WO2022075249A1 - Composition de résine polyamide et procédé de production d'une composition de résine polyamide - Google Patents

Composition de résine polyamide et procédé de production d'une composition de résine polyamide Download PDF

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WO2022075249A1
WO2022075249A1 PCT/JP2021/036587 JP2021036587W WO2022075249A1 WO 2022075249 A1 WO2022075249 A1 WO 2022075249A1 JP 2021036587 W JP2021036587 W JP 2021036587W WO 2022075249 A1 WO2022075249 A1 WO 2022075249A1
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polyamide resin
resin composition
polymerization
mass
polyamide
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PCT/JP2021/036587
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English (en)
Japanese (ja)
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康一 連
剛士 友利
彰太 野口
美穂 中井
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ユニチカ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/04—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—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 polyamide resin composition and a method for producing a polyamide resin composition.
  • the present invention is specifically composed of a cellulose fiber and a polyamide resin, and a polyamide resin composition having improved mechanical properties, particularly excellent tensile elasticity and linear expansion coefficient, and good payout property, and a cellulose fiber.
  • the present invention relates to a method for producing the polyamide resin composition in which cellulose fibers are uniformly dispersed in the resin even if the content is large.
  • a resin composition in which a polyamide resin is reinforced with an inorganic filler such as glass fiber, carbon fiber, talc, or clay is widely known.
  • an inorganic filler such as glass fiber, carbon fiber, talc, or clay
  • a reinforcing material such as these inorganic fillers
  • the mechanical properties and heat resistance are not improved unless a large amount of the inorganic filler is blended, and the mass of the resin composition obtained due to the high specific gravity. There is a problem that becomes large.
  • cellulose as a reinforcing material for resin materials.
  • Cellulose includes those obtained from trees, those obtained from non-wood resources such as rice, cotton, kenaf, bagasse, abaca, and hemp, and bacterial cellulose produced by microorganisms. These are very abundant on Earth. Cellulose has excellent mechanical properties, and by containing it in the resin, it is expected to have the effect of improving the properties of the resin composition. Further, since the specific gravity of cellulose is smaller than that of the inorganic filler, there is no problem that the mass of the resin composition obtained by containing it in the resin becomes large.
  • the flexural modulus is improved, but the tensile modulus is not sufficiently improved.
  • Patent Document 1 an aqueous dispersion of cellulose fibers and a monomer constituting a polyamide resin are mixed and melt-polymerized to obtain a polyamide resin composition having improved mechanical properties and heat resistance. Is disclosed.
  • Patent Document 2 a polyamide resin composition having a specific relative viscosity is increased in molecular weight by solid-phase polymerization to have high strength but good color tone and payout property. It is disclosed that a cellulose-containing polyamide resin composition having a good viscosity can be obtained.
  • Patent Document 3 the raw material is heated by stirring the powder or granular material while keeping the temperature of the inner wall of the reaction vessel lower than the polymerization temperature of the raw material of the powder or granular material, and the temperature of the raw material is higher than the temperature of the inner wall of the reaction vessel.
  • a technique for solid-phase polymerization as a polymerization temperature is described.
  • Patent Document 4 describes a technique for solid-phase polymerization using a low-order condensate of polyamide.
  • Patent Document 5 describes a technique for solid-phase polymerization of a polyamide.
  • Patent Documents 6 and 7 describe that a reinforcing effect can be obtained by blending cellulose.
  • the conventional method it was not possible to obtain a polyamide resin composition having sufficiently excellent bending elastic modulus, tensile elastic modulus and linear expansion coefficient.
  • the conventional polyamide resin composition may not be able to obtain sufficiently excellent heat resistance.
  • the method described in Patent Document 1 since the polymerization temperature is raised above the melting point of the polyamide resin during melt polymerization of the polyamide resin composition, the tensile elastic modulus of the polyamide resin composition cannot be sufficiently improved. Further, the method described in Patent Document 1 may not be able to sufficiently improve the linear expansion coefficient and heat resistance of the polyamide resin composition. Further, the method described in Patent Document 2 improves the flexural modulus of the polyamide resin composition, but cannot sufficiently improve the tensile elastic modulus and the linear expansion coefficient. Further, the method described in Patent Document 2 may not be able to sufficiently improve the heat resistance of the polyamide resin composition.
  • the polymer in any of the methods of Patent Documents 1 and 2, the polymer must be kept in a molten state at the time of producing the resin composition, and as the polymerization progresses, the melt viscosity becomes high and it becomes difficult to dispense the resin composition. There is also a problem that the yield is poor.
