Classifications

• • 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
  • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/16—Compositions of unspecified macromolecular compounds the macromolecular compounds being biodegradable
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer

Definitions

• the present invention relates to a thermoplastic resin composition.
• Plastic waste causes a burden on the global environment, including its impact on the ecosystem, the generation of harmful gases when burned, and global warming due to the large amount of heat generated by combustion.
• Biodegradable materials are considered as materials that can solve this problem.
• the development of synthetic plastics is gaining momentum.
• Patent Document 1 0.1 to 20 parts by weight of poly(3-hydroxyalkanoate) particles with an average particle size of 300 ⁇ m or less are added to 100 parts by weight of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate).
• a thermoplastic resin composition that is biodegradable and has excellent environmental compatibility is described.
• thermoplastic resin According to the technique of blending poly(3-hydroxyalkanoate) particles into a thermoplastic resin, as described in Patent Document 1, the flexibility of the thermoplastic resin can be improved, but the durability of the thermoplastic resin may be improved. It does not contribute to improving impact resistance.
• the present invention aims to provide a thermoplastic resin composition with improved mechanical strength such as impact strength.
• the present invention comprises 40 to 90 parts by weight of a thermoplastic resin (A) and 10 to 60 parts by weight of crosslinked resin particles (B) containing a polyhydroxyalkanoate resin and having a gel fraction of 50% or more. parts [provided that the total amount of (A) and (B) is 100 parts by weight].
• the present invention also relates to a molded article of the thermoplastic resin composition.
• the present invention also relates to a modifier for a thermoplastic resin, which includes crosslinked resin particles (B) containing a polyhydroxyalkanoate resin and having a gel fraction of 50% or more.
• thermoplastic resin composition with improved mechanical strength such as impact strength.
• the thermoplastic resin composition according to the present invention is advantageous in terms of biodegradability because it contains crosslinked resin particles made of a polyhydroxyalkanoate resin.
• the crosslinked resin particles can be used as a modifier or an impact modifier for thermoplastic resins.
• the thermoplastic resin composition according to the present embodiment includes at least a thermoplastic resin (A) and crosslinked resin particles (B) containing a polyhydroxyalkanoate resin and having a gel fraction of 50% or more. It contains.
• the impact strength of the thermoplastic resin (A) is improved and good impact resistance can be exhibited.
• the crosslinked resin particles (B) will be explained.
• the crosslinked resin particles (B) are particles composed of a polyhydroxyalkanoate resin as a main resin component.
• polyhydroxyalkanoate resin may be abbreviated as "PHA”.
• PHA is a general term for polymers containing hydroxyalkanoic acids as monomer units, and is generally biodegradable.
• PHA is an aliphatic polyester, preferably a polyester containing no aromatic rings.
• the PHA is not particularly limited, but includes, for example, polyglycolic acid, poly(3-hydroxyalkanoate) resin, poly(4-hydroxyalkanoate) resin, and the like. As PHA, only one type may be used, or two or more types may be used in combination. Among these, poly(3-hydroxyalkanoate) resins are preferred. Hereinafter, poly(3-hydroxyalkanoate) resin may be abbreviated as "P3HA".
• the P3HA is a 3-hydroxyalkanoic acid repeating unit represented by the formula: [-CHR-CH 2 -CO-O-] (wherein R is an alkyl group represented by C n H 2n+1 , and n is 1 or more is an integer of 15 or less) as an essential repeating unit.
• the P3HA preferably contains the 3-hydroxyalkanoic acid repeating unit in an amount of 50 mol% or more of the total monomer repeating units (100 mol%), more preferably 70 mol% or more.
• P3HA is not particularly limited, but examples include poly(3-hydroxybutyrate) (abbreviation: P3HB), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (abbreviation: P3HB3HH), etc. .
• P3HA poly(3-hydroxybutyrate)
• P3HB3HH poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)
• P3HA3HH poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)
• P3HA can be produced by microorganisms. Such microorganism-produced P3HA is usually P3HA composed only of D-form (R-form) hydroxyalkanoic acid repeating units. Among microorganism-produced P3HA, P3HB and P3HB3HH are preferred, and P3HB3HH is more preferred, since industrial production is easy.
• the composition ratio of 3HB repeating units is 60 to 99 mol% in all monomer repeating units (100 mol%) from the viewpoint of balance between flexibility and strength. It is preferably 65 to 97 mol%, and even more preferably 67 to 95 mol%.
• the composition ratio of 3HB repeating units is 60 mol % or more, handling of the crosslinked resin particles (B) becomes easy.
• the composition ratio of 3HB repeating units is 99 mol % or less, flexibility of the crosslinked resin particles (B) tends to be easily ensured.
• the monomer composition ratio of P3HA can be measured by gas chromatography or the like (for example, see International Publication No. 2014/020838).
• two or more types having mutually different composition ratios of 3HB repeating units may be used in combination.
• the microorganism that produces P3HA is not particularly limited as long as it has the ability to produce P3HA.
• the first P3HB-producing bacterium was Bacillus megaterium, which was discovered in 1925, and other bacteria include Cupriavidus necator (former classification: Alcaligenes eutrophus), Ralstonia eutrophus Hua (Ralstonia eutropha)) , Alcaligenes latus and other natural microorganisms are known. In these microorganisms, P3HB accumulates inside the cells.
