Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

• the present invention relates to a composition.
• Aliphatic polyester polymers are resins with low environmental impact that can be synthesized from renewable resources without using fossil resources, and have excellent moldability and mechanical properties. For this reason, adding aliphatic polyester polymers to various packaging materials, various containers such as bottles, food packaging materials, container caps, stationery, daily necessities, fibers for carpets and sofas, interior and exterior materials for automobiles, electrical and electronic equipment parts, building and residential interior materials, and other construction materials can reduce the environmental impact.
• compositions containing such aliphatic polyester polymers are known, as described in Patent Documents 1 to 3.
• the present invention was made in consideration of the above problems, and aims to provide a composition that contains an aliphatic polyester polymer and can reduce odor generation after molding.
• a composition comprising an olefin polymer A, an aliphatic polyester polymer B, and an inorganic powder C, the inorganic powder C having a pH of 6.5 to 11.5 as evaluated according to JIS M 8016-1991.
• the melt mass flow rate of the aliphatic polyester polymer B measured under conditions of a temperature of 210° C. and a load of 2.16 kgf is defined as MFR(B);
• the present invention provides a composition that contains an aliphatic polyester polymer and yet reduces odor generation after molding.
• composition contains an olefin polymer A, an aliphatic polyester polymer B, and an inorganic powder C.
• the olefin polymer A is a polymer containing 50% by mass or more of structural units derived from an olefin having from 2 to 10 carbon atoms (wherein the total amount of the olefin polymer is taken as 100% by mass).
• Examples of the olefin having from 2 to 10 carbon atoms are ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and 1-decene.
• Olefin polymer A may contain structural units derived from monomers other than olefins having 2 to 10 carbon atoms.
• 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 non-conjugated dienes such as dicyclopentadiene and 5-ethylidene-2-norbornene.
• 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 a combination of any two or more of these.
• An ethylene-based polymer is a polymer that contains 50% or more by mass of structural units derived from ethylene. Examples include ethylene homopolymer, ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, and ethylene-1-butene-1-hexene copolymer.
• An ethylene-based polymer may be a combination of two or more ethylene-based polymers.
• Propylene-based polymers are polymers containing 50% by mass or more of structural units derived from propylene, and examples thereof 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.
• the propylene-based polymer may be a combination of two or more propylene-based polymers. It is preferable that the olefin-based polymer A is a propylene-based polymer.
• Butene polymers are polymers containing 50% by mass or more of structural units derived from 1-butene. Examples include 1-butene homopolymer, 1-butene-ethylene copolymer, 1-butene-propylene copolymer, 1-butene-1-hexene copolymer, 1-butene-1-octene copolymer, 1-butene-ethylene-propylene copolymer, 1-butene-ethylene-1-hexene copolymer, 1-butene-ethylene-1-octene copolymer, 1-butene-propylene-1-hexene copolymer, and 1-butene-propylene-1-octene copolymer.
• the butene polymer may be a combination of two or more butene polymers.
• the above olefin polymer A can be produced by a known polymerization method using a known polymerization catalyst.
• the melt mass flow rate (MFR) of the olefin polymer A measured according to JIS K7210-2014 at a temperature of 230°C or 190°C and a load of 2.16 kgf is preferably 0.1 g/10 min or more and 200 g/10 min or less.
• Aliphatic polyester polymers have a structure of a polycondensation product of an aliphatic polycarboxylic acid component and an aliphatic polyhydric alcohol component, or a polycondensation product of an aliphatic hydroxycarboxylic acid, and the main chain of the repeating unit does not contain an aromatic hydrocarbon structure.
• aliphatic polyester polymers examples include polymers of hydroxycarboxylic acids or lactones, polycondensates of diols and dicarboxylic acids, and copolymers thereof.
• polymer B is a copolymer
• the arrangement of the copolymer may be any of random copolymers, alternating copolymers, block copolymers, graft copolymers, etc.
• At least a portion of these may be crosslinked with a crosslinking agent such as a polyisocyanate such as xylylene diisocyanate or 2,4-tolylene diisocyanate, or a polysaccharide such as cellulose, acetyl cellulose, or ethyl cellulose.
• a crosslinking agent such as a polyisocyanate such as xylylene diisocyanate or 2,4-tolylene diisocyanate, or a polysaccharide such as cellulose, acetyl cellulose, or ethyl cellulose.
