Composition

Abstract

To provide a composition that has excellent transferability of a microstructure pattern even when comprising a thermoplastic polyester.SOLUTION: A composition includes an olefin polymer A and a polymer B. The polymer B is a poly(3-hydroxyalkanoate) polymer with a melting point of 150°C or more, and the content of the polymer A is 51-99.9 pts.mass and the content of the polymer B is 0.1-49 pts.mass relative to a total of 100 pts.mass of the polymer A and the polymer B.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a composition. [Background technology]

[0002] Olefin polymers are inexpensive and lightweight thermoplastic resins that also possess excellent properties such as moldability, mechanical properties, heat resistance, and resistance to long-term heat degradation. For this reason, olefin polymers are used in 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 components, and building materials such as interior materials for buildings and houses. In recent years, there has been a growing demand for improvements in airtightness, paintability, and dyeability of these materials.

[0003] Therefore, as one means of meeting these requirements, a method can be considered in which thermoplastic polyesters, such as polyethylene terephthalate and polybutylene terephthalate, which have superior airtightness, paintability, and dyeability compared to olefin polymers, are blended with olefin polymers, as described in Patent Document 1. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 6-73264 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, olefin polymers and thermoplastic polyesters have poor compatibility. Therefore, even when a melt-kneaded composition containing an olefin polymer and a thermoplastic polyester is introduced into the cavity of a mold having a microstructure pattern, and the mold is cooled to solidify the composition, the phase separation of the olefin polymer and the thermoplastic polyester makes it difficult for the mold cavity and the composition to adhere properly, resulting in a problem of degraded transferability of the microstructure pattern to the molded article.

[0006] The present invention has been made in view of the above problems, and aims to provide a composition that exhibits excellent transferability of microstructure patterns even when thermoplastic polyester is incorporated. [Means for solving the problem]

[0007] One aspect of the present invention is a composition comprising olefin polymer A and polymer B, The polymer B is a poly(3-hydroxyalkanoate) polymer having a melting point of 150°C or higher. With respect 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.

[0008] Here, with respect to a total of 100 parts by mass of polymer A and polymer B, the content of polymer A can be 60.1 to 99.9 parts by mass, and the content of polymer B can be 0.1 to 39.9 parts by mass.

[0009] Furthermore, the polymer A can be a propylene copolymer. [Effects of the Invention]

[0010] According to the present invention, a composition is provided that has excellent transferability of microstructure patterns while being formulated with thermoplastic polyester as the main component. [Modes for carrying out the invention]

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

[0012] The composition according to the present invention comprises an olefin polymer A and a polymer B.

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

[0014] 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 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 unconjugated 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 of these.

[0016] An ethylene-based copolymer is a polymer containing 50% by mass or more of structural units derived from ethylene. Examples thereof include an ethylene homopolymer, an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, an ethylene-1-octene copolymer, and an ethylene-1-butene-1-hexene copolymer. The ethylene-based copolymer may be a combination of two or more ethylene-based 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 preferred that the olefin-based 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-formed 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 above olefin-based polymer A can be produced using a known polymerization method with a known polymerization catalyst.

[0020] ]The melt mass flow rate (MFR) of olefin polymer A, measured under conditions of a temperature of 230°C or 190°C and a load of 2.16 kgf in accordance with JIS K7210-2014, is preferably 0.1 g / 10 min or more and 200 g / 10 min or less.

[0021] <Polymer B> Polymer B is a poly(3-hydroxyalkanoate) polymer with a melting point of 150°C or higher.

[0022] A poly(3-hydroxyalkanoate) polymer is a polyester of polyhydroxyalkanoate, i.e., hydroxyalkanoic acid, and must contain repeating units of 3-hydroxyalkanete 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 included in the composition (e.g., 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. [-O-CHR-CH2-CO-]…(1)

[0023] Examples of halogen atoms are F, Cl, Br, and I.

[0024] Alkyl groups 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 alkyl groups are 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.

[0025] Examples of amino groups with 1 to 11 carbon atoms include the amino group, alkylamino group, dialkylamino group, arylamino group, alkylarylamino group, benzylamino group, and dibenzylamino group. Examples of alkylamino groups 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, and 2-adamantamino group.