• Aeromonas caviae which is a P3HB3HH producing bacterium
• Aeromonas caviae which is a P3HB3HH producing bacterium
• a producing bacterium of copolymers of 3HB and other hydroxyalkanoates in particular, in order to increase the productivity of P3HB3HH, the Alcaligenes eutrophus AC32 strain (FERM BP-6038) into which genes of the P3HA synthetase group were introduced (T. Fukui, Y. Doi, J. Bateriol., 17 9 , p. 4821-4830 (1997)) is preferred. Microbial cells obtained by culturing such microorganisms under appropriate conditions and accumulating P3HA inside the cells are used. In addition to the above, genetically modified microorganisms into which various P3HA synthesis-related genes have been introduced may be used, and culture conditions including the type of substrate may be optimized, depending on the P3HA to be produced.
• the molecular weight of PHA is not particularly limited, but the weight average molecular weight is preferably 50,000 to 3,000,000, preferably 100,000 to 2,000,000, and preferably 150,000 to 1,500,000. More preferred. By setting the weight average molecular weight to 50,000 or more, it is possible to avoid a tendency for the strength of the crosslinked resin particles to decrease, or to avoid a tendency for the crosslinked resin particles to become sticky due to low molecular weight components. On the other hand, PHAs with weight average molecular weights exceeding 3,000,000 may be difficult to produce themselves or to handle for purposes of the present invention.
• the numerical value of the weight average molecular weight is a value measured before performing the crosslinking treatment of PHA.
• the method for measuring the weight average molecular weight is to use gel permeation chromatography (GPC) ("High Performance Liquid Chromatograph 20A System” manufactured by Shimadzu Corporation) and use polystyrene gel ("K-G 4A", "K -806M, etc.), using chloroform as a mobile phase, and calculating the molecular weight in terms of polystyrene.
• GPC gel permeation chromatography
• K-G 4A "K -806M, etc.
• the calibration curve can be created using polystyrene having weight average molecular weights of 31,400, 197,000, 668,000, and 1,920,000.
• a column suitable for measuring the molecular weight may be used as a column in the GPC.
• the crosslinked resin particles (B) have a crosslinked structure in which molecular chains of PHA are bonded to each other. Since the crosslinked resin particles (B) have a certain amount or more of such a crosslinked structure, the crosslinked resin particles (B) exhibit a high gel fraction, specifically, a gel fraction of 50% or more. By exhibiting such a high gel fraction, the effect of improving mechanical strength such as impact strength of the thermoplastic resin (A) can be enhanced.
• the value of the gel fraction is preferably 60% or more, more preferably 70% or more, even more preferably 75% or more, and particularly preferably 80% or more. Further, it may be 85% or more, or 90% or more.
• the upper limit of the gel fraction is not particularly limited and may be 100% or less, but from the viewpoint of production efficiency of crosslinked resin particles (B) and improvement of impact strength, it is preferably 99.5% or less. , more preferably 99% or less. Moreover, it may be 98% or less, 97% or less, or 96% or less.
• the gel fraction is a value measured as follows. Dry crosslinked resin particles (B) are added to chloroform at a concentration of 0.7% by weight, and dissolved at 60° C. for 30 minutes to obtain a chloroform solution. After that, the chloroform solution is left to stand at room temperature for 3 hours, and then filtered through a membrane filter with a pore size of 0.45 ⁇ m. The gel remaining on the filter is dried and weighed together with the filter, and the gel fraction is calculated using the following formula.
• Gel fraction (weight of filter containing dry gel - weight of filter only) / weight of crosslinked resin particles used for measurement x 100 (%)
• the volume average particle diameter of the crosslinked resin particles (B) is preferably within the range of 0.1 ⁇ m or more and 10 ⁇ m or less. By having such a particle size, mechanical strength such as impact strength of the thermoplastic resin (A) can be further improved.
• the lower limit of the particle size is preferably 0.1 ⁇ m or more, more preferably 0.3 ⁇ m or more, and even more preferably 0.5 ⁇ m or more, from the viewpoint of practical use opportunities. Further, from the viewpoint of productivity (PHA production, crosslinking treatment, etc.), the upper limit of the particle size is preferably 8 ⁇ m or less, more preferably 5 ⁇ m or less. However, by melt-kneading the crosslinked resin particles (B) with the thermoplastic resin (A), the original shape of the crosslinked resin particles (B) may collapse and the volume average particle diameter may decrease.
• the volume average particle diameter is a value measured in a state where the crosslinked resin particles (B) are dispersed in an aqueous solvent.
• a general-purpose measuring device can be used, and an example of such a device is Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd.
• the type of crosslinking in the crosslinked resin particles (B) is not particularly limited, but it is preferably crosslinked using a peroxide.
• peroxide radicals generated by decomposition of peroxide act on PHA molecules, and the PHA molecular chains are directly bonded to each other, thereby forming the crosslinked structure.
• the peroxide may be an organic peroxide or an inorganic peroxide.
• Organic peroxides are preferred because they can increase the gel fraction more efficiently.
• the organic peroxide may include diacyl peroxide, alkyl peroxy ester, dialkyl peroxide, hydroperoxide, peroxy ketal, peroxy carbonate, and peroxy, taking into account the heating temperature and time during crosslinking treatment. It is preferred to use at least one selected from the group consisting of dicarbonates.
• organic peroxides include butyl peroxyneododecanoate, octanoyl peroxide, dilauroyl peroxide, succinic peroxide, a mixture of toluoyl peroxide and benzoyl peroxide, and benzoyl peroxide.
• t-butylperoxyisopropyl monocarbonate t-pentylperoxyisopropyl monocarbonate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-pentylperoxy 2-ethylhexyl Monocarbonate, t-hexylperoxy 2-ethylhexyl monocarbonate, t-amylperoxyisopropyl monocarbonate, di-t-hexyl peroxide, t-butylperoxy 2-ethylhexanoate, t-butylperoxyisobutyl rate, t-hexylperoxy 2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, t-butylperoxypivalate, t-hexylperoxypivalate, t-he
• the peroxide is preferably a compound whose 1-hour half-life temperature is 200°C or lower, more preferably 170°C or lower, and 140°C or lower, since the heating temperature during crosslinking treatment can be set low. It is even more preferable that there be.