• at least a portion of these may have any structure, such as a linear, cyclic, branched, star-shaped, or three-dimensional network structure, without any restrictions, and may be a copolymer with a polyolefin resin or a graft polymer with a polyolefin resin.
• this aliphatic polyester polymer B can be used alone or in combination.
• hydroxycarboxylic acids include hydroxycarboxylic acids having 2 to 18 carbon atoms, preferably 6 or less carbon atoms, and most preferably 4 carbon atoms. Specific examples include glycolic acid, L-lactic acid, D-lactic acid, D,L-lactic acid, 3-hydroxybutyrate, 3-hydroxyvalerate, 3-hydroxypropionate, 4-hydroxybutyrate, 4-hydroxyvalerate, 5-hydroxyvalerate, 3-hydroxypentenoate, 3-hydroxyhexanoate, 3-hydroxyheptanoate, 3-hydroxyoctanoate, 3-hydroxynonanoate, and 3-hydroxydecanoate.
• lactones examples include propiolactone, butyrolactone, valerolactone, caprolactone, and laurolactone.
• the diol is preferably a diol having 2 to 10 carbon atoms. Among them, an aliphatic diol having 2 to 4 carbon atoms or an alicyclic diol having 5 or 6 carbon atoms is more preferable. Specific examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethylol, 1,4-cyclohexan
• the dicarboxylic acid is preferably an aliphatic dicarboxylic acid having 2 to 12 carbon atoms. Among them, an aliphatic dicarboxylic acid having 2 to 6 carbon atoms or an alicyclic dicarboxylic acid having 5 to 6 carbon atoms is more preferable.
• these dicarboxylic acids may be derivatives such as alkyl esters and acid anhydrides having 1 to 4 carbon atoms.
• polylactic acid polybutylene succinate, poly(butylene succinate-co-butylene adipate), polycaprolactone, poly(3-hydroxybutyrate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), and polyglycolic acid.
• the polylactic acid When polylactic acid is used as the aliphatic polyester polymer B, the polylactic acid preferably has an L-form ratio of 94 mol % or more in the lactic acid components that make it up. By setting the L-form ratio in this range, it is possible to prevent a decrease in the melting point.
• Poly(3-hydroxyalkanoate)-based polymer Polymer B may be a poly(3-hydroxyalkanoate)-based polymer having a melting point of 150° C. or higher.
• the poly(3-hydroxyalkanoate) polymer is a polyhydroxyalkanoate, i.e., a polycondensate (polyester) of hydroxyalkanoic acid, and necessarily contains a repeating unit of 3-hydroxyalkanoate represented by formula (1).
• 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.
• R is preferably an alkyl group having 1 to 8 carbon atoms, an amide group having 1 to 20 carbon atoms, or an aryl group having 6 to 8 carbon atoms.
• halogen atoms are F, Cl, Br, and I.
• the alkyl group having 1 to 15 carbon atoms may be linear or branched.
• the alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms.
• 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.
• amino groups having 1 to 18 carbon atoms include amino groups, alkylamino groups, dialkylamino groups, arylamino groups, alkylarylamino groups, benzylamino groups, and dibenzylamino groups.
• alkylamino groups include methylamino, ethylamino, propylamino, butylamino, pentylamino, hexylamino, heptylamino, 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-adamantamino, and 2-adamantamino.
• dialkylamino groups are dimethylamino, diethylamino, dipropylamino, dibutylamino, dipentylamino, diisopropylamino, diisobutylamino, diisopentylamino, methylethylamino, methylpropylamino, methylbutylamino, methylisobutylamino, dicyclopropylamino, pyrrolidino, piperidino, and piperazino groups.
• arylamino groups include anilino, 1-naphthylamino, 2-naphthylamino, o-toluidino, m-toluidino, p-toluidino, 1-fluoreneamino, 2-fluoreneamino, 2-thiazoleamino, and p-terphenylamino groups.
• the alkylarylamino group includes an N-methylanilino group, an N-ethylanilino group, an N-propylanilino group, an N-butylanilino group, an N-isopropylanilino group, and an N-pentylanilino group.
• alkoxy groups having 1 to 11 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, cyclopropoxy, cyclobutoxy, and cyclopentoxy.
