WO2021075551A1 - 樹脂組成物、それを含む樹脂成形体および樹脂成形体の製造方法 - Google Patents

樹脂組成物、それを含む樹脂成形体および樹脂成形体の製造方法 Download PDF

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WO2021075551A1
WO2021075551A1 PCT/JP2020/039104 JP2020039104W WO2021075551A1 WO 2021075551 A1 WO2021075551 A1 WO 2021075551A1 JP 2020039104 W JP2020039104 W JP 2020039104W WO 2021075551 A1 WO2021075551 A1 WO 2021075551A1
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Prior art keywords
resin
resin composition
aluminum flake
flake particles
coupling agent
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PCT/JP2020/039104
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English (en)
French (fr)
Japanese (ja)
Inventor
信平 岡崎
杉生 大輔
洋 劉
札場 哲哉
秀一 黒井
Original Assignee
本田技研工業株式会社
東洋アルミニウム株式会社
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Application filed by 本田技研工業株式会社, 東洋アルミニウム株式会社 filed Critical 本田技研工業株式会社
Priority to CN202080068560.4A priority Critical patent/CN114514284A/zh
Priority to JP2021552467A priority patent/JP7385671B2/ja
Publication of WO2021075551A1 publication Critical patent/WO2021075551A1/ja

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • C08K9/06Ingredients treated with organic substances with silicon-containing compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates to a resin composition, a resin molded product containing the same, and a method for producing the resin molded product.
  • a weld line also called a welding line
  • This weld line may cause a poor appearance in the injection molded product and may cause a structural defect.
  • a heat-and-cool method is known in which injection molding is performed by heating the mold temperature to a temperature equal to or higher than the glass transition temperature of the resin used as a raw material for the injection molded product.
  • the resin composition used for producing the injection-molded article is an aluminum pigment for the purpose of giving the injection-molded article a high-class feel and differentiating it from other injection-molded articles. It is known to use a resin composition containing the above. However, when an injection molded product is obtained by using the resin composition as a raw material and performing injection molding using the heat and cool method, the formation of weld lines is prevented, but the aluminum pigment is contained in the mold. It is known that the uneven distribution on the surface of the molten resin causes the resin to adhere to the mold and thus contaminate the mold.
  • JP-A-2016-010957 Patent Document 1
  • JP-A-2014-185328 Patent Document 2
  • Patent Document 1 and Patent Document 2 are required to be further improved in order to suppress mold contamination.
  • the resin coating the aluminum flake particles may melt in the high temperature mold, and the resin melts around the aluminum flake particles. This is because it is presumed that it is insufficient to prevent the aluminum flake particles from being unevenly distributed on the surface of the molten resin by mixing with the molten resin. Therefore, in injection molding in which the formation of weld lines is prevented by using the heat and cool method, a technique for suppressing mold contamination when a resin composition containing an aluminum pigment or the like is used as a raw material is still realized. It has not, and its development is wished.
  • an object of the present invention is to provide a resin composition capable of suppressing mold contamination, a resin molded body containing the resin composition, and a method for producing the resin molded body.
  • the present inventors have completed the present invention through repeated diligent studies in order to solve the above problems. Specifically, although the detailed mechanism is unknown, it was found that the coupling agent acts effectively on suppressing mold contamination among the innumerable additives contained in this type of resin composition. I found out. Based on this finding, when injection molding using the heat and cool method is performed using a resin composition containing a thermoplastic resin and aluminum flake particles having a coupling agent attached to at least a part of the surface, The present invention was reached with the idea that mold contamination can be suppressed.
  • the resin composition according to the present invention is a resin composition used for producing an injection molded product, the resin composition contains a thermoplastic resin and aluminum flake particles, and the aluminum flake particles are the same. Coupling agent is attached to at least a part of the surface.
  • the coupling agent is preferably a silane coupling agent.
  • the coupling agent is more preferably an amino silane coupling agent.
  • the coupling agent is preferably contained in an amount of 0.1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the aluminum flake particles.
  • the aluminum flake particles are preferably contained in an amount of 0.5 parts by mass or more and 230 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin in a state where the coupling agent is attached to the surface.
  • the thermoplastic resin is preferably one or more resins selected from the group consisting of acrylonitrile-butadiene-styrene resin, styrene-acrylonitrile copolymer, polystyrene and polyethylene.
