WO2023204205A1 - 重合体、樹脂添加剤、樹脂組成物、及び成形体 - Google Patents

重合体、樹脂添加剤、樹脂組成物、及び成形体 Download PDF

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WO2023204205A1
WO2023204205A1 PCT/JP2023/015445 JP2023015445W WO2023204205A1 WO 2023204205 A1 WO2023204205 A1 WO 2023204205A1 JP 2023015445 W JP2023015445 W JP 2023015445W WO 2023204205 A1 WO2023204205 A1 WO 2023204205A1
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polymer
resin
parts
mass
polymer portion
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PCT/JP2023/015445
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English (en)
French (fr)
Japanese (ja)
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豊 青木
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三菱ケミカル株式会社
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Priority to CN202380034212.9A priority Critical patent/CN119032117A/zh
Priority to JP2024516266A priority patent/JPWO2023204205A1/ja
Publication of WO2023204205A1 publication Critical patent/WO2023204205A1/ja

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    • 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
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • 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

Definitions

  • the present invention relates to a polymer, a resin additive, a resin composition, and a molded article.
  • Patent Document 1 discloses that polybutylene terephthalate resin, polystyrene resin, and carbon fiber have good low warpage and mechanical properties by using polycarbonate as a compatibilizer.
  • one aspect of the present invention is to develop a polymer that can improve the compatibility when a polyester resin represented by polybutylene terephthalate resin is combined with other resins, and also has excellent tensile elongation of a molded product. The purpose is to provide.
  • One aspect of the present invention is a polymer having a first polymer portion and a second polymer portion, wherein the first polymer portion is a polyester polymer, and the second polymer portion is a polyester polymer.
  • the combined portion has a structural unit different from the structural unit constituting the first polymer portion, and the first polymer portion is contained in a total of 100 parts by mass of the first polymer portion and the second polymer portion.
  • the proportion of the polymer is more than 20 parts by mass and 90 parts by mass or less, and the second polymer part has a structural unit derived from a (meth)acrylate monomer.
  • a polymer or the like that can improve the compatibility of the resins and reduce phase separation when two or more resins are mixed, and also has excellent tensile elongation of a molded article.
  • Example 1 is a cross-sectional photograph of the molded product of Example 1 observed with a transmission electron microscope.
  • 1 is a cross-sectional photograph of a molded article of Comparative Example 1 observed with a transmission electron microscope.
  • the polymer according to the present embodiment includes a first polymer portion that is a polyester polymer, a second polymer portion that has a constitutional unit different from the constitutional unit that constitutes the first polymer portion, (hereinafter sometimes referred to as polymer A).
  • polymer A a resin additive for two or more types of matrix resins including a polyester resin
  • the compatibility with the first matrix resin and the second matrix resin can be improved. Therefore, phase separation between the first matrix resin and the second matrix resin can be reduced.
  • Polymer A is a polymer having a first polymer portion and a second polymer portion, where the first polymer portion is a polyester polymer and the second polymer portion is a polyester polymer.
  • the polymer portion has a structural unit different from the structural unit constituting the first polymer portion, and the first polymer portion in a total of 100 parts by mass of the first polymer portion and the second polymer portion.
  • the ratio of coalescence is more than 20 parts by mass and less than 90 parts by mass
  • the second polymer portion has a structural unit derived from a (meth)acrylate monomer.
  • a polymer having a first polymer portion and a second polymer portion is one in which the first polymer portion and the second polymer portion are covalently bonded. It may also be a polymer with Further, in one embodiment of the present invention, even when the first polymer portion and the second polymer portion are not covalently bonded, the first polymer is encapsulated or externally encapsulated by the second polymer. It also includes polymers.
  • the polymer in which the first polymer part and the second polymer part are covalently bonded examples include a block copolymer having the first polymer part and the second polymer part.
  • the core portion includes one of the first polymer portion and the second polymer portion
  • examples include polymers having a core-shell structure in which the shell portion includes the other polymer portion of the first polymer portion and the second polymer portion. Note that the core-shell structure is a structure in which a portion called a core is included in a portion called a shell.