• amide group refers to a group obtained by removing one hydrogen atom bonded to a nitrogen atom from a carboxylic acid amide.
• the organic group may be an alkyl group, an alkoxy group, or an aryl group, which may be substituted with a halogen atom.
• the amide group is preferably a formamide group, an acetamide group, a propionamide group, a butyroamide group, or a benzamide group.
• aryl groups having 6 to 12 carbon atoms include phenyl, tolyl, xylyl, naphthyl, and biphenyl groups, with phenyl, tolyl, and xylyl being more preferred.
• heteroatoms in monovalent heterocyclic groups having 1 to 9 carbon atoms are N, O, and S, and may be saturated or unsaturated, may contain a single heteroatom, multiple heteroatoms, or may contain different types of heteroatoms.
• heterocyclic groups include thienyl, pyrrolyl, furyl, pyridyl, piperidinyl, quinolinyl, isoquinolinyl, pyrimidinyl, triazinyl, and thiazolyl groups.
• the repeating units of the aliphatic polyester polymer B may consist of only one or more types of 3-hydroxyalkanoates represented by formula (1), or may have one or more types of 3-hydroxyalkanoates represented by formula (1) and one or more types of other hydroxyalkanoates.
• the aliphatic polyester polymer B preferably contains 50 mol% or more of the 3-hydroxyalkanoate repeating units represented by formula (1) relative to the total repeating units of hydroxyalkanoate (100 mol%), more preferably 70 mol% or more.
• 3HB 3-hydroxybutyrate
• 3HH 3-hydroxyhexanoate
• 3HH 3-hydroxyoctanate
• 3HH 3-hydroxyoctadecanate
• 3-hydroxypropionate where R is a hydrogen atom.
• polymer B having only one type of repeating unit represented by formula (1) is poly(3-hydroxybutyrate) (hereinafter sometimes referred to as P3HB).
• polymer B having only multiple types of repeating units represented by formula (1) are poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (hereinafter sometimes written as P3HB3HH), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (hereinafter sometimes written as P3HB3HV), and poly(3-hydroxybutyrate-co-3-hydroxypropionate) (hereinafter sometimes written as P3HB3HP).
• a hydroxyalkanoate other than the 3-hydroxyalkanoate represented by formula (1) is a repeating unit represented by formula (2) (wherein R1 is a hydrogen atom or an alkyl group represented by CnH2n +1 , n is an integer of 1 or more and 15 or less, and m is an integer of 2 to 10).
• polymer B containing repeating units of formulas (1) and (2) is poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (e.g., formula (P3HB4HB) below).
• the repeating units of the aliphatic polyester polymer B contain at least 3-hydroxybutyrate among the 3-hydroxyalkanoates represented by formula (1).
• the aliphatic polyester 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.
• the aliphatic polyester polymer B may have two or more types of ester repeat units, and may be, for example, a di-polymer having two types of repeat units, a tri-copolymer having three types of repeat units, or a tetra-copolymer having four types of repeat units, as described above.
• an example of a tri-copolymer is poly(3-hydroxybutyrate-co-3-hydroxyvalerate-co-3-hydroxyhexanoate) (hereinafter sometimes referred to as (P3HB3HV3HH)).
• the aliphatic polyester polymer B contains 3-hydroxybutyrate among the repeating units of 3-hydroxyalkanoate represented by formula (1).
• the proportion XX of the repeating units of 3-hydroxybutyrate relative to 100 moles of all ester repeating units of hydroxyalkanoate is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 98.0 mol% or more.
• the ratio XX is usually 100 mol% or less, preferably 99.9 mol% or less, and more preferably 99.8 mol% or less.
• the arrangement of the copolymer may be any of a random copolymer, an alternating copolymer, a block copolymer, a graft copolymer, etc.
• Aliphatic polyester polymer B may have other ester repeating units than those of formula (1) and formula (2), but the main chain of the other ester repeating units does not contain an aromatic hydrocarbon structure.
• aliphatic polyester polymer B is an aliphatic polyester.
• composition ratio of the repeating units in the aliphatic polyester polymer B can be calculated from the results of NMR measurements such as 1H-NMR and 13C-NMR, as described in L. Tripathi., M. C. Factories, 11, 44 (2012).