  • the resin molded product according to the present invention contains the above resin composition.
  • the method for producing a resin molded product according to the present invention is a step of preparing the resin composition and maintaining the inner wall surface of the resin composition at a temperature at least 70 ° C. or higher higher than the glass transition temperature of the thermoplastic resin. It includes a step of injection-injecting into a mold and a step of obtaining a resin molded product by cooling the resin composition in the mold.
  • the present invention it is possible to provide a resin composition capable of suppressing mold contamination, a resin molded body containing the resin composition, and a method for producing the resin molded body.
  • the present embodiment will be described in more detail.
  • the notation in the form of "A to B” means the upper and lower limits of the range (that is, A or more and B or less), and when the unit is not described in A and the unit is described only in B, A The unit of and the unit of B are the same.
  • the resin composition according to this embodiment is a resin composition used for producing an injection molded product.
  • the resin composition contains a thermoplastic resin and aluminum flake particles.
  • a coupling agent is attached to at least a part of the surface of the aluminum flake particles.
  • the resin composition having such characteristics can suppress mold contamination when injection molding using the heat and cool method is performed.
  • the resin composition is a resin composition used for producing an injection molded product as described above.
  • the "injection molded product” refers to a molded product obtained by applying a conventionally known injection molding method to a resin composition containing a thermoplastic resin. Specifically, it refers to a molded product obtained by heating and fluidizing the resin composition in a cylinder provided in a conventionally known injection molding machine, injecting the resin composition into a mold, and cooling the resin composition in the mold. .. Further, in the present specification, the “resin molded product” means an injection molded product obtained by applying an injection molding method to the resin composition according to the present embodiment.
  • thermoplastic resin means a resin that can be used in the above-mentioned injection molding method by being softened by heating. Therefore, as long as the resin is softened by heating and can be used in the above-mentioned injection molding method, even a resin generally included in the concept of "thermosetting resin” is treated as "thermoplastic resin” in the present specification. It shall be.
  • thermoplastic resin contained in the above resin composition is, for example, acrylonitrile-butadiene-styrene resin (ABS resin), acrylonitrile-styrene-acrylate resin (ASA resin), acrylonitrile-ethylene-propylene-diene-styrene resin (AES resin).
  • ABS resin acrylonitrile-butadiene-styrene resin
  • ASA resin acrylonitrile-styrene-acrylate resin
  • AES resin acrylonitrile-ethylene-propylene-diene-styrene resin
  • Rubber reinforced resins such as polystyrene (PS resin), styrene-acrylonitrile copolymer (AS resin), styrene-maleic anhydride copolymer, (meth) acrylic acid ester-styrene copolymer and other styrene-based (co) Polymer; Olefin resin such as polyethylene (PE resin) and polypropylene; Cyclic polyolefin resin; Polyester resin; Polyamide resin; Polycarbonate resin; Polyarylate resin; Polyacetal resin; Polyvinyl chloride, Ethylene-vinyl chloride polymer, Poly Vinyl chloride resin such as vinylidene chloride; (meth) acrylic resin such as (co) polymer using one or more (meth) acrylic acid esters such as polymethyl methacrylate (PMMA); polyphenylene ether; polyphenylene sulfide; Fluororesin such as polytetrafluoroethylene and polyvinylidene fluoride; liquid crystal polymer
  • thermoplastic resins may be contained alone in the above-mentioned resin composition, or may be contained by mixing two or more kinds.
  • (meth) acrylic as used herein means at least one of acrylic and methacrylic.
  • (meth) acrylo shall also mean at least one of acrylo and methacrylo.
  • the thermoplastic resin is preferably one or more resins selected from the group consisting of ABS resin, AS resin, PS resin and PE resin.
  • a resin molded product having a desired shape can be molded from the resin composition with good yield, and the resin molded product can be applied to various uses.
  • the weight average molecular weight (Mw) of the thermoplastic resin is preferably 2000 to 7000000, more preferably 2000 to 1000000. Further, as the thermoplastic resin, it is preferable to use a thermoplastic resin having a glass transition temperature of 280 ° C. or lower, and more preferably to use a thermoplastic resin having a glass transition temperature of 150 ° C. or lower. Even when the thermoplastic resin has at least one of the above-mentioned weight average molecular weight and the above-mentioned glass transition temperature, a resin molded product having a desired shape can be molded from the above-mentioned resin composition with good yield. It can be applied to various uses.