• the lower limit may be 50°C or higher, 60°C or higher, or 70°C or higher.
• Organic peroxides exhibiting such a 1-hour half-life temperature include t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, di-sec-butylperoxydicarbonate, and t-butylperoxy.
• the inorganic peroxide may be, for example, hydrogen peroxide, potassium peroxide, calcium peroxide, or Examples include sodium, magnesium peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, and the like.
• hydrogen peroxide, potassium persulfate, sodium persulfate, and ammonium persulfate are preferred because they are easy to handle and have a decomposition temperature suitable for the heating temperature during crosslinking treatment.
• One type of inorganic peroxide may be used alone, or two or more types may be used in combination. Further, organic peroxides and inorganic peroxides may be used in combination.
• the crosslinked structure in the crosslinked resin particles (B) may be introduced using only peroxide, or may be introduced using both peroxide and a polyfunctional compound. good. The latter makes it possible to increase the gel fraction of the crosslinked resin particles (B) with a smaller amount of peroxide.
• the polyfunctional compound refers to a compound that has two or more functional groups in one molecule that can crosslink PHA.
• compounds having reactivity with radicals generated from peroxides are preferred, and compounds having two or more radical-reactive groups in one molecule are particularly preferred.
• the radical-reactive group is preferably at least one selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, or a methacryloyl group.
• Such polyfunctional compounds are not particularly limited, but include, for example, allyl (meth)acrylate; allyl alkyl (meth) acrylates; allyloxyalkyl (meth) acrylates; ethylene glycol di (meth) acrylate, butane diol di (meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol (meth)acrylate, etc.
• Polyfunctional (meth)acrylates having two or more meth)acrylic groups examples include divinylbenzene, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and divinylbenzene.
• examples include divinylbenzene, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, and divinylbenzene.
• Preferred are allyl methacrylate, triallyl isocyanurate, butanediol di(meth)acrylate, and divinylbenzene, and particularly preferred are allyl methacrylate and triallyl isocyanurate.
• the obtained crosslinked resin particles (B) may usually contain a structure derived from the polyfunctional compound.
• the molecular chains of PHA are bonded to each other via a structure derived from the polyfunctional compound.
• the crosslinked resin particles (B) may be composed only of PHA having a crosslinked structure, or may further contain components other than PHA having a crosslinked structure.
• components other than PHA having a crosslinked structure include resins other than PHA, antioxidants, hydrolysis inhibitors, antiblocking agents, crystal nucleating agents, ultraviolet absorbers, and the like.
• the proportion of PHA in the crosslinked resin particles (B) is not particularly limited, but may be 50% by weight or more, preferably 70% by weight or more, more preferably 80% by weight or more, and even more preferably 90% by weight or more. , 95% by weight or more is particularly preferred. It may be 99% by weight or more.
• the upper limit is not particularly limited, as long as it is 100% by weight or less.
• resins other than PHA include aliphatic polyesters having a structure in which aliphatic diols and aliphatic dicarboxylic acids are polycondensed, and aliphatic aromatic polyesters having both an aliphatic compound and an aromatic compound as monomers. It will be done.
• the former include polyethylene succinate, polybutylene succinate (PBS), polyhexamethylene succinate, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polybutylene succinate adipate (PBSA), polyethylene sebacate, poly Examples include butylene sebacate.
• Examples of the latter include poly(butylene adipate-co-butylene terephthalate) (PBAT), poly(butylene sebacate-co-butylene terephthalate), poly(butylene azelate-co-butylene terephthalate), and poly(butylene succinate-co-butylene terephthalate). co-butylene terephthalate) (PBST).
• PBAT poly(butylene adipate-co-butylene terephthalate)
• PBST poly(butylene sebacate-co-butylene terephthalate)
• PBST co-butylene terephthalate
• the other resins may be used alone or in combination of two or more.
• the crosslinked resin particles (B) are different from the foamed resin particles as disclosed in International Publication No. 2007/049694 and International Publication No. 2019/146555, and are not foamed, i.e.
• the particles preferably contain substantially no air bubbles inside the particles.
• the apparent density of the crosslinked resin particles (B) exhibits a relatively large value, preferably exceeding 0.6 g/cm 3 , more preferably 0.7 g/cm 3 or more, and More preferably, it is .9 g/cm 3 or more.
• the apparent density of the crosslinked resin particles (B) can be determined by the method described in JIS K0061 (method for measuring density and specific gravity of chemical products) or JIS Z8807 (method for measuring density and specific gravity of solids).
• the average weight per crosslinked resin particle (B) is not particularly limited, but since the crosslinked resin particle (B) has a small volume average particle size of 10 ⁇ m or less, it is far less than 0.1 mg. It is a value.
• the crosslinked resin particles (B) may be dried.
• the shape after drying can be powder, pellet, crumb, sheet, etc. depending on the drying method.
• the crosslinked resin particles (B) can be produced by crosslinking PHA in the presence of peroxide in an aqueous dispersion containing PHA particles before crosslinking treatment. In order to efficiently crosslink PHA, it is preferable to heat an aqueous dispersion of PHA particles containing peroxide to a temperature suitable for decomposing the peroxide.
• the method for producing crosslinked resin particles (B) includes a step (1) of preparing an aqueous dispersion of PHA particles in which PHA particles before crosslinking treatment are dispersed in water; Step (2) of adding peroxide to the liquid and impregnating the PHA particles with peroxide, and heating the aqueous dispersion of PHA particles impregnated with peroxide to a heating temperature to crosslink the PHA ( 3) is preferably included. Furthermore, it is more preferable to include a step (4) of maintaining the heating temperature after all the peroxide is added.