  • Patent Documents 3 to 5 perform solid-phase polymerization, even if the cellulose fiber compounding techniques described in Patent Documents 6 and 7 are applied to such techniques, the polyamide resin composition is formed. It is not possible to sufficiently improve the mechanical properties (particularly the tensile elastic modulus and the linear expansion coefficient) and the heat resistance of the object.
  • the present invention is a polyamide resin composition in which mechanical properties such as bending elastic modulus, tensile elastic modulus and linear expansion coefficient (particularly both tensile elastic modulus and linear expansion coefficient) are sufficiently improved. It is an object of the present invention to provide the manufacturing method.
  • the present invention also has sufficiently improved mechanical properties such as bending elastic modulus, tensile elastic modulus and linear expansion coefficient (particularly both tensile elastic modulus and linear expansion coefficient), and has good payout property. It is an object of the present invention to provide a composition and a method for producing the same.
  • the present invention also has sufficiently improved mechanical properties such as flexural modulus, tensile modulus and linear expansion coefficient (particularly both tensile modulus and linear expansion coefficient), and has good payout property.
  • flexural modulus tensile modulus and linear expansion coefficient (particularly both tensile modulus and linear expansion coefficient)
  • tensile modulus and linear expansion coefficient particularly both tensile modulus and linear expansion coefficient
  • has good payout property to provide a polyamide resin composition that uniformly contains cellulose fibers even if the content of the cellulose fibers is relatively large (for example, 50 parts by mass or more with respect to 100 parts by mass of the polyamide resin), and a method for producing the same. With the goal.
  • the present invention also relates to a polyamide resin composition having sufficiently improved mechanical properties such as flexural modulus, tensile modulus and linear expansion coefficient (particularly both tensile modulus and linear expansion coefficient) and heat resistance.
  • the purpose is to provide a manufacturing method.
  • the present invention also has sufficiently improved mechanical properties such as flexural modulus, tensile modulus and linear expansion coefficient (particularly both tensile modulus and linear expansion coefficient) and heat resistance, and provides good payout property.
  • An object of the present invention is to provide a polyamide resin composition having a modulus and a method for producing the same.
  • the present invention also has sufficiently improved mechanical properties such as bending elasticity, tensile elasticity and linear expansion coefficient (particularly both tensile elasticity and linear expansion coefficient) and heat resistance, and provides good payout performance.
  • a polyamide resin composition that uniformly contains cellulose fibers even if the content of the cellulose fibers is relatively large (for example, 50 parts by mass or more with respect to 100 parts by mass of the polyamide resin), and a method for producing the same. The purpose is to provide.
  • the present inventors have conducted extensive research to solve such problems. As a result, the present inventors have found that the above object can be achieved by obtaining a polyamide resin composition containing a cellulose fiber by polymerization at a temperature lower than the melting point of the polyamide resin composition, and the present invention has been made. Reached.
  • the gist of the present invention is as follows. ⁇ 1> A polyamide resin composition containing 0.01 to 200 parts by mass of cellulose fibers with respect to 100 parts by mass of the polyamide resin, and the tensile elasticity of the molded product obtained from the polyamide resin composition is 3.0 GPa. Polyamide resin composition characterized by exceeding. ⁇ 2> The polyamide resin composition according to ⁇ 1>, wherein the polyamide resin contains a monomer in a liquid state at a polymerization temperature as a monomer component. ⁇ 3> The polyamide resin composition according to ⁇ 1> or ⁇ 2>, which is produced using water.
  • ⁇ 4> The polyamide resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the linear expansion coefficient of the molded product is 40 ⁇ 10 -6 (1 / ° C.) or less.
  • ⁇ 5> The linear expansion coefficient of the molded product shows a reduction rate of 30% or more based on the linear expansion coefficient of the molded product obtained from the polyamide resin composition produced by the melt polymerization method, according to ⁇ 4>.
  • Polyamide resin composition. ⁇ 6> The polyamide resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the content of the cellulose fiber is 4 to 100 parts by mass with respect to 100 parts by mass of the polyamide resin.
  • the content of the cellulose fiber is 8 to 100 parts by mass with respect to 100 parts by mass of the polyamide resin.
  • the content of the cellulose fiber is 22 to 100 parts by mass with respect to 100 parts by mass of the polyamide resin.
  • ⁇ 9> The polyamide resin composition according to any one of ⁇ 1> to ⁇ 8>, wherein the cellulose fiber (B) has an average fiber diameter of 10 ⁇ m or less.
  • a method for producing a polyamide resin composition which comprises performing a polymerization reaction at a temperature lower than the melting point of the polyamide resin.
  • the method for producing a polyamide resin composition according to ⁇ 10> which uses a monomer in a liquid state at a polymerization temperature and water.