[0026] Examples of dialkylamino groups include dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, dicyclopropylamino group, pyrrolidino group, piperidino group, and piperazine group.

[0027] Examples of arylamino groups include anilino, 1-naphthylamino, 2-naphthylamino, o-toluidino, m-toluidino, p-toluidino, 1-fluoreneamino, 2-fluoreneamino, 2-thiazoleamino, and p-terphenylamino. Examples of alkylarylamino groups include N-methylanilino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropylanilino group, and N-pentylanilino group.

[0028] 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 groups.

[0029] An "amide group" refers to a group obtained by removing one hydrogen atom bonded to the nitrogen atom from a carboxylic acid amide. Examples of amide groups with 2 to 20 carbon atoms include formamide, acetamide, propionamide, butylamide, benzamide, trifluoroacetamide, and pentafluorobenzamide, all of which are -NH-C(=O)-R. A A group represented by (where R A (These are hydrogen atoms or monovalent organic groups), and -N(-C(=O)-R such as diformamide group, diacetamide group, dipropioamide group, dibutyroamide group, dibenzamide group, ditrifluoroacetamide group, and dipentafluorobenzamide group. A )(-C(=O)-R B ) represented by a group (however, R A 、 R B Each of these is independently a hydrogen atom or a monovalent organic group. The organic group can be an alkyl group, alkoxy group, or aryl group, which may be substituted with a halogen atom. Among these, the amide group is preferably formamide, acetamide, propionamide, butyroamide, or benzamide.

[0030] Examples of the aryl group having 6 to 12 carbon atoms include 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 more preferable.

[0031] 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.

[0032] The repeating unit of polymer B 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.

[0033] Polymer B preferably contains 50 mol% or more, more preferably 70 mol% or more, of the repeating unit of 3-hydroxylcanoate represented by formula (1) with respect to all the repeating units (100 mol%) of hydroxyalkanoate.

[0034] Examples of the 3-hydroxyalkanoate represented by formula (1) include 3-hydroxybutyrate (hereinafter sometimes referred to as 3HB) where R is a hydrogen atom or an alkyl group represented by C n H 2n+1 and n is an integer of 1 to 15, 3-hydroxyvalerate (hereinafter sometimes referred to as 3HV) where n = 2, 3-hydroxyhexanoate (hereinafter sometimes referred to as 3HH) where n = 3, 3-hydroxyoctanoate where n = 5, 3-hydroxyoctadecanoate where n = 15, and 3-hydroxypropionate where R is a hydrogen atom.

[0035] An example of polymer B having only one type of repeating unit represented by formula (1) is poly(3-hydroxybutyrate) (hereinafter sometimes referred to as P3HB).

[0036] Examples of polymer B having only the 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-hydroxyvalate) (hereinafter sometimes referred to as P3HB3HV), and poly(3-hydroxybutyrate-co-3-hydroxypropionate) (hereinafter sometimes referred to as P3HB3HP).

[0037] Examples of hydroxyalkanoates other than the 3-hydroxyalkanoate shown in (1) are shown in (2) the repeating unit (wherein R 1 is a hydrogen atom or C n H 2n+1 The alkyl group is represented as follows: n is an integer between 1 and 15, and m is an integer between 2 and 10. [-O-CHR 1 -C m H 2m+1 -CO-]…(2)

[0038] An example of polymer B containing repeating units of equations (1) and (2) is poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (e.g., the formula shown below (P3HB4HB)).

[0039] From the viewpoint of raising the melting point, it is preferable that the repeating units of polymer B contain at least 3-hydroxybutyrate among the 3-hydroxyalkanoates represented by formula (1).

[0040] Polymer B preferably contains 50 mol% or more of 3-hydroxybutyrate repeating units relative to the total repeating units of hydroxyalkanoate (100 mol%), and more preferably 70 mol% or more.

[0041] Polymer B may have two or more repeating ester units. For example, it may be a dipolymer having two repeating units as described above, a tri-copolymer having three repeating units, and a tetra-copolymer having four repeating units.

[0042] For example, an example of a tri-copolymer is poly(3-hydroxybutyrate-co-3-hydroxyvalate-co-3-hydroxyhexanoate) (hereinafter sometimes referred to as (P3HB3HV3HH)).

