WO2014171430A1 - Mousse moulée - Google Patents

Mousse moulée Download PDF

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Publication number
WO2014171430A1
WO2014171430A1 PCT/JP2014/060656 JP2014060656W WO2014171430A1 WO 2014171430 A1 WO2014171430 A1 WO 2014171430A1 JP 2014060656 W JP2014060656 W JP 2014060656W WO 2014171430 A1 WO2014171430 A1 WO 2014171430A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
cellulose
foam
foamed
mass
Prior art date
Application number
PCT/JP2014/060656
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English (en)
Japanese (ja)
Inventor
圭助 木村
中井　美穂
頌平 熊澤
行成 祢宜
Original Assignee
ユニチカ株式会社
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Publication date
Application filed by ユニチカ株式会社 filed Critical ユニチカ株式会社
Priority to JP2015512475A priority Critical patent/JP6351574B2/ja
Publication of WO2014171430A1 publication Critical patent/WO2014171430A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
    • C08J9/0076—Nanofibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/34—Chemical features in the manufacture of articles consisting of a foamed macromolecular core and a macromolecular surface layer having a higher density than the core
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2401/02—Cellulose; Modified cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a foam molded article comprising a resin composition using a polyamide resin, having a good surface appearance and excellent impact resistance.
  • Polyamide resin is excellent in properties such as mechanical properties, chemical resistance, heat resistance, and moldability, and the molded body has been widely used for automobile parts, electronic parts and the like.
  • molded articles are molded using a resin composition reinforced by blending polyamide resin with an inorganic filler such as glass fiber, carbon fiber, talc, or clay.
  • these reinforcing materials have a problem that the mechanical properties and thermal properties of the molded body cannot be improved unless they are blended in a large amount, and the mass of the resulting molded body increases due to its high specific gravity. It was.
  • glass fiber, carbon fiber or the like is used as the reinforcing material
  • the obtained molded product has a problem that warpage becomes large.
  • talc, clay, etc. are used as reinforcing materials, when the obtained molded product is discarded, these reinforcing materials remain as incineration residues, so they are buried in the soil and semi-permanently in the ground. There was a problem of remaining.
  • cellulose has been used as a reinforcing material for resin materials.
  • Cellulose includes those obtained from trees, those obtained from non-wood resources such as rice, cotton, kenaf and hemp, and bacterial cellulose produced by microorganisms. Cellulose is present in large quantities on the earth. . Cellulose is excellent in mechanical properties. By containing this in the resin, an effect of improving the properties of the resin composition, that is, the properties of the molded product is expected.
  • a foamed molded product obtained by foaming by adding a foaming agent to a polyamide resin has been proposed as a molded product that is reduced in weight while utilizing the characteristics of the polyamide resin as described above.
  • Patent Document 1 discloses a thermoplastic resin molded article having a foam structure, which is made of a thermoplastic resin composition containing a thermoplastic resin and cellulose fibers, and also describes a polyamide resin as the thermoplastic resin.
  • mold extruder is used in order to mix a thermoplastic resin and a cellulose fiber.
  • a method of incorporating cellulose into the thermoplastic resin a method of melt-mixing the resin and cellulose fiber is common.
  • the cellulose fibers are mixed in the resin in an aggregated state, they are not uniformly dispersed, and the average fiber diameter of the cellulose fibers is large.
  • Patent Document 1 is intended to obtain a molded article having a touch similar to that of a wooden surface, and in order to achieve this object, a large amount of cellulose fibers are contained to increase the surface roughness of the molded article. It is said. Therefore, the foam molded article described in Patent Document 1 does not have a large amount of foam cells that are uniform in size and fine, and therefore the foam molded article is inferior in surface appearance and has low impact resistance. It was.
  • the present invention solves the above problems, and is a foamed molded article comprising a resin composition containing a polyamide resin and cellulose fibers, and has a large amount of foam cells that are uniform in size and fine,
  • An object of the present invention is to provide a foam molded article having a good surface appearance and excellent impact resistance.
  • the gist of the present invention is as follows.
  • a resin composition comprising 0.1 to 10 parts by mass of cellulose fibers having an average fiber diameter of 10 ⁇ m or less and 0.01 to 15 parts by mass of a foam nucleating agent with respect to 100 parts by mass of a polyamide resin, A foamed molded article having a foamed cell.
  • the polyamide resin and the cellulose fiber constituting the resin composition are obtained by performing a polymerization reaction of the monomer constituting the polyamide resin in the presence of the cellulose fiber containing water.
  • the foamed molded article of the present invention is obtained by foaming a resin composition containing a specific amount of cellulose fibers having a small average fiber diameter and a foam nucleating agent. It will have a large amount. For this reason, the foamed molded article of the present invention has excellent surface appearance and excellent impact resistance.
  • molding processing can be performed by a core back injection molding method, and foam having a core layer and a skin layer. It can be set as a molded body.
  • foaming molding of the present invention includes swirl marks (foam marks generated on the surface of the molding), silver streaks (silver marks generated along the flow direction of the resin on the molding surface), sink marks ( It is excellent in surface appearance without causing a dent or the like on the surface of the molded body.
  • the foamed molded article of the present invention comprises a resin composition containing a polyamide resin, cellulose fibers having an average fiber diameter of 10 ⁇ m or less, and a foam nucleating agent, and has foam cells.
  • the polyamide resin used in the present invention refers to a polymer having an amide bond formed from an amino acid, lactam or diamine and a dicarboxylic acid.
  • Examples of monomers that form such a polyamide resin include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid.
  • Examples of the lactam include ⁇ -caprolactam and ⁇ -laurolactam.
  • diamines examples include tetramethylene diamine, hexamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,2,4- / 2,4,4-trimethylhexamethylene diamine, and 5-methyl.