  • ⁇ 12> The method for producing a polyamide resin composition according to ⁇ 10> or ⁇ 11>, wherein the polymerization temperature is equal to or higher than the melting point of the polyamide resin of ⁇ 75 (° C.) and lower than the melting point of the polyamide resin.
  • ⁇ 13> The method for producing a polyamide resin composition according to any one of ⁇ 10> to ⁇ 12>, which comprises producing the polyamide resin composition according to any one of ⁇ 1> to ⁇ 9>.
  • ⁇ 14> The polyamide resin composition according to any one of ⁇ 1> to ⁇ 9>, which is produced by the method for producing a polyamide resin composition according to any one of ⁇ 10> to ⁇ 13>.
  • ⁇ 15> A molded product obtained by molding the polyamide resin composition according to any one of ⁇ 1> to ⁇ 9> and ⁇ 14>.
  • the polyamide resin composition of the present invention has sufficiently improved mechanical properties (particularly both tensile elastic modulus and linear expansion coefficient) such as bending elastic modulus, tensile elastic modulus and linear expansion coefficient.
  • the polyamide resin composition of the present invention also has good payout properties.
  • the polyamide resin composition of the present invention further contains the cellulose fibers relatively uniformly even if the content of the cellulose fibers is relatively large (for example, 50 parts by mass or more with respect to 100 parts by mass of the polyamide resin). As a result, it is considered that mechanical properties such as bending elastic modulus, tensile elastic modulus and linear expansion coefficient (particularly both tensile elastic modulus and linear expansion coefficient) are sufficiently improved.
  • the polyamide resin composition of the present invention also has sufficiently improved heat resistance.
  • the polyamide resin composition of the present invention also has good recyclability.
  • the polyamide resin composition of the present invention contains a polyamide resin and cellulose fibers dispersed in the polyamide resin.
  • the polyamide resin in the present invention refers to a polymer having an amide bond formed by an aminocarboxylic acid, lactam or diamine and a dicarboxylic acid.
  • aminocarboxylic acid examples include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid.
  • lactam examples include ⁇ -caprolactam and ⁇ -laurolactam.
  • diamine examples include tetramethylenediamine, hexamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5 -Methylnonamethylenediamine, 2,4-dimethyloctamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5 -Trimethylcyclohexane, 3,8-bis (aminomethyl) tricyclodecane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) Examples include propane and bis (aminopropyl) piperazine.
  • dicarboxylic acid examples include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid and 5-methylisophthalic acid. , 5-Sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, diglycolic acid and the like.
  • polyamide resin examples include, for example, polycaproamide (polyamide 6), polytetramethylene adipamide (polyamide 46), polyhexamethylene adipamide (polyamide 66), polyhexamethylene sebacamide (polyamide 610), and the like.
  • Polyhexamethylene dodecamide (polyamide 612), polyundecamethylene adipamide (polyamide 116), polyundecaneamide (polyamide 11), polydodecaneamide (polyamide 12), polytrimethylhexamethylene terephthalamide (polyamide TMHT), poly Hexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene terephthal / isophthalamide (polyamide 6T / 6I), polybis (4-aminocyclohexyl) methadodecamide (polyamide PACM12), polybis (polyamide PACM12).
  • 3-Methyl-4-aminocyclohexyl) methaneddecamide polyamide dimethyl PACM12
  • polymethoxylylen adipamide polyamide MXD6
  • polynonamethylene terephthalamide polyamide 9T
  • polydecamethylene terephthalamide polyamide 10T
  • polyamide 11T undecamethylene terephthalamide
  • polyamide 11T polyundecamethylene hexahydroterephthalamide
  • polyamide 6, polyamide 66, polyamide 11, polyamide 12, or these from the viewpoint of further improving mechanical properties (particularly tensile elastic modulus and linear expansion coefficient), heat resistance, payout property, and cellulose fiber dispersion uniformity.
  • Polyamides and mixtures are preferred.
  • polyamide 6, polyamide 66 or polyamide 12 is more preferable, polyamide 6 or polyamide 12 is further preferable, and polyamide 6 is particularly preferable.
  • mechanical properties are used in a concept that includes flexural modulus, tensile modulus and coefficient of linear expansion (particularly, modulus of tensile modulus and coefficient of linear expansion).
  • the cellulose fiber in the present invention examples include those derived from wood, rice, cotton, kenaf, bagasse, abaca, hemp and the like.
  • biological-derived substances such as bacterial cellulose, valonia cellulose, and ascidian cellulose can also be mentioned.
  • regenerated cellulose, cellulose derivatives and the like can also be mentioned.
  • the cellulose fiber is preferably a cellulose fiber derived from wood.