[0043] As described above, polymer B preferably contains 3-hydroxybutyrate among the repeating units of 3-hydroxyalkanoate represented by formula (1). The ratio XX of repeating units of 3-hydroxybutyrate to 100 moles of total hydroxyalkanoate ester repeating units is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 98.0 mol% or more.

[0044] The proportion XX is usually 100 mol% or less, preferably 99.9 mol% or less, and preferably 99.8 mol% or less.

[0045] The copolymer arrangement can be any of the following: random copolymer, alternating copolymer, block copolymer, graft copolymer, etc.

[0046] Polymer B may have other ester repeating units besides those of formulas (1) and (2), but the main chain of such other ester repeating units does not contain an aromatic hydrocarbon structure. In other words, polymer B is an aliphatic polyester. However, it is possible for a group having an aromatic hydrocarbon group to be bonded to the carbon of the main chain of such other ester repeating units.

[0047] The composition ratio of repeating units in polymer B can be calculated from NMR measurement results such as 1H-NMR and 13C-NMR, as described in L. Tripathi., MCFactories, 11, 44 (2012).

[0048] Furthermore, polymer B may be a blend of two or more poly(3-hydroxyalkanoate) polymers.

[0049] The weight-average molecular weight (Mw) of polymer B can be between 10,000 and 1,000,000, preferably between 20,000 and 800,000, and more preferably between 30,000 and 600,000. By setting the weight-average molecular weight (Mw) to 10,000 or more, it is possible to obtain a molded article with excellent impact strength and tensile elongation. Furthermore, by setting the weight-average molecular weight to 500,000 or less, good dispersibility in olefin polymer A is achieved. The weight-average molecular weight may also 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 the molecular weight standard.

[0050] Polymer B is a thermoplastic resin, and it is preferable that it is crystalline.

[0051] According to JIS K7210-2014, the melt mass flow rate (MFR(B)) of polymer B, measured 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. The MFR(B) may also 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. The MFR(B) may also be 150 g / 10 min or more, or 100 g / 10 min or more.

[0052] The melting point (Tm) of polymer B 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 may be 220°C or lower, and may be 200°C or lower, or 190°C or lower.

[0053] The melting point (Tm) of polymer B is determined by the position of the main peak based on the melting of the crystal, which is obtained by differential scanning calorimeter (DSC) measurement in accordance with JIS K7121.

[0054] The poly(3-hydroxyalkanoate) polymer may be produced by microorganisms or derived from compounds (such as cyclic lactones) derived from petroleum or plant materials.

[0055] Poly(3-hydroxyalkanoate) polymers may consist of only D-isomers (R-isomers) of each repeating unit of hydroxyalkanoate, as is the case with polymers produced from microorganisms, or they may contain both D-isomers (R-isomers) and L-isomers (S-isomers), as is the case with polymers derived from a mixture of D-isomers (R-isomers) and L-isomers (S-isomers).

[0056] In poly(3-hydroxyalkanoate) polymers produced from microorganisms, the repeating unit of equation (1) can be represented as shown in the following equation. In equation (BI-1), n ​​represents the degree of polymerization. [ka]

[0057] For example, poly-(3-hydroxybutyrate) produced from microorganisms has the following structure. (BI-2) In formula n, n represents the degree of polymerization. [ka]

[0058] Furthermore, poly-(3-hydroxybutyrate-co-3-hydroxyhexanoate) produced from microorganisms has the following structure. (BI-3) In formula m and n, m and n represent the degree of polymerization. [ka]

[0059] Furthermore, poly-(3-hydroxybutyrate-co-4-hydroxybutyrate) produced from microorganisms has the following structure. (BI-4) In formula m and n, m and n represent the degree of polymerization. [ka]

[0060] Polymer B may be biodegradable.

[0061] For example, poly(3-hydroxyalkanoate) polymers can be produced by microorganisms such as Alcaligenes eutrophus AC32 strain (international deposit under the Budapest Convention, international depositary authority: Patent Organism Depositary Center, National Institute of Advanced Industrial Science and Technology (1-1-1 Higashi, Tsukuba, 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)).