  • Dicarboxylic acids include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5- Examples include sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and diglycolic acid.
  • the polyamide resin used in the present invention includes polycaproamide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebaca. Mido (nylon 610), polyhexamethylene dodecane (nylon 612), polyundecane methylene adipamide (nylon 116), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polytrimethylhexamethylene terephthalamide (Nylon TMHT), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon 6I), polyhexamethylene terephthalamide / isophthalamide (nylon 6T / 6I), polybis (4-aminocyclo) Xyl) methane dodecamide (nylon PACM12), polybis (3-methyl-4-aminocyclohexyl) methane dodecamide (nylon PACM
  • the above polyamide resin is produced by a polymerization method described later, or by further using a solid phase polymerization method.
  • the cellulose fibers used in the present invention include those derived from wood, rice, cotton, hemp, kenaf and the like, as well as those derived from organisms such as bacterial cellulose, valonia cellulose and squirt cellulose. Also included are regenerated cellulose, cellulose derivatives and the like.
  • the dispersibility of the cellulose fiber to the polyamide resin and the affinity between the polyamide resin and the cellulose fiber are important.
  • the cellulose fiber have properties such as hydroxyl groups as much as possible, it is important to increase the surface area of the cellulose fiber. For this reason, it is necessary to use as fine a cellulose fiber as possible.
  • the cellulose fiber contained in the resin composition in the present invention needs to have an average fiber diameter of 10 ⁇ m or less, and the average fiber diameter is preferably 1 ⁇ m or less, and preferably 500 nm or less. More preferably, it is preferably 300 nm or less, and most preferably 40 to 100 nm.
  • the average fiber diameter of the cellulose fibers contained in the resin composition exceeds 10 ⁇ m, the surface area of the cellulose fibers cannot be increased, and it becomes difficult to improve the dispersibility and affinity for the polyamide resin. For this reason, the foamed molded article obtained does not have uniform foam cell size, the foam cell becomes large, and the cellulose fibers are visually confirmed, resulting in poor surface appearance and impact resistance. .
  • cellulose fibers having an average fiber diameter of 10 ⁇ m or less In order to make the average fiber diameter of the cellulose fibers in the resin composition 10 ⁇ m or less, it is necessary to use cellulose fibers having an average fiber diameter of 10 ⁇ m or less. As such a cellulose fiber, what was microfibrillated by tearing a cellulose fiber is preferable.
  • Various pulverizing apparatuses such as a ball mill, a stone mill, a high-pressure homogenizer, and a mixer can be used as means for microfibrillation.
  • a cellulose fiber what is marketed can use "Serish" by Daicel FineChem, for example.
  • an aggregate of cellulose fibers taken out as scrap yarn can be used.
  • the production process of the textile product includes spinning, woven fabric, nonwoven fabric production, and other textile product processing. Since these cellulose fiber aggregates are scrap fibers after the cellulose fibers have undergone these steps, the cellulose fibers are refined.
  • bacterial cellulose produced by bacteria can be used as the cellulose fiber, and for example, those produced using an Acetobacter acetic acid bacterium as a producing bacterium can be used.
  • Plant cellulose is composed of cellulose molecular chains converged and formed by bundles of very thin microfibrils, whereas cellulose produced from acetic acid bacteria originally has a width of 20-50 nm. It is in the form of a ribbon, and forms an extremely fine network compared to plant cellulose.
  • a refined cellulose fiber obtained by oxidizing the cellulose fiber in the presence of an N-oxyl compound, followed by washing with water and physical defibrating may be used.
  • N-oxyl compounds such as 2,2,6,6-tetramethylpiperidine-1-oxyl radical (hereinafter referred to as TEMPO) as described in Cellulose (1998) 5,153-164. preferable.
  • TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyl radical
  • Such a compound is added to the reaction aqueous solution in a catalytic amount range.
  • sodium hypochlorite or sodium chlorite is added as a co-oxidant, and the reaction is allowed to proceed by adding an alkali metal bromide.
  • An alkaline compound such as an aqueous sodium hydroxide solution is added to maintain the pH at around 10, and the reaction is continued until no change in pH is observed.
  • the reaction temperature may be room temperature.
  • Various methods such as filtration and centrifugation can be employed for washing. Then, using various pulverizers as described above, it is possible to obtain refined cellulose fibers through a physical defibrating process.
  • the cellulose fiber in the resin composition in the present invention preferably has an aspect ratio (average fiber length / average fiber diameter) which is a ratio of an average fiber diameter to an average fiber length of 10 or more, and more preferably 50 or more. It is preferable that it is 100 or more.
  • the aspect ratio is 10 or more, the mechanical properties of the obtained foamed molded product are easily improved.
  • the content of the cellulose fiber in the resin composition constituting the foamed molded article of the present invention needs to be 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyamide resin.
  • the amount is preferably 5 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass.
  • foaming is difficult to foam in foam molding, so foam molding having a large amount of uniform and fine foam cells. A body cannot be obtained, the surface appearance is inferior, and the foaming ratio is lower than the set expansion ratio.
  • the content of the cellulose fiber exceeds 10 parts by mass with respect to 100 parts by mass of the polyamide resin, it becomes difficult to contain the cellulose fiber (A) in the resin composition, or the obtained foamed molded article is A foam cell having a large cell diameter is likely to be generated, the size of the foam cell is not uniform, and the surface appearance and impact resistance are poor.
  • the resin composition in the present invention by obtaining the resin composition in the present invention by a production method as described later, even if the cellulose fiber content is small, it becomes a resin composition uniformly dispersed in the polyamide resin.
  • foam molding it is possible to obtain a foam molded article that is sufficiently foamed, has a uniform size, and has a large amount of fine foam cells. Furthermore, the impact resistance of the obtained foamed molded product can be increased.