  • the polymer A is a polymer that has a core-shell structure and the first polymer portion constitutes the shell portion of the core-shell structure. That is, in Polymer A, a first polymer portion which is a polyester polymer constitutes a shell portion of a core-shell structure, and a first polymer portion having a constitutional unit different from the constitutional unit constituting the first polymer portion. It is preferable that the polymer portion of No. 2 is a polymer constituting the core portion.
  • a preferred form of the polymer A having the core-shell structure will be described in detail.
  • the first polymer portion is composed of a polyester polymer.
  • a polyester-based polymer refers to a polymer composed of structural units containing ester bonds as repeating units, and polyester is synthesized by a polycondensation reaction between a dicarboxylic acid component and a diol component. be done. Since the first polymer portion is composed of a polyester polymer, the affinity with the first matrix resin, which is a polyester resin, is improved, and as a result, the first matrix resin and the second matrix resin are This results in improved compatibilization.
  • the dicarboxylic acid is not particularly limited and includes aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, etc.
  • aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 2, 5-norbonanedicarboxylic acid, 1,4-naphthalic acid, 1,5-naphthalic acid, 4,4-oxybenzoic acid, fumaric acid, maleic anhydride, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedicarboxylic acid acid, tetrahydrophthalic anhydride, tetrahydroterephthalic acid, 5-sodium sulfoisophthalic acid, 5-lithium sulfoisophthalic acid, (anhydrous) trimellitic acid, (anhydrous) pimelitic acid, and the like.
  • diol component examples include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, triethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide and propylene oxide adduct of bisphenyl A, hydrogenated bisphenol Examples include ethylene oxide adducts and propylene oxide adducts of A, polytetramethylene glycol, polyethylene glycol, polypropylene glycol and modified products thereof, sodium sulfobutanediol, and the like.
  • dicarboxylic acid components may be used, and similarly, two or more types of diol components may be used.
  • the first polymer portion may be composed of a plurality of polymers each having a plurality of different structural units.
  • structural units in this case those exemplified as the structural units of the first polymer can be used.
  • the mass average molecular weight of the first polymer portion is not particularly limited, but for ease of powder handling, it is preferably 3000 or more, more preferably 5000 or more, and particularly 7000 or more. preferable.
  • the mass average molecular weight is preferably 200,000 or less, more preferably 100,000 or less, and particularly preferably 50,000 or less. Note that the mass average molecular weight can be measured by gel permeation chromatography (GPC).
  • the glass transition temperature of the first polymer portion is not particularly limited, but in order to ensure powder recovery, it is preferably 40°C or higher, more preferably 45°C or higher, and 50°C or higher. It is particularly preferable that there be. On the other hand, in order to avoid pulverization of the powder, the glass transition temperature is preferably 150°C or lower, more preferably 130°C or lower, and particularly preferably 100°C or lower.
  • the second polymer portion has different constitutional units from those making up the first polymer portion.
  • the second polymer portion has a structural unit derived from a (meth)acrylate monomer. Having a structural unit derived from a (meth)acrylate monomer improves the tensile elongation of the molded article.
  • the second polymer portion preferably has a structural unit other than the structural unit derived from the (meth)acrylate monomer, and such a structural unit has an affinity with the second matrix resin. It is preferable that it is an excellent component. Specifically, it is preferable that at least some of the structural units of the second polymer portion and at least some of the structural units that constitute the second matrix resin are the same.
  • examples of the (meth)acrylate monomer include methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, Butyl methacrylate, propyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, propyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, phenyl acrylate, phenyl methacrylate, hydroxyethyl acrylate, 4-hydroxybutyl acrylate, benzyl acrylate, benzyl methacrylate, polyalkylene glycol Mention may be made of monoacrylates or polyalkylene glycol monomethacrylates. Among these, methyl methacrylate, butyl acrylate, glycidyl methacrylates
  • the amount is preferably 5 parts by mass or more, and on the other hand, 80 parts by mass or less. More preferably, it is 8 parts by mass or more and 60 parts by mass or less.
  • the structural units constituting the second polymer portion other than the structural units derived from the (meth)acrylate monomer are preferably set according to the structure of the second matrix resin to be used.
  • Examples include structural units derived from group vinyl monomers.