  • the resin composition according to the present embodiment contains a thermoplastic resin and aluminum flake particles as described above.
  • a coupling agent is attached to at least a part of the surface of the aluminum flake particles.
  • the term "aluminum flake particles” refers to particles containing aluminum and having a flat flake shape. That is, the aluminum flake particles may be flake-shaped particles made of aluminum or flake-shaped particles made of an aluminum alloy, and may be a base of a metal (such as copper, nickel, iron, tin or an alloy thereof). It may be flaky particles obtained by depositing aluminum on a base material of a material or a non-metal (ceramic particles such as alumina and titania, glass or mica). These aluminum flake particles can be obtained by a conventionally known method.
  • the surface of the aluminum flake particles is preferably smooth from the viewpoint of exhibiting the desired surface glossiness, whiteness and brilliance in the resin composition.
  • the aluminum flake particles are preferably contained in an amount of 0.5 parts by mass or more and 230 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin in a state where the coupling agent described later is attached to the surface thereof. ..
  • the resin composition can more sufficiently suppress mold contamination.
  • the resin composition is not prepared in the form of a masterbatch as described later, in the resin composition, the aluminum flake particles are in a state where the coupling agent described later is attached to the surface thereof, and the thermoplastic resin 100 is attached. It is preferably contained in an amount of 0.5 parts by mass or more and 50 parts by mass or less with respect to parts by mass.
  • the resin composition when the resin composition is not prepared in the form of a masterbatch as described later, when the content of aluminum flake particles is less than 0.5 parts by mass, the desired surface glossiness cannot be obtained in the resin composition. Tend. Further, when the content of the aluminum flake particles exceeds 50 parts by mass, the dispersibility of the aluminum flake particles in the thermoplastic resin deteriorates, so that sufficient strength cannot be obtained in the resin molded product obtained from the above resin composition. Tend. From the viewpoint of more fully exerting the effects of the present invention, when the resin composition is not prepared in the form of a masterbatch as described later, the aluminum flake particles have the thermoplasticity in a state where the coupling agent is attached to the surface thereof. It is more preferable that the resin is contained in an amount of 0.5 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the resin.
  • the above resin composition may be prepared in the form of a masterbatch as described later.
  • the content of the aluminum flake particles is preferably 5 parts by mass or more and 230 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin in a state where the coupling agent described later is attached to the surface thereof.
  • the average particle size (D50) of the aluminum flake particles is preferably 2 to 150 ⁇ m, and more preferably 5 to 50 ⁇ m.
  • the aluminum flake particles preferably have an average thickness (t) of 0.01 to 10 ⁇ m, more preferably 0.08 to 1.6 ⁇ m. Further, the aluminum flake particles preferably have an average aspect ratio of 5 to 2500, and more preferably 10 to 150.
  • the "average aspect ratio” means the ratio of the average particle size (D50) of the aluminum flake particles to the average thickness (t), and specifically, the average particle size (D50) (unit) of the aluminum flake particles. Can be obtained from the formula of ⁇ m) / average thickness (t) of aluminum flake particles (unit: ⁇ m).
  • the average particle size (D50) and average thickness (t) of the aluminum flake particles were obtained by applying an injection molding method to the resin composition when the resin composition was used as a measurement object and by applying an injection molding method to the resin composition. Can be obtained by the following measurement methods, respectively.
  • the average particle size (D50) and average thickness (t) of the aluminum flake particles can be obtained by the following method when the resin composition is used as the measurement target. That is, the particle size of the aluminum flake particles is measured by observing the pellets of the resin composition using a scanning electron microscope (SEM), and the particle size of the aluminum flake particles is measured based on the particle size of the 50 or more particles. Calculate the average particle size.
  • SEM scanning electron microscope
  • a flat surface is formed by polishing the surface of the pellets, or the pellets are made into a film by using a hot press machine, and SEM is used for these.
  • the average particle size of the aluminum flake particles can be calculated.
  • the average thickness of the aluminum flake particles can also be calculated by measuring 50 or more aluminum flake particles using SEM in the same manner as the measurement of the average particle size. Even when it is difficult to observe the thickness of the aluminum flake particles by the pellet, the surface of the pellet is polished or made into a film in the same manner as the measurement of the average particle size, and the average thickness of the aluminum flake particles is measured by SEM. Can be calculated.