  • cellulose fibers have a very high affinity with water, and the smaller the average fiber diameter, the better the dispersion state with respect to water. Further, when water is lost, cellulose fibers are strongly aggregated by hydrogen bonding, and once aggregated, it becomes difficult to achieve a dispersion state similar to that before aggregation. In particular, this tendency becomes more prominent as the average fiber diameter of the cellulose fibers decreases. Therefore, the cellulose fiber is preferably combined with the polyamide resin in a state containing water. Therefore, in the present invention, a polyamide resin composition containing cellulose fibers is obtained by performing a polymerization reaction of monomers constituting the polyamide resin in the presence of cellulose fibers containing water during the polymerization of the polyamide resin. It is preferable to take the method of obtaining. Such a production method makes it possible to uniformly disperse the cellulose fibers in the polyamide resin without aggregating them. Details of this manufacturing method will be described below.
  • a polyamide resin composition containing cellulose fibers (resin composition A) containing cellulose fibers in advance. That is, a polyamide resin having an average fiber diameter of 10 ⁇ m or less is obtained by conducting a polymerization reaction of monomers constituting the polyamide resin in the presence of water-containing cellulose fibers to obtain a polyamide resin. It is preferable to prepare a resin composition (resin composition A). For example, the monomer which comprises a polyamide resin and the aqueous dispersion of the cellulose fiber whose average fiber diameter is 10 micrometers or less are mixed, and a polymerization reaction is performed.
  • the aqueous dispersion of cellulose fibers in this preparation method is obtained by dispersing cellulose fibers having an average fiber diameter of 10 ⁇ m or less in water, and the content of cellulose fibers in the aqueous dispersion is 0.01 to 50% by mass. It is preferable to do.
  • the aqueous dispersion of cellulose fibers can be obtained by stirring purified water and cellulose fibers with a mixer or the like. And the aqueous dispersion of a cellulose fiber and the monomer which comprises a polyamide resin are mixed, and it is set as a uniform dispersion by stirring with a mixer etc.
  • the dispersion is heated, and the temperature is raised to 150 to 270 ° C., followed by stirring to cause a polymerization reaction.
  • water in the aqueous dispersion of cellulose fibers can be discharged by gradually discharging water vapor when the dispersion is heated.
  • a catalyst such as phosphoric acid or phosphorous acid may be added as necessary.
  • a foam nucleating agent may be added during the polyamide polymerization.
  • finish of a polymerization reaction after paying out the obtained resin composition, it is preferable to cut
  • a cellulose fiber aqueous dispersion obtained by immersing bacterial cellulose in purified water and replacing the solvent may be used.
  • cellulose fibers having an average fiber diameter of 10 ⁇ m or less are used, and the cellulose fibers are subjected to a polymerization reaction in an aqueous dispersion, thereby being subjected to a polymerization reaction with good dispersibility.
  • the cellulose fibers subjected to the polymerization reaction are improved in dispersibility by agitation with the monomer and water during the polymerization reaction and by stirring at the above temperature conditions, and the fibers aggregate. It is possible to obtain a resin composition A in which cellulose fibers having a small average fiber diameter are well dispersed.
  • the cellulose fibers contained in the mixture after the completion of the polymerization reaction are more than the average fiber diameter of the cellulose fibers added before the polymerization reaction.
  • the average fiber diameter and fiber length may be smaller.
  • the step of drying the cellulose fibers is not necessary, and the production can be performed without the step of causing the scattering of fine cellulose fibers, so that the resin composition A can be obtained with good operability. Become. Moreover, since it is not necessary to replace water with an organic solvent for the purpose of uniformly dispersing the monomer and cellulose, the handling is excellent and the discharge of chemical substances can be suppressed during the production process.
  • the resin composition A in the present invention is obtained by performing a polymerization reaction of monomers constituting the polyamide resin in the presence of cellulose fibers containing water.
  • the resin composition A means one that also contains the additive.
  • the relative viscosity of the resin composition A prepared by the above method is not particularly limited, but is preferably 1.5 to 5.0, and more preferably 1.7 to 4.0. When the relative viscosity is less than 1.5, it is difficult to form uniform foam cells, foam moldability is lowered, and mechanical properties are also lowered. On the other hand, when the relative viscosity exceeds 5.0, the fluidity of the resin composition A is lowered, and the foam moldability is lowered.
  • 96% sulfuric acid was used as a solvent, and the temperature was 25 ° C. and the concentration was 1 g / 100 ml.
  • the elongation viscosity of the resin composition A is preferably 8.00 ⁇ 10 3 to 6.00 ⁇ 10 5 Pa ⁇ s, and more preferably 1.00 ⁇ 10 4 to 9.50 ⁇ 10 4 Pa ⁇ s. It is preferable that When the extensional viscosity is within the above range, it has a viscosity suitable for foaming, the foam cell size is uniform, and a large number of foam cells of appropriate size are formed. Excellent in properties.
  • the resin composition A having an elongation viscosity of 1.00 ⁇ 10 4 to 9.50 ⁇ 10 4 Pa ⁇ s, which is a preferable range, has the average fiber diameter of the cellulose fibers in the resin composition as described above.
  • the content can be adjusted to 40 to 100 nm, and the cellulose fiber content can be adjusted to 0.5 to 5 parts by mass, which is the most preferable range described above. Even if the average fiber diameter of the cellulose fibers in the resin composition A exceeds the most preferable range of 40 to 100 nm, the elongation viscosity of the resin composition A is 1.00 ⁇ 10 4 to 9.50 ⁇ . Although it may be in the range of 10 4 Pa ⁇ s, when the average fiber diameter of the cellulose fibers exceeds 100 nm, the resulting foamed molded product has foam cells having a large cell diameter and tends to be somewhat inferior in uniformity. Therefore, in the present invention, the resin composition A has an average fiber diameter of 40 to 100 nm and an elongational viscosity of 1.00 ⁇ 10 4 to 9.50 ⁇ 10 4 Pa ⁇ s. Most preferred.