  • the polyamide resin composition of the present invention can improve mechanical properties by uniformly containing cellulose fibers. In order to further sufficiently improve the mechanical properties, it is preferable to disperse the cellulose fibers more uniformly in the resin without agglomerating them. Since the number of hydroxyl groups on the surface of the cellulose fiber in contact with the polyamide resin is larger, the cellulose fiber is more likely to be dispersed, so that it is preferable that the surface area of the cellulose fiber is large as a whole. Therefore, the cellulose fiber is preferably as fine as possible.
  • the cellulose fiber used is not particularly limited as long as it can be uniformly dispersed in the resin composition, whether it is chemically unmodified or chemically modified.
  • the cellulose fibers in the resin composition of the present invention have an average fiber diameter from the viewpoint of further improving mechanical properties (particularly tensile elastic modulus and linear expansion coefficient), heat resistance, payout property, and cellulose fiber dispersion uniformity. It is preferably 10 ⁇ m or less, more preferably 500 nm or less, further preferably 200 nm or less, particularly preferably 150 nm or less, and most preferably 120 nm or less.
  • the lower limit of the average fiber diameter is not particularly limited, but is preferably 4 nm in consideration of the productivity of the cellulose fiber.
  • the aspect ratio (average fiber length / average fiber diameter) of the cellulose fibers in the resin composition of the present invention is preferably 10 or more, more preferably 30 or more, still more preferably 40 or more, and 50 or more. The above is particularly preferable, and 100 or more is most preferable. When the aspect ratio is 10 or more, the mechanical properties of the polyamide resin composition are further improved.
  • the average fiber diameter and the average fiber length of the cellulose fibers in the resin composition refer to the average fiber diameter and the average fiber length in the molded product obtained by using the resin composition, respectively.
  • the average fiber diameter and the average fiber diameter in the dumbbell test piece described in ISO standard 3167 obtained by injection molding a sufficiently dried resin composition using an injection molding machine (NEX110-12E manufactured by Nissei Resin Industry Co., Ltd.). The average fiber length is used.
  • the detailed molding conditions at this time are as follows. When the polyamide resin was polyamide 6, the conditions for injection molding were a resin temperature of 250 ° C., a mold temperature of 70 ° C., an injection time of 12 seconds, and a cooling time of 20 seconds.
  • the injection molding conditions were a resin temperature of 290 ° C., a mold temperature of 80 ° C., an injection time of 12 seconds, and a cooling time of 20 seconds.
  • the conditions for injection molding were a resin temperature of 200 ° C., a mold temperature of 80 ° C., an injection time of 12 seconds, and a cooling time of 20 seconds.
  • the average fiber diameter and average fiber length of the cellulose fibers in the resin composition are almost the same as the average fiber diameter and average fiber length in the molded product obtained by using the resin composition.
  • a cellulose fiber having an average fiber diameter of 10 ⁇ m or less is preferable to use as the cellulose fiber to be blended in the polyamide resin.
  • Cellulose fibers having an average fiber diameter of 10 ⁇ m or less can be obtained by splitting the cellulose fibers into microfibrils. Examples of means for microfibrillation include various crushing devices such as ball mills, stone mill crushers, high-pressure homogenizers, and mixers. Examples of commercially available products of the aqueous dispersion of microfibrillated cellulose fibers include "Cerish" manufactured by Daicel FineChem.
  • an aggregate of the cellulose fiber produced as waste yarn can be used in the manufacturing process of the fiber product using the cellulose fiber.
  • the textile product manufacturing process include spinning, woven fabric, non-woven fabric manufacturing, and processing of textile products. Since the aggregate of these cellulose fibers is a waste thread after the cellulose fibers have undergone these steps, the cellulose fibers are made finer.
  • bacterial cellulose produced by bacteria can also be mentioned.
  • the bacterial cellulose include those produced by producing acetic acid bacteria of the genus Acetobacter.
  • Cellulose in plants is a converged molecular chain of cellulose, and is formed by bundling very thin microfibrils.
  • the cellulose produced by acetic acid bacteria is originally ribbon-shaped with a width of 20 to 50 nm, and forms an extremely fine network shape as compared with the cellulose of plants.
  • Bacterial cellulose may coexist with acetic acid because the bacteria produce acetic acid with the cellulose. In that case, it is preferable to replace the solvent with water.
  • the finely divided cellulose can be produced, for example, by oxidizing the cellulose fibers in an aqueous solution containing an N-oxyl compound, an copolymer and an alkali metal bromide, and then washing and defibrating the cellulose fibers.
  • N-oxyl compound examples include 2,2,6,6-Tempothylpiperidine-1-oxylradical and the like.
  • cooxidant include sodium hypochlorite and sodium chlorite.