  • the average particle size (D50) and average thickness (t) of the aluminum flake particles are calculated by calculating the average particle size and the average thickness of the aluminum flake particles using the resin composition as the measurement target when the resin molded body is the measurement target. It can be the same as the method.
  • the surface of the resin molded product is cut to form a flat cross section, and the cross section is observed by SEM to obtain the above average particle size and average thickness. Can be done.
  • a coupling agent is attached to at least a part of the surface of the aluminum flake particles.
  • the coupling agent has an action of binding the inorganic compound and the organic compound via itself by having a reactive group that chemically bonds with the inorganic compound and a reactive group that chemically bonds with the organic compound in one molecule. Refers to a compound that has.
  • the coupling agent when the coupling agent "adheres" to the surface of the aluminum flake particles, the coupling agent is chemically bonded to the surface of the aluminum flake particles by a reactive group that chemically bonds with the above-mentioned inorganic compound of the coupling agent. Means to do.
  • the coupling agent is preferably a silane coupling agent.
  • the example silane coupling agent, R A -Si (OR B) 3 or R A -SiR B (OR B) 2 (R A,: alkyl group having 2 to 18 carbon atoms, an aryl group or an alkenyl group, R B : It is preferable to use a silane coupling agent represented by the chemical formula (alkyl group having 1 to 3 carbon atoms). Further, RA preferably has a functional group.
  • Examples of the functional group of RA include an amino group, a ureido group, an epoxy group, a sulfide group, a vinyl group, a (meth) acryloxy group, a mercapto group, a ketimino group, a glycidyl group, a phenyl group, an imidazole group and an isocyanate group. can do.
  • the coupling agent is more preferably an amino silane coupling agent.
  • silane coupling agents include ⁇ -methacryloxypropyltrimethoxysilane, vinyltricrolsilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyl-tris ( ⁇ -methoxyethoxy) silane, and vinylmethoxysilane.
  • titanate-based coupling agents include, for example, isopropylisostearoyl diacrylic titanate, isopropyltriisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, and tetra (2,2-diallyloxymethyl-1-butyl) bis (di-). Tridecyl) phosphite titanate and the like can be mentioned.
  • zirconia-based coupling agent examples include tetranormal propoxyzirconium, tetranormalbutoxyzirconium, zirconium tetraacetylacetone, zirconium tributoxyacetylacetone, zirconium tributoxystearate, and zirconyl acetate.
  • aluminum-based coupling agent examples include acetoalkoxyaluminum diisopropyrate, zircoaluminate, alkylacetate aluminum diisopropirate, and acetoalkoxyaluminum diisopropyrate.
  • the coupling agent is preferably contained in an amount of 0.1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the aluminum flake particles.
  • the coupling agent is more preferably contained in an amount of 0.15 to 3 parts by mass, more preferably 0.2 to 2 parts by mass, based on 100 parts by mass of the aluminum flake particles.
  • the content of the coupling agent is less than 0.1 parts by mass with respect to 100 parts by mass of the aluminum flake particles, the adhesion between the aluminum flake particles and the thermoplastic resin tends to be insufficient.
  • the content of the coupling agent exceeds 10 parts by mass with respect to 100 parts by mass of the aluminum flake particles, the aluminum flake particles tend to easily aggregate.
  • the method of adhering the coupling agent to the surface of the aluminum flake particles is not particularly limited as long as the effect of the present invention is not adversely affected, and a conventionally known method can be used.
  • a conventionally known method can be used.
  • the coupling agent can be adhered to the surface of the aluminum flake particles.
  • an organic solvent can be appropriately added.
  • organic solvent for example, one selected from the group consisting of ethanol, isopropyl alcohol, toluene, xylene, MEK, methanol, hexane, butanol, acetone, ethylene glycol, methyl cellosolve and butyl cellosolve can be used alone. It is also possible to use a mixed solvent in which two or more kinds selected from the group consisting of the above-mentioned organic solvents are mixed.
  • the coupling agent and the aluminum flake particles are kneaded using a conventionally known kneader or the like, it is preferable to add deionized water as needed. This makes it easier for the coupling agent to adhere to the surface of the aluminum flake particles.
  • the amount of deionized water added can be 0.03 to 3 parts by mass with respect to 100 parts by mass of the aluminum flake particles.