  • the resin composition in the present invention contains a foam nucleating agent in addition to the above-described polyamide resin and cellulose fiber (resin composition A).
  • foam nucleating agent used in the present invention include titanium oxide, talc, kaolin, clay, calcium silicate, silica, sodium citrate, calcium carbonate, diatomaceous earth, calcined perlite, zeolite, bentonite, glass, limestone, calcium sulfate, aluminum oxide. , Titanium oxide, magnesium carbonate, sodium carbonate, ferric carbonate, polytetrafluoroethylene powder, and the like.
  • the content of the foam nucleating agent in the resin composition is required to be 0.01 to 15 parts by mass with respect to 100 parts by mass of the polyamide resin, and preferably 0.1 to 12 parts by mass. Further, it is preferably 0.2 to 8 parts by mass, and more preferably 0.2 to 5 parts by mass.
  • the content of the foam nucleating agent is less than 0.01 parts by mass, the resulting foamed molded product does not have the effect of adding the foam nucleating agent, and the bubbles are coarse and foaming tends to be insufficient. The apparent overall density is large, and the surface appearance is inferior.
  • the content of the foam nucleating agent exceeds 15 parts by mass, the number of bubbles becomes excessive and bubble breakage is likely to occur, and the foamed molded article is inferior in surface appearance.
  • the resin composition in this invention can be manufactured by mixing a foaming nucleating agent with the resin composition A which consists of the polyamide resin and cellulose fiber obtained by the said preparation method.
  • Examples of the mixing method include mixing during melt kneading and mixing by addition during polymerization.
  • the resin composition in the present invention may contain other polymers as long as the characteristics are not significantly impaired.
  • Such polymers include polybutadiene, butadiene-styrene copolymer, acrylic rubber, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, natural rubber, chlorinated butyl rubber, elastomers such as chlorinated polyethylene, And acid-modified products thereof such as maleic anhydride, styrene-maleic anhydride copolymer, styrene-phenylmaleimide copolymer, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyacetal, polyvinylidene fluoride, polysulfone, polyphenylene sulfide , Polyethersulfone, phenoxy resin, polyphenylene ether, polymethyl methacrylate, polyether ketone, polyarylate, polycarbonate, polytetrafluoro
  • the resin composition in the present invention has layered silicates such as swellable mica, non-swellable mica, and synthetic smectite, glass fiber, carbon fiber, talc, clay, mica, wax, and the like, as long as the characteristics are not significantly impaired.
  • Contains reinforcements such as lastite, calcium carbonate, barium sulfate, heat stabilizers, antioxidants, pigments, anti-coloring agents, weathering agents, flame retardants, plasticizers, crystal nucleating agents, mold release stabilizers, etc.
  • the pigment include nigrosine, carbon black, titanium dioxide, zinc white, zinc sulfide, lithopone, lead white, antimony white, calcium carbonate, alumina white, and metal powder pigment.
  • the foamed molded product of the present invention is composed of the above resin composition and has foamed cells.
  • the resin composition contains a specific amount of cellulose fibers having a small average fiber diameter and a foam nucleating agent, by foaming this resin composition, a large amount of foam cells that are uniform in size and fine are produced.
  • a foamed molded product containing is obtained. Formation of such a foam-molded product has a structure in which the polyamide resin is cross-linked by containing an appropriate amount of fine cellulose fibers in the polyamide resin, and the elongation viscosity of the polyamide resin composition containing cellulose is increased. Furthermore, it is considered that this is due to containing an appropriate amount of a foam nucleating agent in such a polyamide resin.
  • the foaming molding of this invention has a foam cell, it is comprised especially from a core layer and a skin layer, and it is preferable that a core layer has a foam cell.
  • a foamed molded article having a core layer and a skin layer which is molded by a core back injection molding method, is preferable.
  • the core back injection molding method is a molding method in which the crystallization of the resin composition is promoted to some extent during the formation of the skin layer, and then the core portion is retracted.
  • a resin composition having a high crystallization speed is molded by this method, the skin layer is crystallized and at the same time, the resin composition of the core layer portion is crystallized. Can't get.
  • the resin composition constituting the foamed molded article of the present invention has a small average fiber diameter of cellulose fibers contained therein, the crystallization speed of the polyamide resin is not increased, and it has moderate crystallinity.
  • a foamed molded article having a core layer and a skin layer can be obtained.
  • the foamed molded product of the present invention having such a core layer and skin layer is excellent in surface appearance and surface smoothness without causing swirl marks, silver streaks, sink marks and the like in the skin layer. And it can be set as the foaming molding excellent also in impact resistance by having a skin layer.
  • the thickness ratio (core layer / skin layer) of the core layer and the skin layer in the foamed molded article of the present invention is preferably 1/5 to 5/1.
  • the thickness of the skin layer is larger than this range, the number of foamed cells is reduced, the apparent overall density is increased, and tends to exceed 1.1 g / cm 3 .
  • the thickness of the skin layer is smaller than this range, it is difficult to obtain the excellent surface appearance and surface smoothness as described above, and the impact resistance tends to be inferior.
  • the foamed cell of the foamed molded product of the present invention can have a fine size.
  • the maximum cell diameter of the foam cell is preferably 2 mm or less, more preferably 1.5 mm or less, and most preferably 0.9 mm or less. When the maximum cell diameter exceeds 2 mm, the foamed molded article is inferior in surface appearance, does not have impact resistance, and tends to vary due to mechanical properties.
  • the foamed cells of the foamed molded product of the present invention can be made uniform in size.
  • the uniformity was evaluated by the difference between the maximum cell diameter and the average cell diameter of the foamed cells (maximum cell diameter ⁇ average cell diameter). That is, if this difference is small, the foamed cells are assumed to be uniform.