  • the structural units constituting the second polymer portion include structural units derived from the vinyl aromatic monomer, for example, when a polystyrene-containing resin is used as the second matrix resin, the second polymer portion It can be expected that the compatibility between the polystyrene-containing resin and the polystyrene-containing resin becomes better, and as a result, the compatibility between the first matrix resin and the second matrix resin becomes better.
  • the structural unit constituting the second polymer portion is preferably a structural unit derived from an aromatic vinyl monomer having a 6-membered monocyclic structure, and has a substituent. More preferably, it is a structural unit derived from styrene.
  • the styrene-derived structural unit which may have a substituent include a styrene-derived structural unit or an ⁇ -methylstyrene-derived structural unit, and among them, a styrene-derived structural unit is particularly preferable.
  • the amount is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 60 parts by mass or more, particularly preferably 70 parts by mass or more, and on the other hand, 95 parts by mass or more. It is preferably less than 100 parts by mass.
  • the second polymer portion may further include other structural units.
  • the proportion of other structural units in all structural units of the second polymer portion is not particularly limited, but is 50 parts by mass or less in order to further improve the compatibility between the first matrix resin and the second matrix resin. It is preferably 30 parts by mass or less, more preferably 30 parts by mass or less, particularly preferably 20 parts by mass or less, and on the other hand, 0 parts by mass or more.
  • the second polymer portion may be composed of a plurality of polymers having a plurality of different structural units.
  • structural units in this case those exemplified as the structural units of the second polymer can be used.
  • the proportion of the first polymer in the total of 100 parts by mass of the first polymer portion and the second polymer portion is the proportion of the first matrix resin and the second matrix resin using polymer A as a resin additive.
  • the amount is preferably more than 20 parts by mass and not more than 90 parts by mass. More preferably more than 20 parts by mass and not more than 80 parts by mass, still more preferably more than 20 parts by mass and not more than 70 parts by mass, even more preferably more than 20 parts by mass and not more than 60 parts by mass, even more preferably 20 parts by mass.
  • the amount is more than 20 parts by weight and not more than 50 parts by weight, more preferably more than 20 parts by weight and not more than 45 parts by weight, and particularly preferably more than 20 parts by weight and not more than 40 parts by weight.
  • Method for producing polymer A> There are no particular limitations on the method for producing the polymer A when it has a core-shell structure, and it can be produced by known methods such as suspension polymerization, solution polymerization, or emulsion polymerization. Among these, from the viewpoint of ease of production, it is preferable to produce by emulsion polymerization. That is, Polymer A is a polymer obtained by emulsion polymerization of the monomer components constituting the second polymer portion in the presence of the polymer constituting the first polymer portion finally obtained. Preferably, it is a combination. In addition, when carrying out emulsion polymerization, it may be carried out by batch polymerization in which the monomer components are added all at once and polymerized, or it may be carried out by dropwise polymerization in which they are added in stages.
  • a monomer component constituting the second polymer is added to a solution in which a polymer constituting the first polymer portion is dispersed in an arbitrary solvent, and then various mixers are added. It is possible to emulsify using a polymer, add a polymerization initiator, and polymerize.
  • a solution in which the first polymer is dispersed in an arbitrary solvent can be prepared by dispersing the polymer constituting the first polymer portion in water, various alcohols such as isopropyl alcohol, ethanol, methanol, acetone, methyl ethyl ketone, diethyl ether, etc. It can be obtained by adding one or more solvents and stirring while applying shear.
  • the proportion of the first polymer in the dispersion solution is preferably 10% by mass or more since it has excellent dispersibility, and preferably 50% by mass or less from the viewpoint of handleability considering the viscosity of the dispersion solution.
  • a surfactant When adding the monomer component constituting the second polymer portion to a solution in which the polymer constituting the first polymer portion is dispersed in an arbitrary solvent, a surfactant may also be added. good.
  • Surfactants include anionic surfactants, cationic surfactants, and neutral surfactants. One or more types of these may be used.