• the aqueous dispersion of PHA particles is prepared by culturing PHA-producing microorganisms to accumulate PHA in the microbial cells, and then destroying the microbial cells in the culture solution and separating and removing the bacterial components.
• the aqueous dispersion may be the obtained aqueous dispersion, or an aqueous dispersion obtained by concentrating or diluting the aqueous dispersion. According to such a method, the process from producing PHA particles by culturing PHA-producing microorganisms to crosslinking treatment can be carried out without separating the PHA particles from water.
• an aqueous dispersion of PHA particles can also be prepared by dispersing dried PHA particles in water.
• the aqueous dispersion may contain, in addition to water, an organic solvent that is compatible with water.
• the volume average particle diameter of the PHA particles is preferably within the same range as the volume average particle diameter of the crosslinked resin particles (B) described above.
• the volume average particle size can usually be within the above range, so a desired volume average particle size can be achieved without implementing a special process to adjust the particle size.
• An aqueous dispersion of PHA particles can be obtained.
• the concentration of PHA particles in the aqueous dispersion is not particularly limited and can be set as appropriate, but may be, for example, about 1 to 70% by weight, preferably about 5 to 50% by weight.
• the aqueous dispersion of PHA particles preferably contains a dispersant in order to improve the dispersibility of the PHA particles and allow the crosslinking reaction to proceed uniformly.
• dispersants include anionic surfactants such as sodium dioctyl sulfosuccinate, sodium dodecyl sulfate, sodium lauryl sulfate, and sodium oleate; cationic surfactants such as lauryl trimethylammonium chloride; glycerin fatty acid ester, sorbitan fatty acid ester.
• nonionic surfactants such as sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene glycol; polyvinyl alcohol, ethylene-modified polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose, ethylcellulose, Examples include water-soluble polymers such as hydroxymethyl cellulose, hydroxyethyl cellulose, polyacrylic acid, sodium polyacrylate, potassium polyacrylate, polymethacrylic acid, and sodium polymethacrylate. These dispersants may be used alone or in combination of two or more.
• the amount added is not particularly limited, but may be, for example, 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of PHA particles. .
• step (2) peroxide is added to the aqueous dispersion of PHA particles obtained in step (1) to impregnate the PHA particles with peroxide.
• peroxide those mentioned above can be used.
• Peroxide can be added in various forms such as solid or liquid. Alternatively, a liquid diluted with a diluent or the like may be added. Peroxide may be added all at once, continuously or in portions.
• the polyfunctional compound is also added to the aqueous dispersion of PHA particles in this step (2).
• the polyfunctional compound those mentioned above can be used.
• the polyfunctional compound can be added in various forms such as solid or liquid. Alternatively, a liquid diluted with a diluent or the like may be added.
• the polyfunctional compound may be added all at once, continuously or in portions.
• the temperature of the aqueous dispersion is increased, e.g.
• the temperature may be set below a temperature suitable for decomposing the peroxide used in the next step (3), and the temperature may be maintained, for example, for about 1 minute to 5 hours while stirring the aqueous dispersion.
• the temperature of the aqueous dispersion during impregnation may be about 10 to 60°C.
• the amount of peroxide to be used can be appropriately set in consideration of the gel fraction of the crosslinked resin particles (B), but for example, it should be 0.01 to 10 parts by weight based on 100 parts by weight of PHA particles. is preferable, 0.1 to 8 parts by weight is more preferable, even more preferably 0.3 to 5 parts by weight, and particularly preferably 0.5 to 3 parts by weight.
• the amount of the polyfunctional compound to be used may be appropriately determined in consideration of the gel fraction of the crosslinked resin particles (B), and is, for example, 0.01 to 20 parts by weight based on 100 parts by weight of the PHA particles. It is preferably 0.05 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, even more preferably 0.2 to 5 parts by weight, and particularly preferably 0.3 to 3 parts by weight.
• step (3) the aqueous dispersion of PHA particles impregnated with peroxide is heated to a temperature suitable for decomposing the peroxide.
• the heating temperature is preferably within a range of about 25° C. above and below the 1-hour half-life temperature of the peroxide described above. Specifically, the heating temperature is preferably 30 to 140°C, more preferably 50 to 135°C, and even more preferably 60 to 130°C. According to this method, since it is possible to crosslink PHA at a temperature lower than the melting temperature of PHA, it is possible to avoid deterioration of PHA due to heating during crosslinking treatment.
• the heating temperature is not particularly limited, but is preferably from 1 minute to 15 hours, more preferably from 1 hour to 10 hours.
• dry crosslinked resin particles (B) can be obtained by separating the crosslinked resin particles (B) from the aqueous dispersion and removing water.
• the method for separating the crosslinked resin particles (B) is not particularly limited, and for example, filtration, centrifugation, heat drying, freeze drying, spray drying, etc. can be used.
• spray drying dried crosslinked resin particles (B) can be obtained directly from the aqueous dispersion.
• the crosslinked resin particles (B) can be obtained in the form of pellets while completely removing residual moisture.
• a coagulation step using a coagulant or pH adjustment may be carried out.
• the blending amount of the crosslinked resin particles (B) is 10 to 60 parts by weight based on a total of 100 parts by weight of the thermoplastic resin (A) and the crosslinked resin particles (B). It is.
• the blending amount may be 15 parts by weight or more, 20 parts by weight or more, or 25 parts by weight or more.
• the upper limit of the blending amount is preferably 55 parts by weight or less, more preferably 50 parts by weight or less, particularly preferably 45 parts by weight or less.