  • the difference between the maximum cell diameter and the average cell diameter is preferably 1.3 mm or less, more preferably 1.1 mm or less, and most preferably 0.6 mm or less. If this difference exceeds 1.3 mm, the foamed cells have poor uniformity, and the foamed molded product is likely to break starting from the foamed cells when pressure is applied, such as impact resistance. The mechanical properties may be lowered, and the mechanical properties are likely to vary.
  • the foamed molded article of the present invention is measured according to JIS K 7222, and the calculated apparent total density is preferably 1.1 g / cm 3 or less, more preferably 0.9 g / cm 3 or less. Most preferably, it is 0.7 g / cm 3 or less. If the foamed molded body has an apparent total density exceeding 1.1 g / cm 3 , the effect of reducing the weight becomes insufficient. In addition, when the apparent overall density is less than 0.2 g / cm 3 , the amount of the foamed cell is excessively increased, and the impact resistance tends to be low.
  • the foam molded body of the present invention can be obtained by forming a core layer and a skin layer by a core back injection molding method using, for example, a mold having a mirror finish by polishing the mold surface with an abrasive. Can be mirror-finished.
  • a mirror-finished foam molded article is preferably colored black, and is preferably molded using a resin composition containing a black pigment.
  • the black pigment in the present invention include black pigments and black dyes. Specific examples include carbon black, nigrosine, titanium-iron composite oxide, and aniline black. Two or more types of black pigments may be mixed and used.
  • the black pigment content in the foamed molded product of the present invention is preferably 0.1 to 5.0 parts by mass, more preferably 0.1 to 3 parts by mass, with respect to 100 parts by mass of the polyamide resin. preferable.
  • the foamed molded article of the present invention can be obtained by applying a textured surface by forming a core layer and a skin layer by a core back injection molding method using a textured finish mold.
  • the foamed molded product of the present invention is excellent in impact resistance as described above.
  • the impact resistance was evaluated by using notch-free Charpy impact strength according to JIS K 7111-1, using a test piece obtained by cutting a foamed molded product.
  • Charpy impact strength was performed in expanded molded article is preferably at 28kJ / m 2 or more, more preferably 30 kJ / m 2 or more. If the foamed molded article has a Charpy impact strength of less than 28 kJ / m 2 , it has no impact resistance and is not practical.
  • the foamed molded article of the present invention is obtained by foam-molding the above resin composition.
  • foaming agents that can be used for foam molding include pyrolytic foaming agents such as azo, N-nitroso, and heterocyclic nitrogen. Examples thereof include organic compounds containing and decomposable groups such as sulfonyl hydrazide groups, and inorganic compounds such as ammonium carbonate and sodium hydrogen carbonate.
  • azodicarbonamide azobisisobutyronitrile, azocyclohexylnitrile, diazoaminobenzene, dinitrosopentamethylenetetramine, N, N'-dimethyl-N, N'-dinitrosotephthalamide
  • benzenesulfonyl Hydrazide 4,4'-oxy-bis (benzenesulfonyl) hydrazide, diphenylsulfone-3,3'-disulfonylhydrazide, 4-toluenesulfonyl hydrazide, 4,4'-oxy-bis (benzenesulfonyl) semicarbazide
  • 4- Examples include toluenesulfonyl semicarbazide, barium azodicarboxylate, 5-phenyltetrazole, trihydrazinotriazine, 4-toluenesulfonyl azide, 4,4′-diphen
  • liquids such as liquid fluorocarbons and pentanes that are liquid at room temperature, and gaseous fluorocarbons, nitrogen, carbon dioxide, air, helium, argon, and the like that are gaseous or liquefied can be used.
  • the blending amount of the foaming agent in the resin composition is preferably 0.05 to 2 parts by mass and more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the polyamide resin.
  • the blending amount of the foaming agent is less than 0.05 parts by mass, the amount of gas to be foamed is small, the expansion ratio is not increased, the apparent overall density of the resulting foamed molded article is large, and the mass reduction effect cannot be obtained. There is.
  • the blending amount exceeds 2 parts by mass, the mechanical strength of the obtained foamed molded product may be lowered, or the surface appearance such as generation of silver streak or swirl mark may be impaired.
  • the foam molded article of the present invention is foam-molded by a conventional method using the resin composition and the foaming agent described above.
  • the foaming agent when the foaming agent is solid, the obtained resin composition is pelletized or powdered, mixed with the foaming agent, and then the mixture is fed into a molding machine, melted, and injection molded.
  • a foamed molded product can be obtained.
  • the foaming agent may be added directly, or may be added using a master batch pellet obtained by melt-kneading a thermoplastic resin and a foaming agent in advance. Moreover, you may use the masterbatch pellet which pressed the foaming nucleating agent, the binder, etc. with the foaming agent using the disk pelleter.
  • the foaming agent is a gas or liquid, as represented by mucell foaming, the foaming agent is directly added to the molten resin composition and uniformly dispersed, and foamed at the time of molding to obtain a foamed molded article.
  • the core layer in which the foamed cells exist is covered with a skin layer in which the foamed cells do not exist.
  • a foamed molded article is produced, for example, by injecting a molten foamable resin composition into a mold cavity in an injection molding machine, and when the molten resin reaches the vicinity of the flow end for 0.2 to 1.0 seconds.
  • An injection core back type injection molding method in which a holding pressure of 20 to 100 MPa is applied, and then the mold core portion adjacent to the mold cavity is retracted at a speed of 10 to 100 mm / sec in a direction in which the thickness of the middle mold cavity is expanded. Can be obtained at
  • the set foaming ratio (X) is obtained by the following formula from the retreat distance of the die plate and the initial depth of the mold cavity.