  • polymerization initiator those generally used in radical polymerization can be used, and specific examples include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, azobisisobutyronitrile, , 2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), Oil-soluble azo compounds such as 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2'-azobis ⁇ 2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxy ethyl]propionamide ⁇ , 2,2'-azobis ⁇ 2-methyl-N-[2-(1-hydroxyethyl)]propionamide ⁇ , 2,2'-azobis ⁇ 2-methyl-N-[2-( 1-hydroxybutyl)]propionamide ⁇ 2,2'-azobis[2-[2-
  • Preferred radical polymerization methods in one embodiment of the present invention include, for example, a method in which polymerization is carried out using a water-soluble polymerization initiator, and a redox method using an organic peroxide and a reducing agent such as ferrous sulfate or isoascorbic acid. Examples include a method in which polymerization is carried out by reaction.
  • the amount of the polymerization initiator to be used is preferably 0.05 to 1.0 parts by mass based on 100 parts by mass of the monomers constituting the second polymer, with a lower limit of 0.1 parts by mass or more and an upper limit of 0.1 parts by mass or more. More preferably, it is 0.3 parts by mass or less.
  • a peroxide polymerization initiator it can be used as a redox polymerization initiator in combination with a reducing agent.
  • the amount of the reducing agent used is preferably 0.0001 to 1 part by mass based on 100 parts by mass of the monomers constituting the second polymer.
  • the monomer may be polymerized using a known chain transfer agent such as n-dodecylmercaptan, t-dodecylmercaptan, or ⁇ -methylstyrene dimer as a molecular weight regulator.
  • a known chain transfer agent such as n-dodecylmercaptan, t-dodecylmercaptan, or ⁇ -methylstyrene dimer as a molecular weight regulator.
  • the reaction temperature is not particularly limited, but is usually 45°C or higher and 80°C or lower. Further, the reaction time is also not particularly limited, but is usually 30 minutes or more and 300 minutes or less.
  • the latex of polymer A obtained by emulsion polymerization can be recovered as a polymer powder by drying by spray drying or freeze drying, or by coagulating. Among these, drying or coagulation by spray drying method is preferred.
  • any device such as a rotating disk type, a pressure nozzle type, a two-fluid nozzle type, etc. may be used.
  • the temperature of the hot air is preferably 100°C or more and 200°C or less.
  • the hot air temperature is 100° C. or higher, latex can be sufficiently dried, and when the hot air temperature is 200° C. or lower, thermal decomposition of the resulting powder can be suppressed.
  • the latex of polymer A is poured into hot water in which a coagulant has been dissolved, and polymer A is salted out, separated, purified, coagulated, and made into a wet state, which is then dehydrated and dried.
  • the coagulant include inorganic salts such as aluminum chloride, aluminum sulfate, sodium sulfate, magnesium sulfate, sodium nitrate, and calcium acetate, and acids such as sulfuric acid, with calcium acetate being particularly preferred.
  • These coagulants may be used alone or in combination of two or more, but when used in combination, it is preferable to select a combination that does not form water-insoluble salts. For example, it is not preferable to use calcium acetate together with sulfuric acid or its sodium salt because a water-insoluble calcium salt is formed.
  • Polymer A can be used as a resin additive such as a compatibilizer.
  • the resin additive the polymer A may be used as it is, or any auxiliary agent may be added thereto.
  • the auxiliary agent include known ones, such as flame retardants, anti-dripping agents, antioxidants, ultraviolet absorbers, light stabilizers, mold release agents, lubricants, sliding agents, colorants, and optical brighteners. , phosphorescent pigments, fluorescent dyes, antistatic agents, etc.
  • the resin composition according to this embodiment includes a polymer A and a first matrix resin. Moreover, the resin composition may further contain a second matrix resin that is a different resin from the first matrix resin.
  • the ratio of polymer A to 100 parts by mass of the first matrix resin and the second matrix resin is not particularly limited, but is preferably 0.1 to 30 parts by mass, more preferably 5 to 20 parts by mass. If the proportion of the resin additive is 0.1 parts by mass or more, the compatibility between the first matrix resin and the second matrix resin will be further improved, and if the proportion is 30 parts by mass or less, the processability during production of the resin composition will be improved. Excellent in
  • the resin composition according to this embodiment may further contain other components.
  • known auxiliary agents may be added as necessary to impart functionality or improve properties.
  • auxiliary agents include flame retardants, anti-dripping agents, antioxidants, ultraviolet absorbers, light stabilizers, mold release agents, lubricants, sliding agents, colorants, optical brighteners, luminescent pigments, and fluorescent dyes. , antistatic agents, etc.