• the aliphatic polyester polymer B may be a mixture of two or more types of poly(3-hydroxyalkanoate) polymers.
• the weight average molecular weight (Mw) of the aliphatic polyester polymer B can be 10,000 to 1,000,000, preferably 20,000 to 800,000, and more preferably 30,000 to 600,000. By making the weight average molecular weight (Mw) 10,000 or more, it is possible to obtain a molded product with excellent impact strength and tensile elongation. In addition, by making the weight average molecular weight 500,000 or less, the dispersibility in the olefin polymer A is improved. The weight average molecular weight may be 400,000 or less, 300,000 or less, 200,000 or less, or 100,000 or less. In this specification, the weight average molecular weight (Mw) is measured by GPC using standard polystyrene as a molecular weight standard substance.
• the aliphatic polyester polymer B is a thermoplastic resin, and is preferably crystalline.
• the melt mass flow rate (MFR(B)) of the aliphatic polyester polymer B measured according to JIS K7210-2014 at a temperature of 190°C or 170°C and a load of 2.16 kgf is preferably 0.1 g/10 min or more and 200 g/10 min or less.
• MFR(B) may be 1 g/10 min or more, 3 g/10 min or more, 5 g/10 min or more, 7 g/10 min or more, 8 g/10 min or more, 10 g/10 min or more, or 20 g/10 min or more.
• MFR(B) may be 150 g/10 min or less, or 100 g/10 min or less.
• the melting point (Tm) of the aliphatic polyester polymer B is preferably 150°C or higher, and may be 155°C or higher, 160°C or higher, 165°C or higher, 170°C or higher, or 175°C or higher.
• the melting point (Tm) of the polymer B may be 220°C or lower, 200°C or lower, or 190°C or lower.
• the melting point (Tm) of the aliphatic polyester polymer B is measured from the position of the main peak due to the melting of crystals as determined by differential scanning calorimetry (DSC) measurement in accordance with JIS K7121.
• Poly(3-hydroxyalkanoate) polymers may be produced by microorganisms or may be derived from compounds derived from petroleum or plant materials (e.g., cyclic lactones, etc.).
• each repeating unit of hydroxyalkanoate may consist only of the D-form (R-form), such as in those produced from microorganisms, but the repeating units of hydroxyalkanoate may contain both the D-form (R-form) and the L-form (S-form), such as in those derived from a mixture of the D-form (R-form) and the L-form (S-form).
• the repeating unit of formula (1) can be represented by the following formula: (BI-1) where n represents the degree of polymerization.
• poly-(3-hydroxybutyrate) produced from a microorganism has the following structure: (BI-2) where n represents the degree of polymerization.
• poly-(3-hydroxybutyrate-co-3-hydroxyhexanoate) produced from a microorganism has the following structure: (BI-3) where m and n represent the degree of polymerization.
• poly-(3-hydroxybutyrate-co-4-hydroxybutyrate) produced from a microorganism has the following structure: (BI-4) where m and n represent the degree of polymerization.
• the aliphatic polyester polymer B can be biodegradable.
• poly(3-hydroxyalkanoate) polymers can be produced by microorganisms such as Alcaligenes eutrophus AC32 strain (international deposit under the Budapest Treaty, international depositary authority: National Institute of Advanced Industrial Science and Technology Patent Organism Depositary Center (6-1-1 Central, Higashi 1-chome, Tsukuba-shi, Ibaraki-ken, Japan), original deposit date: August 12, 1996, transferred August 7, 1997, accession number FERMBP-6038 (transferred from original deposit FERMP-15786)) (J. Bacteriol., 179, 4821 (1997)), which is an Alcaligenes eutrophus introduced with a PHA synthase gene derived from Aeromonas caviae.
• microorganisms such as Alcaligenes eutrophus AC32 strain (international deposit under the Budapest Treaty, international depositary authority: National Institute of Advanced Industrial Science and Technology Patent Organism Depositary Center (6-1-1 Central, Higashi 1-chome, Tsukuba-shi, Ibaraki-ken, Japan
• the inorganic powder refers to a powder of an inorganic material.
• the inorganic material include a simple metal or metalloid, an alloy of two or more elements selected from the group consisting of metals and metalloids, and a compound containing one element or two or more elements selected from the group consisting of metals and metalloids, such as an oxide, a sulfide, a nitride, a hydroxide, or a salt (sulfate, phosphate, etc.).