  • Set foaming ratio (X) (initial depth + retract distance of die plate) / (initial depth)
  • the actual expansion ratio (Y) of foaming at this time can be calculated as a ratio ( ⁇ 0 / ⁇ 1 ) between the density of the unfoamed body ( ⁇ 0 ) and the density of the foamed molded body ( ⁇ 1 ).
  • the actual expansion ratio is preferably 1.15 to 3.00, more preferably 1.25 to 2.60.
  • the foaming efficiency (Y / X) calculated from the set foaming ratio (X) and the actual foaming ratio (Y) is an index of surface smoothness, preferably 85% or more, and preferably 90% or more. It is more preferable that When the foaming efficiency (Y / X) is 85% or more, the foamed molded body that foams in the mold increases the adhesion to the mold, and the surface smoothness of the foamed molded body is improved.
  • the foamed molded article of the present invention has a good surface appearance and excellent impact resistance, it can be suitably used in applications such as the electric / electronic equipment field, the automobile field, and the machine field.
  • the fiber diameter of 10 cellulose fibers was measured, and the average value of 10 fibers was calculated as the average fiber diameter.
  • a 10 ⁇ m section was cut out with a microtome, or the foamed molded product was observed as it was using a stereomicroscope (OLYMPUS SZ-40). The fiber diameter was measured in the same manner as described above from the obtained image, and the average fiber diameter was determined.
  • the line segment of the maximum length is calculated
  • the length is set to P,
  • the line segment The cell length in a direction passing through the midpoint and perpendicular to the line segment was determined, the length was defined as Q, and (P + Q) / 2 was defined as the cell diameter.
  • the cell diameter was measured for the foamed cell considered to be the maximum, and this was taken as the maximum cell diameter.
  • the measurement surface was divided into 6 equal parts by 5 line segments parallel to the thickness direction, and the cell diameter was measured for 10 foam cells existing near the midpoint of each line segment, for a total of 50 cells.
  • the average value of the cell diameter was calculated and used as the average cell diameter (b).
  • Example 1 As an aqueous dispersion of cellulose fibers, serisch KY100G (manufactured by Daicel Finechem Co., Ltd .: containing 10% by mass of cellulose fibers having an average fiber diameter of 125 nm) was added to this, and purified water was added thereto, followed by stirring with a mixer. An aqueous dispersion having a fiber content of 3% by mass was prepared. 70 parts by mass of this aqueous dispersion of cellulose fibers and 100 parts by mass of ⁇ -caprolactam were further stirred and mixed with a mixer until a uniform dispersion was obtained. Subsequently, the mixed dispersion was heated to 240 ° C.
  • the resin composition was manufactured by dry blending with the black pigment mixture. Core back injection molding was performed using the obtained resin composition.
  • the resin composition was put into an injection molding machine (S-2000i manufactured by FANUC) equipped with a shut-off nozzle, and a mold finished with a mirror finish under conditions of a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. Injection molded.
  • the test piece was filled in 0.2 seconds to the flow end and then subjected to a pressure holding process at 75 MPa for 0.5 seconds.
  • the die plate of the injection molding machine was set at 60 mm / second. It was made to recede so as to be 5 times to obtain a mirror-finished foamed molded article composed of a core layer and a skin layer.
  • injection molding was performed under the same conditions as above to obtain a textured foamed molded article.
  • Production Example 1 Production of bacterial cellulose 50 ml of a medium composed of 0.5 mass% glucose, 0.5 mass% polypeptone, 0.5 mass% yeast extract and 0.1 mass% magnesium sulfate heptahydrate was added to 200 ml. The solution was dispensed into a conical flask and steam sterilized at 120 ° C. for 20 minutes in an autoclave. One platinum ear of Gluconacetobacter xylinus (NBRC 16670) grown on a test tube slant agar medium was inoculated, and left to stand at 30 ° C. for 7 days. Seven days later, a white gel film-like bacterial cellulose was formed in the upper layer of the culture solution.
  • NBRC 16670 Gluconacetobacter xylinus
  • Example 2 The bacterial cellulose obtained in Production Example 1 was used as the cellulose fiber. Bacterial cellulose was crushed with a mixer, and then water substitution was performed by repeating immersion and washing with water. 35 parts by mass of an aqueous dispersion of bacterial cellulose after water replacement (containing 6.5% by mass of bacterial cellulose having an average fiber diameter of 60 nm), 194 parts by mass of ⁇ -caprolactam, 40 parts by mass of aminocaproic acid, 90 parts by mass of purified water was stirred and mixed with a mixer until a uniform dispersion was obtained. Subsequently, the mixed dispersion is gradually heated, and the temperature is raised to 240 ° C. while discharging steam during the heating, and the mixture is stirred at 240 ° C.
  • Example 1 The resin composition A containing this was obtained.
  • the resin composition A was discharged, cut into pellets, treated with hot water at 95 ° C., scoured, and dried.
  • Example 3 Purified water was added to the aggregate of cellulose fibers produced as waste yarn in the nonwoven fabric manufacturing process, and the mixture was stirred with a mixer to prepare an aqueous dispersion containing 3% by mass of cellulose fibers having an average fiber diameter of 120 nm. 170 parts by mass of this aqueous dispersion of cellulose fibers, 216 parts by mass of ⁇ -caprolactam, and 44 parts by mass of aminocaproic acid were stirred and mixed with a mixer until a uniform dispersion was obtained. Subsequently, the mixed dispersion is gradually heated, and the temperature is raised to 240 ° C. while discharging steam during the heating, and the mixture is stirred at 240 ° C.
  • Example 5 The cellulose fiber content is the same as in Example 1 except that serisch KY110N (manufactured by Daicel Finechem Co., Ltd .: cellulose fiber having an average fiber diameter of 150 nm) is used as the aqueous dispersion of cellulose fibers.