  • the first matrix resin is not particularly limited, but is preferably a polyester resin, such as polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), etc. ), polybutylene naphthalate (PBN), polybutylene succinate (PBS), polyhydroxyalkanoic acid (PHA), and polylactic acid (PLA). Moreover, recycled materials may be used for these.
  • PBT polybutylene terephthalate
  • PET polyethylene terephthalate
  • PTT polytrimethylene terephthalate
  • PEN polyethylene naphthalate
  • PBN polybutylene naphthalate
  • PBS polybutylene succinate
  • PHA polyhydroxyalkanoic acid
  • PLA polylactic acid
  • the second matrix resin is not particularly limited as long as it is different from the first matrix resin, but examples thereof include polystyrene-containing resins such as polystyrene, high impact polystyrene (HIPS), and acrylonitrile-containing resin. Polystyrene-containing resins such as butadiene-styrene copolymer (ABS) can be used. Moreover, recycled materials may be used for these. At least some of the constituent units constituting the second matrix resin are preferably the same as at least some of the constituent units of the second polymer portion in polymer A, from the viewpoint of improving compatibility. .
  • the proportion of the first matrix resin in a total of 100 parts by mass of the first matrix resin and the second matrix resin is not particularly limited, but it is preferably 5 parts by mass or more, and preferably 10 parts by mass or more. The amount is more preferably 20 parts by mass or more, even more preferably 25 parts by mass or more. On the other hand, the proportion of the first matrix resin is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, even more preferably 80 parts by mass or less, and 75 parts by mass or less. is particularly preferred.
  • Manufacturing method of resin composition Although there are no particular restrictions on the method for producing the resin composition, it can be produced by mixing or melt-kneading the polymer A, the first matrix resin, and the second matrix resin in the form of powder.
  • a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a two-roll machine, a kneader, a Brabender, etc. are used for mixing or melt kneading.
  • the resin composition according to this embodiment can be molded into a molded body.
  • the resin composition according to the present embodiment may be mixed with other materials and then molded to form a molded body. That is, the molded article may contain a resin composition.
  • a known method can be used as a molding method, and examples thereof include compression molding, transfer molding, injection molding, blow molding, vacuum molding, extrusion molding, lamination molding, and calendar molding.
  • the first polymer has a constitutional unit different from the constitutional unit constituting the first polymer portion, and the first polymer portion has a constitutional unit different from the constitutional unit constituting the first polymer portion, and the first polymer portion is contained in a total of 100 parts by mass of the first polymer portion and the second polymer portion.
  • the polymer has a core-shell structure, the first polymer portion constitutes a shell portion of the core-shell structure, and the second polymer portion constitutes a core portion of the core-shell structure, [1] to [ 4].
  • a resin additive comprising the polymer according to any one of [1] to [6].
  • a resin composition comprising the polymer according to any one of [1] to [6] and a polyester resin as a first matrix resin.
  • a resin composition comprising: at least some of the structural units of the second polymer portion and at least some of the structural units of the second matrix resin are the same. Composition.
  • a molded article comprising the resin composition according to any one of [8] to [11].
  • phase size of some of the molded bodies was observed using a transmission electron microscope (TEM) (model name "H-7600", manufactured by Hitachi).
  • TEM transmission electron microscope
  • the test piece was stained with osmium tetroxide for 12 hours and then stained with ruthenium tetroxide for 5 hours to prepare observation sections.
  • the average diameter of the longer diameter portions of arbitrary 30 dispersed phases in the TEM photograph was determined and determined as the phase size.
  • polymer A1 After 1 hour, the temperature was raised to 60°C, held for 2 hours, and cooled to obtain a latex of polymer A1 according to one embodiment of the present invention.
  • the obtained polymer A1 latex was added to 460 parts of deionized water containing 5 parts by mass of calcium acetate, coagulated, washed with water, dehydrated, and dried to obtain polymer A1 in the form of a powder.
  • the production method was the same as in Production Example 1, except that the amount of the first polymer portion used, the type of radically polymerizable monomer, and the amount of copolymerization were changed as shown in Table 1 below.
  • Polymers A2 to A6 and polymers B1 to B3 according to comparative examples were obtained.