  • the temperature inside the cylinder of the kneader containing the coupling agent and the aluminum flake particles is heated to 20 to 80 ° C., or the kneading is performed.
  • the temperature of the kneaded product containing the coupling agent and the aluminum flake particles obtained by using the machine can be heated to 20 to 80 ° C.
  • the aluminum flake particles have one or more organic compounds selected from the group consisting of fatty acids such as oleic acid and stearic acid, aliphatic amines, aliphatic amides, aliphatic alcohols and ester compounds attached to the surface thereof. May be good. These organic compounds can improve the surface glossiness by suppressing unnecessary oxidation of the surface of aluminum flake particles.
  • the organic compound may be added as a grinding aid when obtained by grinding aluminum flake particles from aluminum powder.
  • the content of the organic compound is preferably less than 2 parts by mass with respect to 100 parts by mass of the aluminum flake particles.
  • the coupling agent and the organic compound are mixed on the surface of the aluminum flake particles by a chemical equilibrium. Or it is presumed that it exists as a coexisting layer.
  • the resin composition according to the present embodiment may further contain the following additives depending on the purpose, as long as the effects of the present invention are not adversely affected.
  • Additives include, for example, mica, color pigments, phosphorescent pigments, color dyes, colorants such as fluorescent dyes, fillers, antioxidants, antioxidants, heat stabilizers, weather stabilizers, UV absorbers, infrared absorbers.
  • the resin composition according to this embodiment can be produced by a conventionally known method.
  • the above resin composition can be obtained by the following production method. That is, first, by kneading the coupling agent and the aluminum flake particles using a kneader or the like as described above, the aluminum flake particles to which the coupling agent adheres to the surface (hereinafter, “aluminum flake particles adhering to the coupling agent”). ”) Is prepared.
  • the coupling agent-attached aluminum flake particles and the above-mentioned thermoplastic resin are selected from the group consisting of a Banbury mixer, a single-screw vented extruder, a twin-screw vented extruder, a kneader, a roll, and a feeder ruder.
  • the resin composition can be obtained by melt-kneading using the melt-kneading machine.
  • the temperature at the time of melt-kneading may be appropriately selected based on the glass transition temperature of the resin used as the thermoplastic resin, and may be, for example, 100 to 300 ° C.
  • the resin composition obtained by the above-mentioned production method is a masterbatch in which a predetermined amount of aluminum flake particles is filled in a thermoplastic resin for the purpose of obtaining better dispersibility of aluminum flake particles in a resin molded product described later. It can be prepared as a form of.
  • the content of the aluminum flake particles in the resin composition may be 5 parts by mass or more and 230 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin in a state where the coupling agent is attached to the surface thereof. preferable.
  • the resin molded product according to the present embodiment contains the above resin composition. This makes it possible to provide resin molded products having various shapes having brilliant properties without contaminating the mold. In the resin molded body, the formation of weld lines is also suppressed.
  • the resin molded body is a resin molded body having a brilliant property, for example, a housing of an electronic device such as a notebook computer or a mobile phone, a housing of a household electric machine such as a vacuum cleaner, a fan, a telephone, a printer, or a housing of an office device. It is suitable for applications such as interior and exterior parts of automobiles, miscellaneous goods, and housing equipment.
  • the resin molded product can be applied not only to the final product but also as a part in the product. Therefore, it can be applied not only to the above-mentioned applications but also to a wide range of applications.
  • the method for producing a resin molded product according to the present embodiment includes a step of preparing the resin composition (first step) and a temperature at which the resin composition is at least 70 ° C. higher than the glass transition temperature of the thermoplastic resin. Including a step of injection-injecting into a mold in which the inner wall surface is maintained (second step) and a step of obtaining a resin molded product by cooling the resin composition in the mold (third step).
  • the first step is a step of preparing the resin composition. Specifically, in this step, the resin composition can be prepared by executing the method for producing the resin composition described above.
  • the second step is a step of injecting the resin composition into a mold having an inner wall surface maintained at a temperature at least 70 ° C. or higher higher than the glass transition temperature of the thermoplastic resin.
  • a mold for injection molding is first prepared according to a conventionally known heat and cool method, and the temperature of the inner wall surface of the mold is adjusted by using a conventionally known mold temperature adjusting means. The temperature is at least 70 ° C. higher than the glass transition temperature of the thermoplastic resin.