  • a cellulose aqueous dispersion was prepared so as to be 3% by mass. 70 parts by mass of this aqueous dispersion of cellulose fibers and 200 parts by mass of ⁇ -caprolactam were further stirred and mixed with a mixer until a uniform dispersion was obtained. Subsequently, the mixed dispersion was heated to 240 ° C. with stirring, and the pressure was increased from 0 MPa to 0.7 MPa while gradually releasing water vapor.
  • a polymerization reaction was carried out at 240 ° C. for 3 hours to obtain a resin composition A containing a polyamide resin and cellulose fibers.
  • eta relative viscosity
  • Example 9 The cellulose fiber content is the same as in Example 1 except that serisch KY100S (manufactured by Daicel Finechem: 25% by mass of cellulose fibers having an average fiber diameter of 180 nm) is used as the aqueous dispersion of cellulose fibers.
  • a cellulose aqueous dispersion was prepared so as to be 3% by mass, and polymerization was performed in the same manner as in Example 1 to obtain pellets of the resin composition A.
  • Example 10 Celish KY100S was used as an aqueous dispersion of cellulose fibers. 49 parts by mass of this cellulose fiber aqueous dispersion, 216 parts by mass of ⁇ -caprolactam, 44 parts by mass of aminocaproic acid, and 157 parts by mass of purified water were stirred and mixed with a mixer until a uniform dispersion was obtained. Subsequently, the mixed dispersion is gradually heated, and the temperature is raised to 240 ° C. while discharging steam during the heating, and the mixture is stirred at 240 ° C. for 1 hour to perform a polymerization reaction. The resin composition A containing this was obtained.
  • the resin composition A was discharged, cut into pellets, treated with hot water at 95 ° C., scoured, and dried.
  • Example 13 As an aqueous dispersion of cellulose fiber, purified water was added to SERISH KY100G and stirred with a mixer to prepare a cellulose fiber content of 3% by mass. 170 parts by mass of an aqueous dispersion of this cellulose fiber, 254 parts by mass of ⁇ -caprolactam, 2.5 parts by mass of swellable fluorinated mica as a layered silicate (manufactured by Corp Chemical Chemical Co., Ltd .: ME-100), phosphorous acid 0.25 parts by mass (0.14 mol% based on ⁇ -caprolactam) was stirred and mixed with a mixer until a uniform dispersion was obtained. Subsequently, the mixed solution was heated to 240 ° C.
  • Comparative Example 2 Except having used the cotton short fiber (average fiber diameter of 16 micrometers) as a cellulose fiber, it carried out similarly to Example 1, and obtained the pellet of the resin composition A containing a polyamide resin and a cellulose fiber.
  • Comparative Example 3 As cellulose fiber, serisch KY100S was freeze-dried and then pulverized to prepare a powder.
  • a twin screw extruder having a screw diameter of 30 mm and an average groove depth of 2.5 mm is blended with 100 parts by mass of nylon 6 (BRL number average molecular weight 17000 manufactured by Unitika Ltd.) and 2 parts by mass of the obtained powdery cellulose. (PCM-30 manufactured by Ikegai Co., Ltd.) and melt kneaded at a barrel temperature of 240 ° C., a screw rotation speed of 120 rpm, and a residence time of 2.7 minutes. The melt-kneaded product was discharged, cut into pellets, and the resulting pellets were dried.
  • PCM-30 manufactured by Ikegai Co., Ltd.
  • Comparative Example 4 Resin composition A pellets were obtained in the same manner as in Example 10 except that the polymerization reaction was carried out so that the cellulose fiber content was as shown in Table 1.
  • Comparative Example 7 254 parts by mass of ⁇ -caprolactam, 10.2 parts by mass of layered silicate (swelling fluorinated mica) and 0.25 parts by mass of phosphorous acid (0.14 mol% with respect to ⁇ -caprolactam) were heated to 80 ° C. The mixture was stirred and mixed with a homogenizer until a uniform solution was obtained while heating. Subsequently, the mixed solution was heated to 240 ° C. with stirring, and the pressure was increased from 0 MPa to 0.7 MPa while gradually releasing water vapor. Thereafter, the pressure was released to atmospheric pressure, and a polymerization reaction was performed at 240 ° C.
  • a resin composition B containing a polyamide resin and a layered silicate.
  • the resin composition B was discharged, cut into pellets, treated with hot water at 95 ° C., scoured, and dried.
  • Table 1 shows the measurement results of the characteristic values of the foam molded articles obtained in Examples 1 to 13 and Comparative Examples 1 to 7. In the measurement of the characteristic value of the foam, a mirror-finished foam was used except for the appearance evaluation.
  • Examples 1 to 13 as described above, an aqueous dispersion of cellulose fibers having an average fiber diameter of 10 ⁇ m or less and a monomer constituting the polyamide resin are mixed, and the polymerization reaction of the monomer is performed, whereby the polyamide resin is mixed.
  • a fine cellulose fiber was uniformly dispersed without agglomeration, and a resin composition obtained by adding a foam nucleating agent thereto was injection molded by the core back method to obtain a foam molded article. Therefore, the foam molded articles obtained in Examples 1 to 13 are composed of a core layer and a skin layer, and the core layer has foam cells.
  • the obtained foamed molded article has a maximum cell diameter of 0.8 mm or less, a uniformity of 0.5 mm or less, a particularly large size and a large amount of fine foam cells, and a surface appearance.
  • the impact resistance was very good.
  • Comparative Example 1 since the resin composition did not contain cellulose fibers, the foaming ratio was low and it was difficult to foam, and the obtained foamed molded article had large foam cells and was not uniform. there were.