• metals constituting the inorganic material are Al, Li, Ti, Fe, Mg, K, Na, Ca, Zn, Pb, Cu, Cr, Ba, Rb, Cs, Mn, V, Be, Ni, and Co.
• metalloids are Si and B.
• the inorganic material may be carbon.
• the inorganic material may be a natural mineral or an artificially synthesized material.
• the powder of the inorganic material may be surface-modified.
• the pH of inorganic powder C as evaluated by JIS M 8016-1991 is 6.5 to 11.5.
• the pH of inorganic powder C as evaluated by JIS M 8016-1991 may be 8.5 or more and 9.5 or less.
• the pH of the above inorganic powder C is obtained by adding 20 g of inorganic powder C to 80 mL of pure water, stirring, and measuring the pH of the liquid.
• the pH of inorganic powder C is determined by the surface condition of the inorganic powder, i.e., the surface functional groups. Therefore, the pH of inorganic powders such as talc exemplified in this embodiment does not necessarily fall within the range of 6.5 to 11.5, and the pH of the inorganic powder varies depending on the manufacturing method of the inorganic powder, whether or not the surface is treated, the type of treatment agent, etc.
• Inorganic powder C may be a powder of a single element or compound that exhibits a pH of 6.5 to 11.5, or may be a mixture of powders of two or more materials selected from the group consisting of elements and compounds that exhibit a pH of 6.5 to 11.5.
• inorganic powder C examples include at least one selected from the group consisting of glass beads, glass balloons, glass flakes, asbestos, mica, calcium-based compounds, talc, silica, calcium silicate, hydrotalcite, titanium oxide, kaolinite, wollastonite, diatomaceous earth, graphite, pumice, and barium sulfate.
• inorganic powder C preferably contains at least one selected from the group consisting of mica, calcium-based compounds, talc, silica, hydrotalcite, and wollastonite, more preferably contains at least one selected from the group consisting of mica, calcium-based compounds, talc, silica, and hydrotalcite, and even more preferably contains at least one selected from the group consisting of mica, calcium-based compounds, and talc.
• mica examples include muscovite, aluminoceladonite, ferroaluminoceladonite, celadonite, ferroceladonites, Roscoe mica, chromphyllite, boromuscovite, sodalite, nanpingite, tobe mica, iron mica, phlogopite, siderophyllite, eastonite, muscovite, Hendricksite, Montdorite, yangzhuming mica, tainiolite, polylithiomica, trilithiomica, These are Masutomi mica, Norrishite, tetra-ferri-annite, tetra-ferriphlogopite, sodalite, Preiswerkite, Ephesite, nacre, Chernykhite, Clintonite, Bityite, Anandite, Kinoshita mica, fluorkinoshita mica, illite, glauconite, Brammallite, Wonesite, biot
• Examples of the calcium-based compound include calcium ascorbate, calcium sulfite, calcium bisulfite, calcium monophosphate, Egyptian blue, calcium chloride, calcium chloride hydroxide, calcium chlorate, calcium peroxide, casein phosphopeptide, kalimate, calcium superphosphate, calcium cyanamide, calcium formate, calcium gluconate, calcium glutamate, calcium chromate, chrome tin pink, calcium silicate, anhydrite, calcium acetate, calcium oxide, calcium hypochlorite, calcium cyanide, calcium bromide, calcium triple superphosphate, calcium oxalate, calcium bromate, calcium tartrate, calcium nitrate, calcium hydroxide, calcium hydride, gypsum, calcium carbide, calcium carbonate, calcium hydrogen carbonate, calcium titanate, calcium lactate, tricalcium diphosphate, calcium fluoride, POs-Ca, calcium polycarbophil, calcium iodide, calcium iodate, lysol rubin BK, calcium sulfide, calcium
• Examples of calcium carbonate include FP#300, KS#500, KS#800, KS#1000, KS#1200, ACE#25, SST#40, Kansui-seki 3-minute, Escalon#200, Escalon#1500, Escalon#2000, and Escalon#2300 manufactured by Hayashi Kasei.
• talc examples include Hayashi Kasei's Talcan Powder series, Micron White series, GH series, and KHP series, and Nippon Talc's Nano Ace series and ultrafine powder talc series.