[0062] <Composition of the composition> In the composition, the content of olefin polymer A is 51 to 99.9 parts by mass and the content of polymer B is 0.1 to 49 parts by mass, based on a total of 100 parts by mass of olefin polymer A and polymer B.

[0063] The content of olefin polymer A can be 60.1 to 99.9 parts by mass and the content of polymer B can be 0.1 to 39.9 parts by mass; the content of olefin polymer A can be 70 to 99.9 parts by mass and the content of polymer B can be 0.1 to 30 parts by mass; and the content of olefin polymer A can be 75 to 99.9 parts by mass and the content of polymer B can be 0.1 to 25 parts by mass. If the content of polymer B is too high, the transferability of the mold's surface and the release properties from the mold's surface may decrease. Furthermore, from the viewpoint of forming cocrystals of polymer A and polymer B and exhibiting a crystallization delay effect in the composition, the content of olefin polymer A may be 60 to 99.9 parts by mass and polymer B may be 0.1 to 40 parts by mass, the content of olefin polymer A may be 70 to 99.9 parts by mass and polymer B may be 0.1 to 30 parts by mass, and the content of olefin polymer A may be 80 to 99.9 parts by mass and polymer B may be 0.1 to 20 parts by mass.

[0064] The content of olefin polymer A may be 80 to 99.9 parts by mass and polymer B may be 0.1 to 20 parts by mass, the content of olefin polymer A may be 85 to 99.9 parts by mass and polymer B may be 0.1 to 15 parts by mass, or the content of olefin polymer A may be 90 to 99.9 parts by mass and polymer B may be 0.1 to 10 parts by mass.

[0065] The total proportion 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.

[0066] In the composition, polymer B may or may not form a dispersed phase. When polymer B forms a dispersed phase, it means that the composition has a sea-island structure in which olefin polymer A forms a continuous phase (sea portion) and polymer B forms a dispersed phase (island portion). The average equivalent circle diameter of the dispersed phase (island portion) can be between 10 nm and 400 μm.

[0067] (Additives) The composition may optionally contain additives. The additives 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 and inorganic composite fibers, inorganic whiskers, and fillers.

[0068] Examples of stabilizers include at least one selected from the group consisting of lubricants, anti-aging agents, heat stabilizers, light stabilizers, weather stabilizers, metal deactivators, ultraviolet absorbers, light stabilizers, and copper damage inhibitors. An example of a light stabilizer is a hindered amine light stabilizer.

[0069] An example of a coloring agent is at least one selected from the group consisting of titanium dioxide, carbon black, and organic pigments. An example of a metal powder is ferrite.

[0070] An example of an organic powder is 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.

[0071] Examples of fillers include 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, evo powder, cotton floc, cork powder, barium sulfate, fluororesin, cellulose powder, and wood powder.

[0072] The composition may contain only one of the above-mentioned additives, or it may contain a combination of two or more additives.

[0073] In the composition, the additive may be contained in either olefin polymer A or polymer B. The additive may also form a dispersed phase separate from polymer B within the continuous phase of olefin polymer A.

[0074] The curve of the loss modulus E'' of the composition with respect to temperature, obtained by dynamic mechanical analysis (DMA), may have multiple peaks (e.g., two peaks), but it is preferable that there be only one peak (a single peak). The DMA method involves cutting a 0.3 mm thick sample into strips, measuring it at a measurement frequency of 5 Hz in tensile mode, and gradually increasing the temperature from -150°C at a heating rate of 2°C / minute until the sample melts and measurement becomes impossible. The strain was kept within the range of 0.1% or less. If 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 between -70°C and 150°C. The composition may have a cocrystal of olefin polymer A and polymer B. The presence or absence of a cocrystal can be confirmed by the presence or absence of peaks in the 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 polypropylene single crystal appear at 2θ = approximately 14°, 17°, and 18.5°, the peaks of P3HB3HH appear at 2θ = approximately 13.5° and 17°, and the cocrystal peak appears at approximately 16°. The peaks of the polypropylene single crystal were referenced from J. Polymer Sci. B Polymer Physics Vol. 24, 461-491 (1986). The eutectic ratio (the volume fraction of the co-crystal structure within the overall structure) in the composition can be 0.1% or more. The eutectic ratio can be calculated as the total area of ​​the co-crystal peaks relative to the total area of ​​the single crystal peaks and co-crystal peaks of the olefin polymer A. For example, the calculation for a mixture of polypropylene and P3HB3HH can be performed as follows. First, the two-dimensional pattern of the X-ray diffraction of the composition is evaluated, and the obtained two-dimensional pattern of X-ray diffraction is averaged around the circumference for all azimuthal angles to convert it into a diffraction angle-intensity profile. Then, the eutectic ratio can be calculated from the ratio of the area of ​​the 2θ=16° peak to the total area of ​​the peak originating from the polypropylene single crystal and the 2θ=16° peak. When a composition has cocrystals, its crystallization rate is delayed. Compositions with a slow crystallization rate are useful in terms of the transferability of microstructure patterns, etc.