  • the oxidation reaction of the cellulose fibers is carried out from the point where an alkaline compound such as an aqueous solution of sodium hydroxide is added to bring the pH to around 10 until the pH does not change.
  • the reaction temperature is preferably room temperature. After the reaction, it is preferable to remove the N-oxyl compound, the copolymer, and the alkali metal bromide remaining in the system.
  • the washing method include filtration and centrifugation.
  • the defibration method include methods using various crushing devices exemplified as the above-mentioned device for microfibrillation.
  • the cellulose fiber may be an unmodified cellulose fiber in which the cellulose-derived hydroxyl group is not modified by any substituent, or the cellulose-derived hydroxyl group (particularly a part thereof) is modified (or substituted). It may be a modified cellulose fiber.
  • the substituent introduced into the hydroxyl group derived from cellulose is not particularly limited, and examples thereof include a hydrophilic substituent and a hydrophobic substituent.
  • the hydroxyl group modified (or substituted) by the substituent is a part of the hydroxyl groups derived from cellulose, and the degree of substitution thereof is preferably 0.05 to 2.0. It is more preferably 1 to 1.0, and even more preferably 0.1 to 0.8.
  • the degree of substitution represents the number of introduced substituents per unit structure (glucopyranose ring) constituting cellulose. That is, it is defined as "the value obtained by dividing the number of moles of the introduced substituent by the total number of moles of the glucopyranose ring". Since pure cellulose has three substitutable hydroxyl groups per unit structure (glucopyranose ring), the theoretical maximum value of the degree of substitution of the cellulose fiber of the present invention is 3, and the theoretical minimum value is 0.
  • the hydrophilic substituent include a carboxyl group, a carboxymethyl group, a phosphate ester group and the like.
  • the hydrophobic substituent include a silyl ether group, an alkyl ether group, an alkyl ester group and the like.
  • the content of cellulose fibers in the polyamide resin composition of the present invention needs to be 0.01 to 200 parts by mass with respect to 100 parts by mass of the polyamide resin, and has mechanical properties (particularly tensile elasticity and linear expansion). From the viewpoint of further improving the coefficient), heat resistance, payout property, and cellulose fiber dispersion uniformity, it is preferably 1 to 100 parts by mass, more preferably 4 to 100 parts by mass, and 8 to 100 parts by mass. It is more preferably 18 to 100 parts by mass, particularly preferably 22 to 100 parts by mass, and most preferably 22 to 80 parts by mass.
  • the content of the cellulose fiber is less than 0.01 part by mass with respect to 100 parts by mass of the polyamide resin, there is no effect of improving the mechanical properties and heat resistance.
  • the content of the cellulose fiber exceeds 200 parts by mass with respect to 100 parts by mass of the polyamide resin, it is difficult to contain the cellulose fiber in the resin composition, or the obtained resin composition is colored. It may occur.
  • the polyamide resin composition of the present invention By obtaining the polyamide resin composition of the present invention by the production method of the present invention as described later, even if the content of the cellulose fibers is small, it is uniformly dispersed in the polyamide resin, so that the polyamide resin Sufficient mechanical properties and heat resistance improving effect can be obtained in the composition. That is, even if the content of the cellulose fiber is 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyamide resin, the polyamide resin composition has improved mechanical properties, particularly the tensile elastic modulus and the linear expansion coefficient. It will be excellent for both.
  • the content of the cellulose fiber is 22 to 100 parts by mass, preferably 30 to 100 parts by mass, more preferably 50 to 100 parts by mass, and further preferably 50 to 80 parts by mass with respect to 100 parts by mass of the polyamide resin.
  • the mechanical properties and heat resistance of the polyamide resin composition are improved, and the tensile elasticity and the linear expansion coefficient are particularly excellent.
  • the polyamide resin composition of the present invention containing the above-mentioned polyamide resin and cellulose fibers has a number average molecular weight of 10,000 to 10 of the polyamide resin from the viewpoint of further improving mechanical properties and heat resistance and improving moldability. It is preferably 10,000.
  • the number average molecular weight is a value obtained by PMMA conversion at 40 ° C. using a gel permeation chromatography (GPC) apparatus equipped with a differential refractive index detector and using hexafluoroisopropanol as an eluent.
  • GPC gel permeation chromatography
  • the molecular weight of the polyamide resin composition of the present invention can also be controlled by adjusting the terminal group concentration of the polyamide.
  • Examples of the method for adjusting the terminal group concentration include addition of a known terminal blocker.
  • Examples of the terminal blocking agent include monoamines and monocarboxylic acids.
  • Examples of monoamines include stearylamine, octylamine, cyclohexylamine, aniline and the like.