• thermoplastic resin (A) that is the matrix resin is not particularly limited as long as it is a resin that can be molded into a desired shape by melting by heating and then cooling and solidifying.
• polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polyurethane, polytetrafluoroethylene, acrylic resins such as polymethyl methacrylic acid, AS resins, polyamides, polyacetals, polycarbonates, Examples include modified polyphenylene ether, polyester resin, and cyclic polyolefin.
• These thermoplastic resins may be used alone or in combination of two or more.
• polyester resin is particularly preferred.
• the polyester resin include PHA such as polyglycolic acid, poly(3-hydroxyalkanoate) resin, and poly(4-hydroxyalkanoate) resin; polylactic acid; aliphatic diol and aliphatic dicarboxylic acid.
• PHA polyglycolic acid
• poly(4-hydroxyalkanoate) resin poly(4-hydroxyalkanoate) resin
• polylactic acid aliphatic diol and aliphatic dicarboxylic acid
• aliphatic polyesters such as polyesters having a polycondensed structure, and aliphatic aromatic polyesters containing both an aliphatic compound and an aromatic compound as monomers.
• aliphatic polyesters other than PHA examples include polycaprolactone, polyethylene succinate, polybutylene succinate (PBS), polyhexamethylene succinate, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polybutylene succinate adipate (PBSA), polyethylene sebacate, polybutylene sebacate, and the like.
• polyesters examples include poly(butylene adipate-co-butylene terephthalate) (PBAT), poly(butylene sebacate-co-butylene terephthalate), poly(butylene azelate-co-butylene terephthalate), poly( Examples include butylene succinate (co-butylene terephthalate) (PBST), polyethylene furanoate, and the like. These polyester resins may be used alone or in combination of two or more.
• thermoplastic resin (A) also contains a biodegradable resin. In this case, the biodegradability of the thermoplastic resin composition as a whole can be improved.
• thermoplastic resin (A) is also a resin produced from plant-derived raw materials.
• thermoplastic resin (A) contains a biodegradable resin
• the content thereof is preferably 10 to 100% by weight, more preferably 30% by weight or more, based on the entire thermoplastic resin (A). It is more preferably 50% by weight or more, even more preferably 70% by weight or more, and particularly preferably 90% by weight or more.
• the biodegradable resin used as the thermoplastic resin (A) preferably contains the above-mentioned aliphatic polyester, since the crosslinked resin particles (B) have an excellent effect of improving impact resistance, and preferably contains PHA and/or polylactic acid. It is particularly preferred to include. Note that the PHA used as the thermoplastic resin (A) preferably does not have a crosslinked structure.
• thermoplastic resin (A) contains PHA and/or polylactic acid
• the content thereof is preferably 10 to 100% by weight, more preferably 30% by weight or more based on the entire thermoplastic resin (A). It is preferably at least 50% by weight, more preferably at least 70% by weight, even more preferably at least 90% by weight.
• thermoplastic resin (A) that can be used as the thermoplastic resin (A) is not particularly limited, and examples thereof include polyglycolic acid, P3HA, poly(4-hydroxyalkanoate)-based resins, and the like.
• PHA only one type may be used, or two or more types may be used in combination. Among these, P3HA is particularly preferred.
• the P3HA that can be used as the thermoplastic resin (A) is the same as the P3HA associated with the crosslinked resin particles (B), and the various P3HAs described above can be used.
• the P3HA used as the thermoplastic resin (A) is preferably different from the P3HA used for the crosslinked resin particles (B), and is preferably a harder resin than the P3HA used for the crosslinked resin particles (B). More preferred.
• thermoplastic resin (A) contains 3-hydroxybutanoic acid (3HB) repeating units
• 3HB repeating units are included in all monomer repeating units (100 mol%).
• the composition ratio is preferably 80 to 99 mol%, more preferably 82 to 97 mol%.
• the composition ratio of 3HB repeating units is 80 mol% or more, the rigidity of P3HA can be further improved.
• the composition ratio of 3HB repeating units is 99 mol% or less, the flexibility of P3HA tends to be further improved.
• two or more types having mutually different composition ratios of 3HB repeating units may be used in combination.
• the molecular weight of PHA used as the thermoplastic resin (A) is not particularly limited, but the weight average molecular weight is preferably 50,000 to 3,000,000, preferably 100,000 to 2,000,000, and 150 ,000 to 1,500,000 is more preferable. By setting the weight average molecular weight to 50,000 or more, sufficient rigidity and strength can be obtained in the thermoplastic resin composition according to the present embodiment. On the other hand, PHA with a weight average molecular weight exceeding 3,000,000 may be difficult to produce itself or to handle in order to achieve the purpose of the present invention.
• polylactic acid that can be used as the thermoplastic resin (A)
• conventionally known polylactic acids can be used, and they may be either crystalline or amorphous.
• Polylactic acid may be a homopolymer of lactic acid or a copolymer of lactic acid and other monomers. Moreover, a blend of these may be used.
• the other monomers include aliphatic hydroxycarboxylic acids other than lactic acid, aliphatic polyhydric alcohols, aliphatic polycarboxylic acids, and polyfunctional polysaccharides.
• the lactic acid raw material for producing polylactic acid is not particularly limited, and may include L-lactic acid, D-lactic acid, DL-lactic acid, or mixtures thereof, L-lactide, D-lactide, meso-lactide, or mixtures thereof. etc. can be used. Lactic acid obtained by microbial fermentation from plant-derived renewable raw materials such as starch can be suitably used.
• known methods such as dehydration condensation polymerization method and ring-opening polymerization method can be applied, and are not particularly limited.