[0075] (Method of manufacturing the composition) The above composition can be obtained by melt-kneading olefin polymer A, polymer B, and additives as needed. The kneading temperature (set temperature of the kneader) is preferably 150 to 300°C, and more preferably 170 to 280°C. Alternatively, a pre-kneaded product can be obtained by melt-kneading a portion of each of olefin polymer A and polymer B, and then the remaining olefin polymer A and polymer B can be added to the pre-kneaded product and further melt-kneaded to obtain the composition.

[0076] (Method for manufacturing a molded body of a composition) A molded article of the above composition having the required shape can be obtained using known resin molding methods such as injection molding, extrusion molding, vacuum molding, pressure molding, press molding, foam molding, blow molding, and rotational molding.

[0077] Furthermore, the above composition can be laminated with other materials such as other resins, metals, paper, or leather to obtain a multilayer structure.

[0078] The surface of a molded article of the composition of the present invention may be subjected to a surface treatment. Examples of surface treatment methods include embossing, corona discharge treatment, flame treatment, plasma treatment, and ozone treatment.

[0079] The above composition can be widely used as a resin material. Applications of the composition of the present invention include exterior components, furniture and interior decoration components, house components, toy components, gardening components, automobile components, and packaging materials. Examples of exterior components include carport components, fence components, gate components, gatepost components, post components, cycle port components, deck components, sunroom components, roof components, terrace components, handrail components, shade components, and awning components. Examples of furniture and interior decoration components include sofa components, table components, chair components, bed components, chest of drawers components, cabinet components, and dresser components. Examples of home appliance components include clock components, mobile phone components, and white goods components. Examples of toy components include plastic model components, diorama components, and video game console components. Examples of gardening components include planter components, vase components, and flowerpot components. Examples of automobile components include bumper components, instrument panel components, and airbag cover components. Examples of packaging materials include food packaging materials, textile packaging materials, and general merchandise packaging materials. Furthermore, other applications include, for example, components for monitors, office automation (OA) equipment, medical components, drain pans, toiletry components, bottles, containers, snow removal equipment components, and various building components. [Examples]

[0080] The present invention will be described below using examples and comparative examples. The olefin polymer (A) and thermoplastic ester polymer (B) used in the examples and comparative examples are shown below.

[0081] (1) Olefin polymer A (A-1) Propylene homopolymer MFR (230℃, 2.16kg load): 7g / 10min Melting point (Tm): 163℃

[0082] (A-2) Ethylene homopolymer (high-density polyethylene) (Product Name) KEIYO Polyethylene G2500: Manufactured by Keiyo Polyethylene Co., Ltd. MFR (190℃, 2.16kg load): 5.4g / 10min Melting point (Tm): 131℃

[0083] (2) Polymer B (B-1) Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) Structural formula: (BI-3) formula Comonomer (3HH) content (mol%): 1.1 mol% Weight average molecular weight (Mw): 79000 MFR (190℃, 2.16kg load): 38g / 10min Melting point (Tm): 175℃

[0084] (B-2) Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) Structural formula: (BI-3) formula Comonomer (3HH) content (mol%): 0.2 mol% Weight average molecular weight (Mw): 104000 MFR (190℃, 2.16kg load): 7.8g / 10min Melting point (Tm): 175℃

[0085] (B-3) Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) Structural formula: (BI-4) formula (Product name) M4300: Manufactured by CJ CheilJedang Co., Ltd. Comonomer (3HH) content (mol%): 45 mol% Weight average molecular weight (Mw): 216000 MFR (190℃, 2.16kg load): 4.0g / 10min Melting point (Tm): 48.7℃