  • monocarboxylic acids include acetic acid, lauric acid, stearic acid, and benzoic acid.
  • the polyamide resin composition of the present invention is a pigment, a heat stabilizer, an antioxidant, a weathering agent, a plasticizer, a lubricant, a mold release agent, an antistatic agent, an impact resistant agent, and a flame retardant, as long as the characteristics are not significantly impaired.
  • Additives such as compatibilizers may be contained.
  • the polyamide resin composition of the present invention may contain a polymer other than the polyamide resin as long as its characteristics are not significantly impaired.
  • examples of other polymers include polyolefins, polyesters, polycarbonates, polystyrenes, polymethyl (meth) acrylates, poly (acrylonitrile-butadiene-styrene) copolymers, liquid crystal polymers, polyacetals and the like.
  • the polyamide resin composition of the present invention can be produced, for example, by adding cellulose fibers during the polymerization of the polyamide resin and carrying out the polymerization reaction at a temperature lower than the "melting point of the polyamide resin". Specifically, the polyamide resin composition of the present invention heats a mixed dispersion obtained by uniformly mixing a monomer constituting the polyamide resin and an aqueous dispersion of cellulose fibers to a temperature lower than the "melting point of the polyamide resin". It can be produced by subjecting it to a polymerization reaction.
  • the polyamide resin composition of the present invention can be produced by using a monomer and water, and more specifically, by polymerizing using a monomer and water at a temperature lower than the "melting point of the polyamide resin".
  • water is usually a medium for an aqueous dispersion of cellulose fibers.
  • it is possible to sufficiently and uniformly disperse the cellulose fibers while sufficiently suppressing the deterioration of the cellulose fibers by carrying out a polymerization reaction using a monomer and water at a temperature lower than the “melting point of the polyamide resin”. can.
  • the time of polymerization of the polyamide resin includes not only the time of polymerization using the monomers constituting the polyamide resin but also the time of polymerization using a monomer salt or a prepolymer capable of constituting the polyamide resin. Therefore, the monomer to be polymerized may be a monomer salt or a prepolymer.
  • the monomer salt is a salt of a diamine and a dicarboxylic acid that can constitute a polyamide resin.
  • a prepolymer is an intermediate product in the process of polymerizing a monomer.
  • the cellulose fiber cannot be uniformly dispersed. Specific properties (eg, tensile elasticity and / or linear expansion coefficient) are reduced and / or heat resistance is reduced.
  • the polymerization temperature is lower than the "melting point of the polyamide resin".
  • the “melting point of the polyamide resin” is the “melting point of the target polyamide resin", and more specifically, the monomer of the polyamide resin constituting the polyamide resin composition of the present invention (may be a monomer salt or a prepolymer). It is the melting point of the polyamide resin obtained by sufficiently polymerizing by the melt polymerization method using only.
  • the melt polymerization method is a method in which a polyamide resin is obtained in a molten state by sufficiently polymerizing by heating without using a solvent.
  • the polymerization temperature in the melt polymerization method is higher than the melting point of the obtained polyamide resin (that is, the "target polyamide resin").
  • the polymerization temperature in such a melt polymerization method is, for example, 230 to 250 ° C. (particularly 240 ° C.) in the case of polyamide 6, and 250 to 290 ° C. (particularly 280 ° C.) in the case of polyamide 66, for example. Further, for example, in the case of polyamide 12, the temperature is 220 to 240 ° C. (particularly 230 ° C.).
  • the polymerization time in the melt polymerization method is usually 0.5 to 2 hours, particularly 1 hour.
  • the polymerization temperature is higher than or higher than the "melting point of the polyamide resin" (particularly, the temperature exceeds the “melting point of the polyamide resin"), the cellulose fibers are deteriorated, so that mechanical properties (for example, tensile elasticity and / or linear expansion coefficient) occur. ) Decreases and / or heat resistance decreases.
  • the polyamide resin composition of the present invention when producing the polyamide resin composition of the present invention, first, sufficient polymerization is carried out by the above-mentioned melt polymerization method using only the monomer (which may be a monomer salt or a prepolymer) as a raw material to be used. This is performed to obtain a polyamide resin (specifically, "target polyamide resin”). Then, the melting point of the obtained polyamide resin is measured. For example, when the "target polyamide resin” is polyamide 6, the “melting point of the target polyamide resin” is usually 220 ° C. Further, for example, when the "target polyamide resin” is polyamide 66, the “melting point of the target polyamide resin” is usually 270 ° C.
  • the “melting point of the target polyamide resin” is usually 175 ° C.