  • As the radically polymerizable monomer one or two types of (meth)acrylates were used. In Table 1, two types of (meth)acrylates are indicated as "a1" and "a2", respectively.
  • Example 1 70 parts of polybutylene terephthalate (PBT, manufactured by Mitsubishi Engineering Plastics Co., Ltd.: Novaduran 5010R) as the first matrix resin, 30 parts of polystyrene (PS, manufactured by Toyo Styrene Co., Ltd.: Toyo Styrene GP200) as the second matrix resin, 10 parts of the polymer A1 produced in Production Example 1 was placed in a polyethylene bag. After hand-blending the polyethylene bag by shaking it well, it was melt-kneaded at 250°C using a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., trade name: TEM35B), and the extruded strands were cut to form pellets. I got it.
  • PBT polybutylene terephthalate
  • PS manufactured by Toyo Styrene Co., Ltd.: Toyo Styrene GP200
  • the obtained pellets were molded using an injection molding machine (manufactured by Toshiba Machine Co., Ltd., product name: IS100EN) at a molding temperature of 250°C and a mold temperature of 60°C to produce a dumbbell-shaped molded product in accordance with JIS K7139.
  • a molded article according to Example 1 was obtained.
  • the molded body was subjected to cross-sectional observation using a transmission electron microscope (TEM) and a tensile test.
  • TEM transmission electron microscope
  • a TEM photograph of the cross section of the molded body is shown in FIG.
  • the average diameter of the long axis portion of any 30 dispersed phases in the TEM photograph was 0.58 ⁇ m.
  • the tensile modulus of the molded article in the tensile test was 2.2 GPa, and the tensile elongation was 3.1%.
  • Example 2 The second matrix resin was changed to high impact polystyrene (HIPS, manufactured by Toyo Styrene: Toyostyrene H350), or the ratio of the first matrix resin and the second matrix resin, the type of polymer used, and the amount added were changed.
  • HIPS high impact polystyrene
  • Example 1 A resin composition and a molded body were manufactured in the same manner as in Example 1, except that the polymer A1 obtained in Production Example 1 was not added, and a molded body according to Comparative Example 1 was obtained.
  • the molded body was subjected to cross-sectional observation using TEM and a tensile test.
  • a TEM photograph of the cross section of the molded body is shown in FIG.
  • the average diameter of the long axis portion of any 30 dispersed phases in the TEM photograph was 1.01 ⁇ m.
  • the tensile modulus of the molded article in the tensile test was 2.1 GPa, and the tensile elongation was 2.9%.
  • the polymer according to one embodiment of the present invention is used when the ratio of the first matrix resin to the second matrix resin is 70/30 (first matrix resin/second matrix resin).
  • Comparative Example 1 in which the polymer according to one embodiment of the present invention was used, the average diameter of the dispersed phase was significantly smaller, and the tensile elongation of the molded article was significantly smaller than that in Comparative Example 1. It can be seen that there is an improvement of 7% when 100%.
  • the average diameter of the dispersed phase and the tensile elongation of the molded body were similarly improved in Examples 4 and 6 in which the polymer according to one embodiment of the present invention was used. Recognize.
  • the compatibility between the first matrix resin and the second matrix resin and the tensile elongation of the molded article are improved.
  • the improved tensile elongation improves the toughness of the molded product, which has high industrial utility value.
  • Comparative Example 5 which used a polymer with a small proportion of the first polymer part
  • Example 2 in which the proportion of the first polymer part was sufficient
  • the average diameter of the dispersed phase was small, and It was confirmed that the tensile elongation of the molded article was also improved by 3% when Comparative Example 5 was taken as 100%.
  • Comparative Example 4 which used a polymer with a small proportion of the first polymer portion, and Example 7, in which the proportion of the first polymer portion was sufficient, the average diameter of the dispersed phase and the tensile strength of the molded body were It can be seen that the stretchability has improved.
  • the compatibility between the first matrix resin and the second matrix resin and the tensile elongation of the molded article are improved.
  • the improved tensile elongation improves the toughness of the molded product, which has high industrial utility value.