• the molecular weight of polylactic acid (A) used as the thermoplastic resin (A) is not particularly limited, but the weight average molecular weight is preferably 50,000 to 1,000,000, and preferably 70,000 to 700,000. , 100,000 to 400,000 is more preferable. By setting the weight average molecular weight to 50,000 or more, sufficient rigidity and strength can be obtained in the thermoplastic resin composition according to the present embodiment. On the other hand, polylactic acid having a weight average molecular weight exceeding 1,000,000 may be difficult to produce itself or to handle in order to achieve the purpose of the present invention.
• the thermoplastic resin composition may further contain a crystal nucleating agent.
• a crystal nucleating agent By containing the crystal nucleating agent in the thermoplastic resin composition, when the thermoplastic resin (A) is a crystalline resin, crystallization during molding is promoted, improving molding processability, productivity, etc. It is possible. Furthermore, a thermoplastic resin composition with excellent heat resistance or mechanical properties can be obtained.
• the crystal nucleating agent is not particularly limited, and conventionally known ones can be used, such as talc, kaolinite, montmorinite, mica, synthetic mica, clay, zeolite, silica, carbon black, graphite, and boron nitride.
• inorganic substances such as zinc oxide, titanium oxide, tin oxide, calcium carbonate, magnesium carbonate, aluminum oxide, neodymium oxide, barium sulfate, sodium chloride, metal phosphates; natural substances such as erythritol, pentaerythritol, galactitol, mannitol, arabitol, etc.
• polysaccharides such as chitin and chitosan
• polyols such as aliphatic alcohols (polyols), polyvinyl alcohol, and polyethylene oxide
• the content of the crystal nucleating agent is not particularly limited as long as it can promote crystallization of the thermoplastic resin (A), but it is preferably 0.05 to 12 parts by weight based on 100 parts by weight of the thermoplastic resin (A). , more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 8 parts by weight.
• the content of the crystal nucleating agent is within the above range, the effect as a crystal nucleating agent can be obtained while suppressing deterioration of the viscosity during molding and the physical properties of the molded article.
• the thermoplastic resin composition may further contain a lubricant.
• a lubricant By containing a lubricant, the surface smoothness of the obtained molded article can be improved.
• the lubricant include, but are not limited to, fatty acid metal salts such as magnesium stearate and calcium stearate, behenic acid amide, stearic acid amide, erucic acid amide, oleic acid amide, methylene bis stearic acid amide, ethylene bis stearic acid amide, etc.
• fatty acid amides polyethylene wax, oxidized polyester wax, glycerin monofatty acid esters such as glycerin monostearate, glycerin monobehenate, glycerin monolaurate; organic acid monoglycerides such as succinic acid saturated fatty acid monoglyceride; sorbitan behenate, sorbitan stear sorbitan fatty acid esters such as sorbitan laurate and sorbitan laurate; polyglycerin fatty acid esters such as diglycerin stearate, diglycerin laurate, tetraglycerin stearate, tetraglycerin laurate, decaglycerin stearate, and decaglycerin laurate; stearyl stearate Examples include higher alcohol fatty acid esters such as, but are not limited to.
• the lubricants may be used alone or in combination of two or more.
• the content of the lubricant is not particularly limited as long as it can impart lubricity to the molded article, but it is 0.01 parts by weight per 100 parts by weight of the thermoplastic resin (A). -20 parts by weight is preferred, more preferably 0.05-10 parts by weight, even more preferably 0.1-10 parts by weight, even more preferably 0.2-5 parts by weight, and even more preferably 0.3-4 parts by weight. part is particularly preferred.
• the content of the lubricant is within the above range, the lubricant effect can be obtained while avoiding bleeding out of the lubricant onto the surface of the molded article.
• the thermoplastic resin composition according to the present embodiment includes a plasticizer; an organic filler; an inorganic filler; an antioxidant; a hydrolysis inhibitor; an ultraviolet absorber; a dye; It may contain other components such as colorants such as pigments and antistatic agents.
• the plasticizer is not particularly limited, but includes, for example, polyester plasticizers such as polypropylene glycol sebacate; fats such as di-1-butyl adipate, di-n-butyl sebacate, and di-2-ethylhexyl azelate.
• polyester plasticizers such as polypropylene glycol sebacate
• fats such as di-1-butyl adipate, di-n-butyl sebacate, and di-2-ethylhexyl azelate.
• Group dibasic acid ester plasticizers Glycerin plasticizers such as glycerin diacetomonolaurate, glycerin diacetomonocaprylate, and glycerin diacetomonodecanoate; Polyvalent carboxylic acid ester plasticizer; polyalkylene glycol plasticizer such as polyethylene glycol, polypropylene glycol, poly(ethylene oxide/propylene oxide) block and/or random copolymer, polytetramethylene glycol; diphenyl-2-phosphate Phosphate ester plasticizers such as ethylhexyl and diphenyloctyl phosphate; Epoxy plasticizers such as epoxidized soybean oil and epoxidized linseed oil fatty acid butyl ester; Castor oil fatty acid ester, methyl ricinoleate, ethyl ricinoleate, isopropyl ricinoleate , butyl ricinoleate,
• the organic filler is not particularly limited, but includes, for example, wood-based materials such as wood chips, wood flour, and sawdust, and naturally derived materials such as rice husk, rice flour, starch, corn starch, rice straw, wheat straw, and natural rubber.
• fillers organic fibers such as vegetable natural fibers, animal natural fibers, and synthetic fibers; polyester, polyacrylic, polyamide, nylon, polyethylene, polyolefin, polyvinyl alcohol, polyvinyl chloride, polyurethane, polyacetal, aramid, PBO (
• fillers include synthetic resin materials such as poly(p-phenylenebenzobisoxazole), polyphenylene sulfide, acetyl cellulose, polybenzazole, polyarylate, polyvinyl acetate, and synthetic rubber.