  • the method for measuring the melting point is not particularly limited, and for example, it can be measured by a differential scanning calorimeter. Then, the polyamide resin composition of the present invention is subjected to a polymerization reaction at a temperature lower than the "melting point" of a mixed dispersion containing a monomer (which may be a monomer salt or a prepolymer) and an aqueous dispersion of cellulose fibers. Can be manufactured.
  • polymerization is carried out at a lower temperature than the conventional melt polymerization method, so such polymerization can be referred to as "low temperature polymerization".
  • the polyamide resin composition of the present invention obtained by low temperature polymerization is obtained in a solid state (or a solid phase state).
  • the water dispersion of cellulose fibers can be obtained by stirring purified water and cellulose fibers with a mixer or the like.
  • the content of the cellulose fibers in the aqueous dispersion is preferably 0.01 to 50% by mass, particularly preferably 1 to 30% by mass.
  • a polymerization catalyst may be added if necessary.
  • the polymerization catalyst is not particularly limited as long as it is usually used for melt polymerization of polyamide. Of these, phosphorus compounds are preferable, and phosphorous acid or sodium hypophosphite is preferably used.
  • the polymerization temperature is, specifically, Mp-75 (° C.) or higher, Mp, where the "melting point of the target polyamide resin" is Mp (° C.). It is necessary that it is less than Mp-55 (° C.), preferably Mp-55 (° C.) or higher and Mp-15 (° C.) or lower, and more preferably Mp-45 (° C.) or higher and Mp-15 (° C.) or lower.
  • Mp-45 (° C.) or higher and Mp-25 (° C.) or lower
  • Mp-35 (° C.) or higher and Mp-25 (° C.) or lower.
  • the polymerization temperature is less than Mp-75 (° C.)
  • the reaction rate becomes slow and the time until the practically required degree of polymerization is reached becomes long.
  • the polymerization temperature is Mp or higher
  • the produced polymer may be melted, and the operability may be lowered or coloring may occur due to the accompanying increase in viscosity. Further, since the heat deterioration of the cellulose fiber occurs, the mechanical properties of the obtained polyamide resin composition are not sufficiently improved.
  • the polymerization time is usually the time during which the polyamide resin constituting the polyamide resin composition has the "melting point of the target polyamide resin", for example. , 8 hours or more (particularly 8 to 24 hours), preferably 10 to 20 hours, more preferably 10 to 14 hours.
  • the low-temperature polymerization may be carried out under the flow of an inert gas, may be carried out in an air atmosphere without the flow of the inert gas, or may be carried out under pressure or reduced pressure. From the viewpoint of further improving mechanical properties (particularly tensile elasticity and linear expansion coefficient), heat resistance, payout property and cellulose fiber dispersion uniformity, it is preferably carried out under the flow of an inert gas. Since the monomer constituting the polyamide resin has a cyclic structure, when it is difficult to initiate polymerization, it is preferable to temporarily or continuously pressurize the inside of the system during low temperature polymerization.
  • the monomer to be polymerized preferably contains a monomer that is in a liquid state at the polymerization temperature from the viewpoint of further improving mechanical properties (particularly tensile elastic modulus and linear expansion coefficient), heat resistance, payout property, and cellulose fiber dispersion uniformity. .. That is, it is preferable that the polyamide resin contained in the polyamide resin composition of the present invention contains a monomer that is in a liquid state at the polymerization temperature as a monomer component.
  • the monomer that is in a liquid state at the polymerization temperature is a monomer that is in a molten state at the polymerization temperature (specifically, a monomer having a melting point equal to or lower than the polymerization temperature).
  • the polymerization temperature is the polymerization temperature at the time of low-temperature polymerization for obtaining the polyamide resin composition of the present invention.
  • the monomer component is a raw material component used as a raw material (that is, a raw material component or compound used for polymerization). Therefore, in the present invention, the polyamide resin contains a monomer that is in a liquid state at the polymerization temperature as a raw material component.
  • the polyamide resin contains a monomer that is in a liquid state at the polymerization temperature as a raw material component.
  • by performing low-temperature polymerization and using a monomer that is in a liquid state at the polymerization temperature as a raw material component it is possible to more uniformly disperse the cellulose fibers while suppressing deterioration of the cellulose fibers more sufficiently. can.
  • mechanical properties such as flexural modulus, tensile modulus and coefficient of linear expansion (particularly both modulus of tensile modulus and coefficient of linear expansion) and heat resistance are further sufficiently improved
  • the monomer constituting the polyamide resin of the present invention preferably contains at least one type of monomer that is in a liquid state at the polymerization temperature.
  • the polyamide resin of the present invention preferably contains 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more of the monomers in a liquid state at the polymerization temperature with respect to all the monomers constituting the polyamide resin. , Particularly preferably in an amount of 80% by mass or more.