  • Comparative Example 2 since the resin composition contained cellulose fibers having an average fiber diameter exceeding 10 ⁇ m, the obtained foamed molded article was foam-molded in Example 1 in which the content of cellulose fibers was the same. Compared with the body, the foam cells are large and uneven, cellulose aggregates are observed, silver streaks, swirl marks, sink marks, etc. are confirmed, the surface appearance is inferior, and the impact resistance is also inferior. It was.
  • Comparative Example 3 since the polyamide resin and the cellulose fiber were melt-kneaded, the dispersibility of the cellulose fiber was low, and the resin composition was able to visually confirm the aggregation of the cellulose fiber, and contained a cellulose fiber having a large average fiber diameter. It was a thing.
  • the foamed molded product obtained from this resin composition has a large and non-uniform foamed cell as compared with the foamed molded product of Example 9 in which the type and content of cellulose fibers are the same, and the surface appearance is inferior. It was also inferior in impact resistance.
  • Comparative Example 4 since the resin composition contained excessive cellulose fibers, the obtained foamed molded article had a small number of foam cells and a small average cell diameter.

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  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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  • Injection Moulding Of Plastics Or The Like (AREA)
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Abstract

　L'invention concerne une mousse moulée caractérisée d'une part en ce qu'elle comprend une composition de résine contenant de 0,1 à 10 parties en masse d'une fibre de cellulose ayant un diamètre moyen de fibre inférieur ou égal à 10 µm et de 0,01 à 15 parties en masse d'un agent de nucléation de mousse, pour 100 parties en masse d'une résine de polyamide ; et d'autre part en ce qu'elle comprend des alvéoles de mousse.
PCT/JP2014/060656 2013-04-17 2014-04-15 Mousse moulée WO2014171430A1 (fr)

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JP2017031246A (ja) * 2015-07-29 2017-02-09 ユニチカ株式会社 発泡成形体
JP2017177669A (ja) * 2016-03-31 2017-10-05 国立大学法人京都大学 発泡樹脂成形品の製造方法および発泡樹脂成形品
JP2018177888A (ja) * 2017-04-06 2018-11-15 ユニチカ株式会社 ポリアミド樹脂組成物およびそれからなる発泡成形体
WO2019212460A1 (fr) * 2018-04-30 2019-11-07 Owens Corning Intellectual Capital, Llc Mousse polymère comprenant de la cellulose nanocristalline
JP2020076039A (ja) * 2018-11-05 2020-05-21 ユニチカ株式会社 発泡成形用樹脂組成物およびその発泡成形体
WO2021070798A1 (fr) * 2019-10-10 2021-04-15 昭和電工マテリアルズ株式会社 Produit moulé en mousse, procédé de fabrication de produit moulé en mousse et procédé de suppression de l'aspect médiocre de produit moulé en mousse
WO2021085056A1 (fr) * 2019-10-30 2021-05-06 ユニチカ株式会社 Composition de résine de polyamide et article moulé la comprenant

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JP7291898B2 (ja) 2019-02-08 2023-06-16 パナソニックＩｐマネジメント株式会社 発泡成形体
EP3986958A1 (fr) 2019-06-18 2022-04-27 3M Innovative Properties Company Compositions et compositions de mousse contenant des particules composites, articles, particules composites et procédés
CN116731511B (zh) * 2023-08-02 2023-10-31 巴斯夫新材料有限公司 热塑性聚酰胺组合物及其制备方法、注塑成型制件和用途

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Publication number Priority date Publication date Assignee Title
JP2017031246A (ja) * 2015-07-29 2017-02-09 ユニチカ株式会社 発泡成形体
JP2017177669A (ja) * 2016-03-31 2017-10-05 国立大学法人京都大学 発泡樹脂成形品の製造方法および発泡樹脂成形品
JP2018177888A (ja) * 2017-04-06 2018-11-15 ユニチカ株式会社 ポリアミド樹脂組成物およびそれからなる発泡成形体
WO2019212460A1 (fr) * 2018-04-30 2019-11-07 Owens Corning Intellectual Capital, Llc Mousse polymère comprenant de la cellulose nanocristalline
JP2020076039A (ja) * 2018-11-05 2020-05-21 ユニチカ株式会社 発泡成形用樹脂組成物およびその発泡成形体
JP7265745B2 (ja) 2018-11-05 2023-04-27 ユニチカ株式会社 物理発泡成形体およびその製造方法
JP2021169619A (ja) * 2019-10-10 2021-10-28 昭和電工マテリアルズ株式会社 発泡成形体、発泡成形体の製造方法、及び発泡成形体の外観不良の抑制方法
JPWO2021070798A1 (ja) * 2019-10-10 2021-10-21 昭和電工マテリアルズ株式会社 発泡成形体、発泡成形体の製造方法、及び発泡成形体の外観不良の抑制方法
JP7259894B2 (ja) 2019-10-10 2023-04-18 株式会社レゾナック 発泡成形体、発泡成形体の製造方法、及び発泡成形体の外観不良の抑制方法
WO2021070798A1 (fr) * 2019-10-10 2021-04-15 昭和電工マテリアルズ株式会社 Produit moulé en mousse, procédé de fabrication de produit moulé en mousse et procédé de suppression de l'aspect médiocre de produit moulé en mousse
JP7505618B2 (ja) 2019-10-10 2024-06-25 株式会社レゾナック 発泡成形体、発泡成形体の製造方法、及び発泡成形体の外観不良の抑制方法
JP6886219B1 (ja) * 2019-10-30 2021-06-16 ユニチカ株式会社 ポリアミド樹脂組成物およびそれからなる成形体
WO2021085056A1 (fr) * 2019-10-30 2021-05-06 ユニチカ株式会社 Composition de résine de polyamide et article moulé la comprenant
CN114616287A (zh) * 2019-10-30 2022-06-10 尤尼吉可株式会社 聚酰胺树脂组合物和由该聚酰胺树脂组合物构成的成型体

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