• Examples of the vegetable natural fibers include kenaf fiber, abaca fiber, bamboo fiber, jute fiber, hemp fiber, linen fiber, heneken (sisal hemp), ramie fiber, hemp, cotton, banana fiber, coconut fiber, coconut fiber, palm fiber, etc. , mulberry, mulberry, bagasse, etc.
• Other examples include pulp processed from plant fibers, cellulose fibers, and recycled fibers such as rayon.
• Examples of animal natural fibers include wool, silk, cashmere, and mohair.
• the inorganic filler is not particularly limited, but includes, for example, silica such as quartz, fumed silica, silicic anhydride, fused silica, crystalline silica, amorphous silica, filler formed by condensing alkoxysilane, and ultrafine amorphous silica.
• silica such as quartz, fumed silica, silicic anhydride, fused silica, crystalline silica, amorphous silica, filler formed by condensing alkoxysilane, and ultrafine amorphous silica.
• Inorganic fillers alumina, zircon, iron oxide, zinc oxide, titanium oxide, silicon nitride, boron nitride, aluminum nitride, silicon carbide, glass, silicone rubber, silicone resin, titanium oxide, carbon fiber, mica, graphite, carbon black, Examples include ferrite, graphite, diatomaceous earth, clay, clay, talc, calcium carbonate, manganese carbonate, magnesium carbonate, barium sulfate, and silver powder. These may be surface-treated to improve dispersibility in the resin composition. Further, these may be used alone or in combination of two or more.
• the antioxidant is not particularly limited, but examples thereof include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. These may be used alone or in combination of two or more.
• the hydrolysis inhibitor is not particularly limited, but includes, for example, carbodiimide compounds, epoxy compounds, isocyanate compounds, oxazoline compounds, and the like. These may be used alone or in combination of two or more.
• the ultraviolet absorber is not particularly limited, but includes, for example, benzophenone compounds, benzotriazole compounds, triazine compounds, salicylic acid compounds, cyanoacrylate compounds, nickel complex compounds, and the like. These may be used alone or in combination of two or more.
• the colorants such as pigments and dyes are not particularly limited, but include inorganic colorants such as titanium oxide, calcium carbonate, chromium oxide, cuprous oxide, calcium silicate, iron oxide, carbon black, graphite, titanium yellow, and cobalt blue.
• Colorants such as Lake Red, Lysol Red, Brilliant Carmine, insoluble azo pigments such as Dinitriane Orange, Fast Yellow, phthalocyanine pigments such as Monochlorophthalocyanine Blue, Polychlorophthalocyanine Blue, Polybromophthalocyanine Green, Indigo Blue
• Examples include fused polycyclic pigments such as perylene red, isoindolinone yellow, and quinacridone red, and dyes such as oracet yellow. These may be used alone or in combination of two or more.
• the antistatic agent is not particularly limited, but examples include low molecular weight antistatic agents such as fatty acid ester compounds, aliphatic ethanolamine compounds, aliphatic ethanolamide compounds, and polymeric antistatic agents. can. These may be used alone or in combination of two or more.
• the thermoplastic resin composition according to the present embodiment also contains catalyst deactivators (hindered phenol compounds, thioether compounds, vitamin compounds, triazole compounds, polyvalent amine compounds, hydrazine derivative compounds, phosphorus compounds, etc.). compounds), mold release agents (montanic acid and its salts, its esters, its half esters, stearyl alcohol, stearamide and polyethylene wax, etc.), color inhibitors (phosphites, hypophosphites, etc.), silane cups Ring agents (epoxy silane coupling agents, amino silane coupling agents, (meth)acrylic silane coupling agents, isocyanate silane coupling agents, etc.), flame retardants (red phosphorus, phosphoric acid esters, brominated polystyrene, brominated polyphenylene ether, bromine) polycarbonate, aluminum hydroxide, magnesium hydroxide, melamine and cyanuric acid or its salts, silicon compounds, etc.), conductive agents (carbon black, etc.), sliding properties improver
• thermoplastic resin composition can be manufactured by a known method. Specifically, the thermoplastic resin (A), crosslinked resin particles (B), and optional components such as a crystal nucleating agent, a lubricant, and other components are mixed using an extruder, kneader, Banbury mixer, kneading roll, etc. Examples include a method of melt-kneading. When melt-kneading, it is preferable to mix while paying attention to molecular weight reduction due to thermal decomposition.
• the thermoplastic resin composition can also be produced by dissolving each component in a soluble solvent and then removing the solvent.
• each component When producing by melt-kneading, each component may be individually charged into an extruder, etc., or each component may be mixed in advance and then charged into an extruder, etc.
• an aqueous dispersion of thermoplastic resin (A) and an aqueous dispersion of crosslinked resin particles (B) may be mixed, dried to obtain a mixed powder, and the mixed powder may be fed into an extruder or the like.
• thermoplastic resin composition When melt-kneaded using an extruder, the resulting thermoplastic resin composition is extruded into strands and then cut to produce particle shapes such as bar, cylinder, elliptical cylinder, sphere, cube, and rectangular parallelepiped. It may be processed into
• the resin temperature during melt-kneading cannot be determined unconditionally because it depends on the melting point and melt viscosity of the resin used, but it is necessary to uniformly disperse the crosslinked resin particles (B) while avoiding thermal decomposition of the thermoplastic resin (A).
• the temperature is preferably 140 to 220°C, more preferably 150 to 210°C, and even more preferably 160 to 200°C.
• a molded article can be manufactured from the thermoplastic resin composition according to this embodiment.