• Components that are preferably not contained in inorganic powder C are a fatty acid metal salt such as a long-chain fatty acid metal salt.
• a long-chain fatty acid refers to a fatty acid having 13 or more carbon atoms. Examples of fatty acids are stearic acid, lauric acid, and palmitic acid. Examples of metal salts are magnesium salts, calcium salts, zinc salts, lithium salts, and barium salts.
• the surface of the inorganic powder does not have a long-chain fatty acid metal salt.
• long-chain fatty acid metal salts are metal salts of stearic acid such as magnesium stearate, calcium stearate, and zinc stearate, magnesium laurate, and calcium palmitate.
• fatty acid metal salts such as long-chain fatty acid metal salts are present on the surface of inorganic powder C, the pH tends to decrease and fall outside the range of 6.5 to 11.5.
• composition suitably does not contain inorganic powders having a pH of less than 6.5 or more than 11.5 as evaluated by JIS M 8016-1991.
• the median diameter D50 of the inorganic powder C may be 30 ⁇ m or less, 25 ⁇ m or less, or 20 ⁇ m or less. If D50 is too large, mechanical strength such as bending modulus is likely to decrease. From the viewpoint of improving mechanical strength such as bending elastic modulus, the median diameter D50 of the inorganic powder C may be 0.05 ⁇ m or more, 0.5 ⁇ m or more, 1 ⁇ m or more, or 5 ⁇ m or more.
• the median diameter D50 can be determined by measuring the particle size distribution by weight in accordance with JIS R1629 using a laser diffraction particle size distribution measuring instrument, and then reading the particle size value at a cumulative amount of 50% by weight from the resulting cumulative particle size distribution curve.
• a laser diffraction particle size distribution measuring instrument is the MT-3300EX-II manufactured by Nikkiso Co., Ltd.
• MFR(X)/MFR(B) The melt mass flow rate of the aliphatic polyester polymer B measured under conditions of a temperature of 210° C. and a load of 2.16 kgf is defined as MFR(B),
• MFR(X)/MFR(B) When a mixture X containing 0.5 parts by mass of inorganic powder C per 100 parts by mass of the total of aliphatic polyester polymer B and inorganic powder C has a melt mass flow rate measured at a temperature of 210° C. and a load of 2.16 kgf as MFR(X), it is preferable that MFR(X)/MFR(B) is 1.0 or less.
• MFR(X) becomes greater than MFR(B).
• MFR(X) becomes smaller than MFR(B).
• MFR(X)/MFR(B) being 1.0 or less means that inorganic powder C is a compound that is unlikely to cause significant deterioration of aliphatic polyester polymer B due to heating.
• the composition may contain additives as necessary, which may be at least one selected from the group consisting of stabilizers, antibacterial agents, antifungal agents, dispersants, plasticizers, flame retardants, tackifiers, colorants, metal powders, organic powders, inorganic fibers, organic fibers, organic and inorganic composite fibers, inorganic whiskers, and fillers.
• additives as necessary, which may be at least one selected from the group consisting of stabilizers, antibacterial agents, antifungal agents, dispersants, plasticizers, flame retardants, tackifiers, colorants, metal powders, organic powders, inorganic fibers, organic fibers, organic and inorganic composite fibers, inorganic whiskers, and fillers.
• An example of the stabilizer is at least one selected from the group consisting of a lubricant, an anti-aging agent, a heat stabilizer, a light resistance agent, a weather resistance agent, a metal deactivator, an ultraviolet absorber, a light stabilizer, and a copper damage inhibitor.
• a lubricant an anti-aging agent
• a heat stabilizer a heat stabilizer
• a light resistance agent a weather resistance agent
• a metal deactivator an ultraviolet absorber
• a light stabilizer and a copper damage inhibitor.
• An example of the light resistance agent is a hindered amine-based light resistance agent.
• An example of a colorant is at least one selected from the group consisting of titanium oxide, carbon black, and organic pigments.
• An example of a metal powder is ferrite.
• An example of an organic powder is protein.
• inorganic fibers are glass fibers and metal fibers.
• organic fibers are carbon fibers and aramid fibers.
• An example of an inorganic whisker is potassium titanate whiskers.