[0086] (B-4) Polyethylene terephthalate (Product Name) Bellpet EFG70: Manufactured by Bell Polyester Products Co., Ltd. Intrinsic viscosity: 0.75dl / g Melting point (Tm): 255℃

[0087] (B-5) Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) Structural formula: (BI-3) formula Comonomer (3HH) content (mol%): 20 mol% MFR (170℃, 2.16kg load): 38g / 10min Melting point (Tm): 74℃

[0088] (B-6) Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) Structural formula: (BI-3) formula Comonomer (3HH) content (mol%): 12 mol% Weight average molecular weight (Mw):850000 MFR (190℃, 2.16kg load): 3.5g / 10min Melting point (Tm): 129℃

[0089] (B-7) Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) Structural formula: (BI-3) formula Comonomer (3HH) content (mol%): 8.5 mol% Weight average molecular weight (Mw):850000 MFR (190℃, 2.16kg load): 3.7g / 10min Melting point (Tm): 148℃

[0090] The physical properties of each polymer and composition were measured according to the method shown below.

[0091] (1) Meltmass flow rate (MFR, unit: g / 10 min) Measurements were taken 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.

[0092] (2) Weight average molecular weight (Mw) The weight-average molecular weight (Mw) was calculated based on the results of gel permeation chromatography (GPC). For the GPC measurement, a Waters GPC-150C was used as the measuring instrument, an orthodichlorobenzene solution with a polymer concentration of 0.05 wt% was used, a mixed polystyrene gel column (PSKgelGMH6-HT, manufactured by Tosoh Corporation) was used as the column, and the measurement temperature was 135°C.

[0093] (3) Melting point (Tm) of polymers Measurements were taken 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.

[0094] (4) Content of the comonomer component of polymer B The comonomer content is 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 the hydroxyalkanoate in polymer B. The comonomer content was determined using the 1H-NMR spectrum method described in L. Tripathi., MCFactories, 11, 44 (2012). [Measurement conditions] Model: BrukerAVANCE600 Probe: 10mm cryopreve Measurement temperature: 135℃ Pulse repetition time: 1 second Pulse width: 45° Total number of times: 700 Magnetic field strength: 600MHz

[0095] (5) Measurement of the Tg of the composition The temperature-storage modulus curve of the composition was obtained using a viscoelastic device (SII Nanotechnology Co., Ltd.; DMS200), and the number of peaks was counted.

[0096] (6) Microstructure pattern transferability Using a Shindo Metal Industries compression molding machine (P-37), the resin was preheated at 200°C for 5 minutes on a textured plate with a microstructure pattern having a surface roughness (Ra) of 60 μm. The resin was then pressed onto the textured plate at 200°C, 1 MPa pressure, and 30 seconds to obtain a molded body. The surface roughness of the molded body was evaluated. The closer the surface roughness is to 60 μm, the higher the transferability of the microstructure pattern.

[0097] (7) Surface roughness (Ra) Using a three-dimensional surface roughness measuring instrument, SurfCorder SE-30K (manufactured by Kosaka Laboratory Co., Ltd.), measurements were taken in the X direction at a speed of 0.5 mm / second over an area of ​​2 mm in the X direction and 0.99 mm in the Y direction (Y direction pitch was 2 μm). The arithmetic mean surface roughness (Ra) was calculated from the measurement results.

[0098] (8) Mold releasability Using a Shindo Metal Industries compression molding machine (P-37), the resin was preheated at 200°C for 5 minutes on a textured plate with a fine structure pattern having a surface roughness (Ra) of 60 μm. The resin was then pressed onto the textured plate at 200°C, 1 MPa pressure, and 30 seconds to obtain a molded body. When peeling the molded body from the textured plate at a 45° angle, if the body tore, it was marked with ×; if it did not tear, it was marked with ○. (9) Cocrystal The two-dimensional X-ray diffraction pattern of the composition was evaluated, and the obtained two-dimensional X-ray diffraction pattern was averaged around all azimuthal angles to convert it into a diffraction angle-intensity profile. The presence of a cocrystal was confirmed by the presence or absence of a peak corresponding to diffraction based on the cocrystal (2θ=16°). Furthermore, the eutectic ratio was calculated based on the area of ​​the cocrystal peak and the single crystal peak of polypropylene. The specific method for calculating the eutectic ratio involved peak fitting of the two-dimensional X-ray diffraction pattern, calculating the area value for each, and following the formula below. Eutecticity = 16° peak area value / (14° peak area value + 17° peak area value + 18.5° peak area value + 16° peak area value) (10) Crystallization rate The composition was rapidly cooled from 190°C to 125°C, and then differential scanning thermal analysis was performed while maintaining the temperature to measure the crystallization rate (semi-crystallization time t1 / 2).