  • the thermoplastic resin contained in the resin composition is melted by heating in a cylinder of a conventionally known injection molding machine or the like.
  • the resin composition containing the molten thermoplastic resin is injected and injected into the mold whose inner wall surface is maintained at the above temperature.
  • the temperature of the inner wall surface of the mold is preferably a temperature 70 ° C. or higher higher than the glass transition temperature of the thermoplastic resin as described above, and is higher than the glass transition temperature of the thermoplastic resin by 80 ° C. or more. It is more preferable that the temperature is higher than, for example, 90 ° C.
  • the upper limit of the temperature of the inner wall surface of the mold may be the same as the molding temperature of the thermoplastic resin.
  • the glass transition temperature of the thermoplastic resin can be measured by using a differential thermal analysis method (DTA: Differential thermal analysis).
  • the third step is a step of obtaining a resin molded product by cooling the resin composition in the mold. Specifically, in this step, the resin composition injected and injected into the mold is cooled according to a conventionally known heat and cool method. After that, a resin molded product can be obtained by splitting the mold. Since the resin molded product is manufactured by using the heat and cool method, it is possible to prevent the formation of weld lines. Furthermore, since the adhesion between the aluminum flake particles and the thermoplastic resin is improved by the coupling agent, it is possible to prevent the aluminum flake particles from being unevenly distributed on the surface of the molten thermoplastic resin in the mold, and the metal is divided. It is possible to prevent the mold from being contaminated by aluminum flake particles. Since the resin molded product is prevented from being unevenly distributed on the surface of the molten resin of the aluminum flake particles, high smoothness can be obtained on the surface of the resin molded product.
  • Example 1 Aluminum paste prepared in the form of a paste containing aluminum flake particles having an average particle size (d50) of 21 ⁇ m and an average thickness (t) of 0.5 ⁇ m (trade name (product number): “5422NS”, manufactured by Toyo Aluminum Co., Ltd.) , Solid content (500 g) was dispersed in 2 L of mineral spirit to obtain a dispersion. Aluminum flake particles were obtained by filtering and washing this dispersion.
  • Example 2 The resin composition (masterbatch) was obtained by carrying out the same method for producing a resin composition as in Example 1 except that the amount of deionized water contained in the above treatment solution was 1 g and the amount of ⁇ -aminopropyltriethoxysilane was 1 g. ) Was manufactured.
  • Example 3 By executing the same method for producing a resin composition as in Example 1 except that the amount of deionized water contained in the above treatment solution was 25 g and the amount of ⁇ -aminopropyltriethoxysilane was 25 g, the resin composition (masterbatch) was carried out. ) Was manufactured.
  • An aluminum flake particle dispersion having a solid content of 55% by mass was prepared from the above dispersion without kneading.
  • the above aluminum flake particle dispersion (solid content 400 g) and the same ABS resin as in Example 1 are mixed to obtain a mixture, and the above mixture is used in the same extruder as in Example 1 and is the same as in Example 1.
  • a resin composition (masterbatch) formed into pellets was produced by kneading and granulating under the conditions.
  • ⁇ Comparative example 2> A resin-coated aluminum paste containing aluminum flake particles having an average particle size (d50) of 21 ⁇ m and an average thickness (t) of 0.5 ⁇ m, and the surface of the aluminum flake particles coated with an acrylic resin (trade name (product number)). : "FZ5422", manufactured by Toyo Aluminum Co., Ltd.) was prepared. Next, this resin-coated aluminum paste (solid content 400 g) is mixed with the same ABS resin as in Example 1 to obtain a mixture, and the above mixture is used in the same extruder as in Example 1 and under the same conditions as in Example 1. A resin composition (masterbatch) formed into pellets was produced by kneading and granulating with.
  • Second step 42 g of the resin composition (masterbatch) and 800 g of the ABS resin are put into a twin-screw extruder with a vent and a diameter of 20 mm (trade name: "ZSK type twin-screw extruder", manufactured by Coperion Co., Ltd.). Was melt-mixed and extruded at a temperature in the cylinder of 220 ° C. to prepare a molding resin composition having an aluminum flake particle content of 1% by mass (first step).
  • the resin composition for molding has a rectangular shape of width 120 mm ⁇ length 150 mm ⁇ thickness 5 mm and has a plurality of through holes.