• Examples of the filler include at least one selected from the group consisting of ebonized powder, cotton flock, cork powder, cellulose powder, and wood powder.
• composition may contain only one of the above additives, or a combination of two or more of them.
• composition of the composition there is no particular limitation on the contents of the olefin polymer A and the aliphatic polyester polymer B relative to 100 parts by mass in total of the olefin polymer A and the aliphatic polyester polymer B. From the viewpoint of enhancing mechanical strength such as flexural modulus, the content of the olefin polymer A may be 51 to 99.9 parts by mass, and the content of the aliphatic polyester polymer B may be 0.1 to 49 parts by mass.
• the content of the olefin polymer A may be 60 parts by mass or more, 70 parts by mass or more, 80 parts by mass or more, or 90 parts by mass or more, relative to 100 parts by mass in total of the olefin polymer A and the aliphatic polyester polymer B.
• inorganic powder C there is no particular limit to the content of inorganic powder C relative to 100 parts by mass of the total of olefin polymer A and aliphatic polyester polymer B, but it is preferably 0.01 to 40 parts by mass.
• the content of inorganic powder C may be 0.1 parts by mass or more, 1 part by mass or more, or 20 parts by mass or less.
• the total proportion of the olefin polymer A, the aliphatic polyester polymer B, and the inorganic powder C in the entire composition may be 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more.
• Olefin polymer A can account for more than 50% by mass of the composition, and can account for 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more.
• the aliphatic polyester polymer B may account for 0.1 to 20 parts by mass of the composition.
• the generation of odor is suppressed by containing the inorganic powder C having a specific pH.
• the reason for this is not clear, but it is thought that, for example, it is due to the suppression of thermal decomposition of the aliphatic polyester polymer B.
• the composition ratio of the olefin polymer A and the aliphatic polyester polymer B is within a specific range and the median diameter D50 of the inorganic powder C is within the above-mentioned specific range, the mechanical strength of the molded product, such as the flexural modulus (FM), is further increased.
• FM flexural modulus
• the inorganic powder C can suppress the thermal decomposition of not only the aliphatic polyester polymer B but also the olefin polymer A during molding (melt-kneading).
• the composition can be obtained by melt-kneading the respective raw material components.
• the mixing temperature (mixer temperature setting) is preferably 150 to 300°C, and more preferably 170°C to 280°C. It is also possible to process at a temperature of 210°C or higher.
• the composition can be produced by melt-kneading the olefin polymer A, the aliphatic polyester polymer B, the inorganic powder C, and any additives that are added as required all at once.
• the composition may be produced by a first step of melt-kneading a portion of the olefin polymer A, all of the aliphatic polyester polymer B, some or all of the inorganic powder C, and some or all of the additives added as needed to produce a preliminary composition, and then a second step of melt-kneading the preliminary composition with the remainder of the olefin polymer A, the remainder of the inorganic powder C, and the remainder of the additives added as needed. It is not necessary to add any olefin polymer in the first step.
• a molded article having a desired shape can be obtained from the above composition using a known resin molding method such as injection molding, extrusion molding, vacuum molding, pressure molding, press molding, foam molding, blow molding, or rotational molding.
• the above composition can also be laminated with other materials such as other resins, metals, paper, leather, etc. to obtain a multi-layer structure.
• the surface of the molded article of the composition of the present invention may be subjected to a surface treatment.
• the surface treatment method include embossing, corona discharge treatment, flame treatment, plasma treatment, and ozone treatment.
• the above composition can be widely used as a resin material.
• Applications of the resin composition of the present invention include textile materials, exterior components, furniture and interior decoration components, house components, toy components, gardening components, automotive components, and packaging materials.
• the textile materials include fabric materials for clothing, fabric materials for interior use, and textile materials for industrial use.
• the exterior materials include carport materials, fence materials, gate materials, gatepost materials, post materials, cycle port materials, deck materials, sunroom materials, roof materials, terrace materials, handrail materials, shade materials, and awning materials.
• Examples of the furniture and interior decoration materials include sofa materials, table materials, chair materials, bed materials, chest materials, cab net materials, and dresser materials.
• Examples of the home appliance materials include clock materials, mobile phone materials, and white goods home appliance materials.
• Examples of the toy materials include plastic model materials, diorama materials, and video game main body materials.