• the molding method is not particularly limited, and commonly used molding methods can be applied, but specifically, blown film molding, extrusion blow molding, injection blow molding, extrusion molding, calendar molding, vacuum molding, injection molding Examples include.
• molded products with improved impact resistance can be produced with good productivity, specifically, sheets, films, blow molded products, extrusion molded products, vacuum molded products, Injection molded products can be manufactured.
• the molded body made of the thermoplastic resin composition according to the present embodiment is suitable for agriculture, fishing, forestry, horticulture, medicine, sanitary products, food industry, clothing, non-clothing, packaging, automobiles, building materials, and other fields. It can be used for.
• thermoplastic resin composition 40 to 90 parts by weight of thermoplastic resin (A), and 10 to 60 parts by weight of crosslinked resin particles (B) containing a polyhydroxyalkanoate resin and having a gel fraction of 50% or more [However, the total amount of (A) and (B) is 100 parts by weight ], a thermoplastic resin composition.
• thermoplastic resin composition according to claim 1, wherein the polyhydroxyalkanoate-based resin is a poly(3-hydroxyalkanoate)-based resin.
• thermoplastic resin composition according to item 1 or 2 wherein the crosslinked resin particles (B) have a volume average particle diameter of 0.1 ⁇ m or more and 10 ⁇ m or less.
• thermoplastic resin composition according to any one of items 1 to 3 wherein the crosslinked resin particles (B) are crosslinked using a peroxide.
• thermoplastic resin composition according to any one of items 1 to 4 wherein the crosslinked resin particles (B) are further crosslinked in the presence of a polyfunctional compound.
• thermoplastic resin composition according to any one of items 1 to 5 wherein the crosslinked resin particles (B) are not foamed.
• thermoplastic resin composition according to any one of items 1 to 7 wherein the thermoplastic resin (A) contains a biodegradable resin.
• thermoplastic resin composition according to item 8 wherein the biodegradable resin is a polyester resin.
• thermoplastic resin composition according to any one of items 1 to 9 further comprising a crystal nucleating agent and/or a lubricant.
• the molded article according to item 11 which is a sheet, a film, a blow molded product, an extrusion molded product, a vacuum molded product, or an injection molded product.
• a modifier for a thermoplastic resin comprising crosslinked resin particles (B) containing a polyhydroxyalkanoate resin and having a gel fraction of 50% or more.
• volume average Particle Diameter The volume average particle diameter of crosslinked resin particles or uncrosslinked resin particles was measured in the state of resin particle latex.
• Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd. was used as a measuring device.
• Peroxide PO-1 t-butyl peroxypivalate (“Luperox 11” manufactured by Arkema Yoshitomi Co., Ltd., 1 hour half-life temperature: 76°C)
• PO-2 t-butylperoxy-2-ethylhexanoate (“Luperox 26” manufactured by Arkema Yoshitomi Co., Ltd., 1 hour half-life temperature: 95°C)
• PO-3 t-butylperoxy-2-ethylhexyl monocarbonate (“Perbutyl E” manufactured by NOF Corporation, 1 hour half-life temperature: 119°C)
• PO-4 Di-sec-butyl peroxydicarbonate (“Luperox 225” manufactured by Arkema Yoshitomi Co., Ltd., 1 hour half-life temperature: 69°C) 2-3.
• Polyfunctional compound CA-1 allyl methacrylate
• CA-2 triallyl isocyanurate
• the volume average particle diameter and gel fraction of the uncrosslinked resin particles before carrying out the crosslinking reaction were measured by the method described above, and the results are shown in Table 1 as a reference example.
• the uncrosslinked resin particles or their aqueous dispersions were used in Comparative Examples 2-4 and 8.
• test pieces Examples 1 to 21 and Comparative Examples 1 to 4.
• the mixture of (a), (b), (c), and (d) was heated to the barrel temperature listed in Table 2 in a small twin-screw kneader (DSM Xplore MC5) at a screw rotation speed.
• the mixture was kneaded for 180 seconds at 100 rpm to obtain a kneaded product.
• This kneaded product was dried in a dryer at 80° C. for 4 hours to sufficiently reduce the water content, and then press-molded at 165° C. to a predetermined thickness to prepare a test piece.
• Example 22 An aqueous dispersion in which thermoplastic resin (A) particles are dispersed and an aqueous dispersion of crosslinked resin particles (B) produced in Production Example 11 are mixed so that the weight ratio of the solid content is 70/30%. After adjusting the pH to 3.8, the resin mixture was dried in an oven to obtain a resin mixture. The resin mixture and the mixture of (c) and (d) were kneaded under the same conditions as above to prepare a test piece.
• test pieces (Examples 23 to 29 and Comparative Examples 5 to 8)
• the mixture of (a) and (b) was kneaded for 180 seconds at a screw rotation speed of 100 rpm in a small twin-screw kneader (DSM Xplore MC5) heated to a barrel temperature of 175°C. I got something.
• This kneaded product was dried in a dryer at 90° C. for 2 hours to sufficiently reduce the water content, and then press-molded at 170° C. to a predetermined thickness to prepare a test piece.
• the mixture was kneaded under certain conditions to obtain a kneaded product.
• This kneaded product was dried in a dryer at 80° C. for 4 hours to sufficiently reduce the moisture content.
• a 30MT injection molding machine Si-30IV manufactured by Toyo Kikai Kinzoku Co., Ltd.
• a cylinder temperature 140 to 165°C
• a mold temperature 40°C
• a volume of 328 ml a thickness of 1.2 mm
• an opening diameter of 66 mm an opening diameter of 66 mm
• a high A bottle-shaped molded body with a length of 1010 mm was produced.

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• 2023
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