  • the resin composition for molding has a rectangular shape of width 120 mm ⁇ length 150 mm ⁇ thickness 5 mm and has a plurality of through holes.
  • the temperature inside the cylinder provided in the injection molding machine was set to 240 ° C.
  • plate molding dies heated to 80 ° C, 120 ° C, 130 ° C, 140 ° C, 150 ° C, 160 ° C, 170 ° C, 180 ° C, 190 ° C and 200 ° C, respectively, are prepared and injected.
  • the above molding resin composition was injection-injected from the molding machine into each plate molding die.
  • each plate molding die is set to 30 ° C. to cool the molding resin composition in the die, and then the molding resin composition is cooled.
  • a resin molded body was manufactured by dividing each plate molding die (third step). That is, for plate molding in which the temperature of the inner wall surface is heated to 80 ° C., 120 ° C., 130 ° C., 140 ° C., 150 ° C., 160 ° C., 170 ° C., 180 ° C., 190 ° C. and 200 ° C. by executing the third step.
  • Each resin molded body (10 pieces in total) molded using a mold was manufactured.
  • the above-mentioned plate molding die has a plurality of through holes, a portion where the molten resin joins is generated in the die. Therefore, when injection molding is performed without using the heat-and-cool method and without heating the inner wall temperature of the mold to at least 70 ° C. or higher than the glass transition temperature of the ABS resin, the molten resin is formed in the mold in the resin molded body. Weld lines may be formed at the points corresponding to the merging parts.
  • a transparent adhesive tape having a length of 80 mm and a width of 24 mm (trade name: "Cellotape (registered trademark)", manufactured by Nichiban Co., Ltd.) on the surfaces of the resin molded bodies of Examples 1 to 3 and Comparative Examples 1 to 2. ), And by rubbing the tape with your fingertips, the transparent adhesive tape is brought into close contact with the surfaces of the resin molded bodies of Examples 1 to 3 and Comparative Examples 1 to 2, and then from the surface. The transparent adhesive tape was peeled off so as to be peeled off at 180 degrees.
  • the transparent adhesive tape peeled off from the surface of the resin molded product was attached to a black mount, and a digital microscope (trade name: "VHX-6000", manufactured by KEYENCE CORPORATION) was used at a magnification of 500 times.
  • the number of aluminum flake particles adhering to the transparent adhesive tape was determined.
  • the evaluation was performed in one field of view (400 ⁇ m ⁇ 600 ⁇ m) and ranked based on the following criteria. The results are shown in Table 1.
  • the number of aluminum flake particles adhering to the transparent adhesive tape shows a positive correlation with the number of aluminum flake particles that cause mold contamination due to uneven distribution on the surface of the molten resin in the mold. Is presumed.
  • the resins of Examples 1 to 3 and Comparative Examples 1 to 2 are obtained by determining the number of aluminum flake particles adhering to the transparent adhesive tape and ranking them based on the following criteria. It is possible to evaluate whether or not the composition can suppress mold contamination when injection molding using the heat and cool method is performed.
  • A It is estimated that the number of aluminum flake particles is 3 or less, and mold contamination can be suppressed more sufficiently.
  • B The number of aluminum flake particles is 4 to 10, and it is estimated that mold contamination can be suppressed.
  • C It is estimated that the number of aluminum flake particles is 11 or more, and the suppression of mold contamination is insufficient.
  • the resin compositions of Examples 1 to 3 and the resin molded product containing the same were injection-molded using a mold heated to at least 70 ° C. or higher than the glass transition temperature of the thermoplastic resin. In this case, the formation of weld lines can be prevented in the same manner as in the conventional (Comparative Examples 1 and 2) resin molded products. Further, according to Table 1, the resin compositions of Examples 1 to 3 and the resin molded product containing the same are injected using a mold heated to at least 70 ° C. or higher than the glass transition temperature of the thermoplastic resin. It is understood that when molding is performed, it is possible to suppress uneven distribution of aluminum flake particles on the surface of the molten resin as compared with Comparative Example 1 and Comparative Example 2, and thus mold contamination can be suppressed.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
PCT/JP2020/039104 2019-10-18 2020-10-16 樹脂組成物、それを含む樹脂成形体および樹脂成形体の製造方法 WO2021075551A1 (ja)

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