• Examples of the gardening materials include planter materials, flower vase materials, and flower pot materials.
• Examples of the automobile materials include bumper materials, instrument panel materials, and airbag cover materials.
• Examples of the packaging materials include food packaging materials, textile packaging materials, and miscellaneous packaging materials.
• Other applications include, for example, monitor components, office automation (OA) equipment components, medical components, drainage pans, toiletry components, bottles, containers, snow removal equipment components, and various construction components.
• OA office automation
• the present invention will be explained below using examples and comparative examples.
• the olefin polymer A, aliphatic polyester polymer B, and inorganic powder C used in the examples and comparative examples are shown below.
• Olefin Polymer A (A-1) Propylene homopolymer MFR (230°C, 2.16 kg load): 7g/10min Melting point (Tm): 163°C
• MFR(B-1) Melt mass flow rate (MFR, unit: g/10 min) Measurement was performed according to the method specified in JIS K7210-2014. The measurement temperature was 230° C., 210° C., or 190° C., and the load was 2.16 kg. The cylinder in which the resin was melted and kneaded was made of metal, and light was not irradiated onto the resin.
• the above MFR(X) is a melt mass flow rate of a mixture X containing 0.5 parts by mass of any one of the inorganic powders C-1 to C-5 per 100 parts by mass of the total of the polymer B-1 and any one of the inorganic powders C-1 to C-5, measured at a temperature of 210° C. and a load of 2.16 kgf.
• MFR(B-1) is the melt mass flow rate of polymer B-1 measured under conditions of a temperature of 210° C. and a load of 2.16 kgf.
• Weight average molecular weight (Mw) The weight average molecular weight (Mw) was calculated based on the results of gel permeation chromatography (GPC). In the GPC measurement, a Waters GPC-150C measuring device was used, an orthodichlorobenzene solution with a polymer concentration of 0.05% by weight was used, and a mixed polystyrene gel column (Tosoh PSKgel GMH6-HT) was used as the column, at a measurement temperature of 135°C.
• GPC gel permeation chromatography
• Tm Melting point
• the content of the comonomer component refers to the molar ratio of repeating units other than 3-hydroxybutyrate (3-hydroxyhexanoate (3HH) or 4-hydroxybutyrate (4HB)) to the number of all ester repeating units of hydroxyalkanoate in the aliphatic polyester polymer B.
• the content of the comonomer component was determined by a method using 1H-NMR spectrum described in L. Tripathhi., M. C. Factories, 11, 44 (2012). ⁇ Measurement condition ⁇ Model: Bruker AVANCE600 Probe: 10 mm cryoprobe Measurement temperature: 135°C Pulse repetition time: 1 second Pulse width: 45° Number of times: 700 Magnetic field strength: 600 MHz
• pH of inorganic powder was evaluated according to JIS M 8016-1991 by adding 20 g of the inorganic powder to 80 mL of pure water, stirring the mixture, and using LAQUAtwin manufactured by Horiba Advanced Techno Co., Ltd.
• Example 1 5.0% by mass of the polymer (B-1), 85% by mass of the polymer (A-1), and 10.0% by mass of the inorganic powder (C-1) were mixed and melt-kneaded using a 15 mm twin-screw extruder KZW15-45MG (manufactured by Technovel) under the conditions of a cylinder set temperature of 210° C., a screw rotation speed of 500 rpm, and an extrusion rate of about 4 kg/hour to obtain a resin composition (Q-1).
• KZW15-45MG manufactured by Technovel
• Example 2 A resin composition (Q-1) was obtained in the same manner as in Example 1, except that the inorganic powder (C-2) was used.
• Example 3 A resin composition (Q-1) was obtained in the same manner as in Example 1, except that the inorganic powder (C-3) was used.
• Example 4 A resin composition (Q-1) was obtained in the same manner as in Example 1, except that the inorganic powder (C-4) was used.
• Example 1 to 4 in which inorganic powders C1 to C4 having a pH in the range of 6.5 to 11.5 were used, the amount of detection was smaller than that in Comparative Examples 1 and 2. In particular, in Examples 1 to 3, in which the pH was 9.5 or less, the amount of detection was particularly small.

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• 2022
  • 2022-10-11 JP JP2022163012A patent/JP2024056260A/ja active Pending
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