except that 90% by mass of polymer (A-1) and 10% by mass of polymer (B-2) were used.

[0199] (Example 4)

[0200] The procedure was carried out in the same manner as in Example 1, except that 90% by mass of polymer (A-2) and 10% by mass of polymer (B-1) were used.

[0201] (Example 5)

[0202] The procedure was carried out in the same manner as in Example 1, except that 65.2% by mass of polymer (A-1) and 34.8% by mass of polymer (B-1) were used.

[0203] (Comparative Example 1)

[0204] The procedure was carried out in the same manner as in Example 1, except that only 100% by mass of the polymer (A-1) was used.

[0205] (Comparative Example 2)

[0206] The procedure was carried out in the same manner as in Example 1, except that 47.8% by mass of polymer (A-1) and 52.2% by mass of polymer (B-1) were used.

[0207] (Comparative Example 3)

[0208] The procedure was carried out in the same manner as in Example 1, except that 90% by mass of polymer (A-1) and 10% by mass of polymer (B-3) were used.

[0209] (Comparative Example 4)

[0210] The procedure was carried out in the same manner as in Example 1, except that 95% by mass of polymer (A-1) and 5% by mass of polymer (B-5) were used.

[0211] (Comparative Example 5)

[0212] The procedure was carried out in the same manner as in Example 1, except that 95% by mass of polymer (A-1) and 5% by mass of polymer (B-6) were used.

[0213] (Comparative Example 6)

[0214] The procedure was carried out in the same manner as in Example 1, except that 95% by mass of polymer (A-1) and 5% by mass of polymer (B-4) were used.

[0215] The results are shown in Table 3.

[0216]

[0217] It was confirmed that by incorporating a suitable amount of olefin polymer into a high-melting-point poly(3-hydroxyalkanoate) polymer, the transferability improved even with the addition of thermoplastic polyester. Furthermore, in Examples 1-3, a delay in crystallization rate was also observed.

Claims

1. A composition comprising an olefin polymer A and a polymer B, wherein, The polymer B is a poly(3-hydroxyalkanoate) polymer with a melting point above 150°C, and Relative to a total of 100 parts by weight of polymer A and polymer B, the content of polymer A is 90 parts by weight to 99.9 parts by weight, and the content of polymer B is 0.1 parts by weight to 10 parts by weight. Polymer A is a propylene polymer. The repeating units of polymer B contain at least 3-hydroxybutyrate.

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