[0099] The properties of polymer A and polymer B are shown in Tables 1 and 2, respectively.

[0100] [Table 1]

[0101] [Table 2]

[0102] (Example 1) A polymer (A-1) containing 95.8% by mass and a polymer (B-1) containing 4.2% by mass were uniformly mixed in powder form. The mixture was then supplied to a small kneader (Xplore; manufactured by DSM) and kneaded 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 microstructure pattern transferability of the resin composition was evaluated.

[0103] (Example 2) The procedure was the same as in Example 1, except that a polymer of 95% by mass (A-1) and a polymer of 5% by mass (B-2) were used.

[0104] (Example 3) The procedure was the same as in Example 1, except that 90% by mass of polymer (A-1) and 10% by mass of polymer (B-2) were used.

[0105] (Example 4) The procedure was the same as in Example 1, except that 90% by mass of polymer (A-2) and 10% by mass of polymer (B-1) were used.

[0106] (Example 5) The procedure was the same 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.

[0107] (Comparative Example 1) The procedure was the same as in Example 1, except that only 100% by mass of polymer (A-1) was used.

[0108] (Comparative Example 2) The procedure was the same as in Example 1, except that a polymer (A-1) at 47.8% by mass and a polymer (B-1) at 52.2% by mass were used.

[0109] (Comparative Example 3) The procedure was the same as in Example 1, except that 90% by mass of polymer (A-1) and 10% by mass of polymer (B-3) were used.

[0110] (Comparative Example 4) The procedure was the same as in Example 1, except that 95% by mass of polymer (A-1) and 5% by mass of polymer (B-5) were used.

[0111] (Comparative Example 5) The procedure was the same as in Example 1, except that 95% by mass of polymer (A-1) and 5% by mass of polymer (B-6) were used.

[0112] (Comparative Example 6) The procedure was the same as in Example 1, except that 95% by mass of polymer (A-1) and 5% by mass of polymer (B-4) were used.

[0113] The results are shown in Table 3.

[0114] [Table 3]

[0115] It was confirmed that by mixing an appropriate amount of a poly(3-hydroxyalkanoate) polymer with a high melting point into an olefin polymer, the transferability was improved even when a thermoplastic polyester was added. Furthermore, in Examples 1 to 3, a delay in the crystallization rate was also observed.

Claims

1. A composition comprising olefin polymer A and polymer B, The polymer B is a poly(3-hydroxyalkanoate) polymer having a melting point of 150°C or higher. A composition for transferring microstructure patterns, wherein, with a total of 100 parts by mass of polymer A and polymer B, the content of polymer A is 90 to 99.9 parts by mass, and the content of polymer B is 0.1 to 10 parts by mass.

2. A composition comprising olefin polymer A and polymer B, The polymer B is a poly(3-hydroxyalkanoate) polymer having a melting point of 150°C or higher. The polymer B has a ratio of 3-hydroxybutyrate repeating units of 98.0 to 99.9 mol% relative to 100 mol% of total hydroxyalkanoate ester repeating units. A composition in which, with a total of 100 parts by mass of polymer A and polymer B, the content of polymer A is 90 to 99.9 parts by mass, and the content of polymer B is 0.1 to 10 parts by mass.

3. The composition according to claim 1 or 2, wherein polymer A is a propylene-based polymer.

4. The composition according to claim 1 or 2, having 0.1 volume% or more of a cocrystal.

5. The composition according to claim 1 or 2, wherein the peak in the curve of the loss modulus E'' of the composition with respect to temperature, as determined by dynamic mechanical analysis (DMA), is unimodal.

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