  • Example 2 in which the second polymer part contained a (meth)acrylate monomer , 5, and 7, it was confirmed that the average diameter of the dispersed phase was small, and the tensile elongation of the molded product was improved. It was confirmed that the tensile elongation of Examples 2, 5, and 7 was improved by 20%, 44%, and 96%, respectively, when the tensile elongation of Comparative Example 6 was taken as 100%.
  • the above results show that by using the polymer according to one embodiment of the present invention as a resin additive, the compatibility between the first matrix resin and the second matrix resin and the tensile elongation of the molded article are improved. .
  • the improved tensile elongation increases the toughness of the molded product, so it has high industrial value.
  • Example 3 in which the ratio of the first matrix resin to the second matrix resin is 90/10 (first matrix resin/second matrix resin) uses the polymer according to one embodiment of the present invention. It can be seen that the average diameter of the dispersed phase is significantly smaller and the tensile elongation of the molded article is improved by 29% when Comparative Example 2 is taken as 100%. From the above results, it can be seen that by using the polymer according to one embodiment of the present invention as a resin additive, the compatibility between the first matrix resin and the second matrix resin and the tensile elongation of the molded article are improved. The improved tensile elongation increases the toughness of the molded product, so it has high industrial value.
  • Example 8 in which HIPS was used as the second matrix resin, the average diameter of the dispersed phase was significantly smaller than in Comparative Example 3 in which the polymer according to one embodiment of the present invention was not used, and the molded article was It can be seen that the tensile elongation is improved by 14% when Comparative Example 3 is taken as 100%. From the above results, it can be seen that by using the polymer according to one embodiment of the present invention as a resin additive, the compatibility between the first matrix resin and the second matrix resin and the tensile elongation of the molded article are improved. . The improved tensile elongation increases the toughness of the molded product, so it has high industrial value.
  • Comparative Example 7 in which a polymer without a second polymer portion was used, the polymerization stability of the polymer was poor, and the tensile elongation of the molded article was lower than in Comparative Example 1, which did not have a polymer. Because of its inferiority, its value for industrial use is inferior.
  • the polymer according to one embodiment of the present invention can reduce phase separation of the resins when two or more types of resins are mixed, and can also provide compatibilization with excellent tensile elongation when a resin composition containing the polymer is made into a molded product. It can be suitably used as an agent.

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PCT/JP2023/015445 2022-04-19 2023-04-18 重合体、樹脂添加剤、樹脂組成物、及び成形体 WO2023204205A1 (ja)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150225562A1 (en) * 2013-02-12 2015-08-13 Vladimir Alonso Escobar Barrios Compatibilizer based on interpenetrating polymer networks (ipn) for recycling polymer blends
JP2016135858A (ja) * 2015-01-23 2016-07-28 ゼロックス コーポレイションＸｅｒｏｘ Ｃｏｒｐｏｒａｔｉｏｎ コア−シェル金属ナノ粒子コンポジット
JP2016161782A (ja) * 2015-03-02 2016-09-05 コニカミノルタ株式会社 静電荷像現像用トナー
JP2017088868A (ja) * 2015-11-10 2017-05-25 ゼロックス コーポレイションＸｅｒｏｘ Ｃｏｒｐｏｒａｔｉｏｎ スチレン／アクリレートおよびポリエステル樹脂粒子
JP2019219643A (ja) * 2018-06-13 2019-12-26 キヤノン株式会社 トナー及びトナーの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150225562A1 (en) * 2013-02-12 2015-08-13 Vladimir Alonso Escobar Barrios Compatibilizer based on interpenetrating polymer networks (ipn) for recycling polymer blends
JP2016135858A (ja) * 2015-01-23 2016-07-28 ゼロックス コーポレイションＸｅｒｏｘ Ｃｏｒｐｏｒａｔｉｏｎ コア−シェル金属ナノ粒子コンポジット
JP2016161782A (ja) * 2015-03-02 2016-09-05 コニカミノルタ株式会社 静電荷像現像用トナー
JP2017088868A (ja) * 2015-11-10 2017-05-25 ゼロックス コーポレイションＸｅｒｏｘ Ｃｏｒｐｏｒａｔｉｏｎ スチレン／アクリレートおよびポリエステル樹脂粒子
JP2019219643A (ja) * 2018-06-13 2019-12-26 キヤノン株式会社 トナー及びトナーの製造方法

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