  • the content of the monomer in a liquid state at the polymerization temperature is usually 100% by mass or less, and may be 90% by mass or less, particularly with respect to all the monomers constituting the polyamide resin of the present invention.
  • the melting point ⁇ (° C) of the monomer that is in a liquid state at the polymerization temperature has mechanical properties (particularly tensile elasticity and linear expansion coefficient), heat resistance, payout property, and cellulose fiber.
  • the monomer that is in a liquid state at the polymerization temperature cannot be unconditionally defined because it depends on the polymerization temperature (particularly, the composition of the polyamide resin to be obtained).
  • ⁇ -caprolactam (melting point of about 69 ° C.) can be mentioned as a monomer that can be in a liquid state at the polymerization temperature.
  • isomorphic salts of adipic acid (melting point about 152 ° C.), hexamethylenediamine (melting point about 42 ° C.), and hexamethylenediamine-azipic acid (melting point) as monomers that can be in a liquid state at the polymerization temperature.
  • the equimolar salt of hexamethylenediamine-azipic acid as a raw material of the polyamide 66 has a melting point of about 200 ° C., it may not be in a liquid state at the polymerization temperature.
  • ⁇ -laurolactam melting point of about 153 ° C.
  • the produced polyamide since the polyamide is polymerized at a temperature lower than Mp, the produced polyamide may not be melted and may shift to solid phase polymerization. If necessary, the produced polyamide resin composition may be crushed and / or refined, and then further increased in molecular weight by solid phase polymerization.
  • the produced polyamide resin composition referred to here also contains intermediate products during the polymerization of the monomer, that is, oligomers and low polymers.
  • the polyamide resin composition obtained by the production method of the present invention or, if necessary, the polyamide resin composition after crushing and / or refining is used as an inert gas. It is preferably carried out by heating under circulation or under reduced pressure at a temperature lower than the "melting point of the polyamide resin composition" for 30 minutes or more, and preferably by heating for 1 hour or more (for example, 1 to 10 hours).
  • the “melting point of the polyamide resin composition” can be measured by the same method as the above-mentioned method for measuring the melting point, except that the polyamide resin composition is used.
  • the “melting point of the polyamide resin composition” may be the same temperature as the above-mentioned “melting point of the polyamide resin”.
  • the heating temperature during solid-phase polymerization is usually Mp'-75 (° C) or more and less than Mp'when the "melting point of the polyamide resin composition" is Mp'(° C), and is Mp'-55 (° C). As described above, it is preferably Mp'-15 (° C.) or lower, more preferably Mp'-45 (° C.) or higher, Mp'-25 (° C.) or lower, Mp'-35 (° C.) or higher, Mp. It is more preferably -25 (° C.) or less. If the heating temperature is less than Mp'-75 (° C.), the reaction rate may slow down. On the other hand, when the heating temperature is Mp'or higher, the polymer (that is, polyamide) constituting the polyamide resin composition may be fused or colored.
  • the polyamide resin composition obtained by the production method of the present invention can be crushed into a powder shape (or a flake shape). Further, the polyamide resin composition can be supplied to an extruder and pelletized by a strand cutter.
  • the polyamide resin composition obtained by the production method of the present invention is preferably immersed in water at 90 to 100 ° C. and refined in order to remove unreacted monomers and oligomers.
  • the additives and other polymers may be mixed in the mixed dispersion before low-temperature polymerization. Further, the additive and other polymers may be blended in the polyamide resin composition after low temperature polymerization by melt-kneading or the like.
  • the polyamide resin composition of the present invention may be obtained as a masterbatch.
  • the polyamide resin composition of the present invention having a relatively high content of cellulose fibers may be used as a masterbatch.
  • the polyamide resin composition of the present invention (that is, a masterbatch) can be melt-kneaded together with a polyamide resin containing no cellulose fiber for the purpose of dilution to adjust the content of the cellulose fiber to a desired value.
  • two or more kinds of polyamide resin compositions of the present invention having different contents of cellulose fibers may be mixed and melt-kneaded with each other.
  • the method for producing a polyamide resin composition of the present invention low-temperature polymerization is performed as described above, so that thermal deterioration of cellulose fibers is sufficiently suppressed. Therefore, in the polyamide resin composition of the present invention, not only the cellulose fibers are more uniformly dispersed, but also the thermal deterioration of the cellulose fibers is more sufficiently suppressed. As a result, the polyamide resin compositions of the present invention have higher mechanical properties and heat resistance.
  • the polyamide resin composition of the present invention has at least a higher tensile modulus. In a more preferred embodiment, the polyamide resin composition of the present invention has a higher tensile modulus and a lower coefficient of linear expansion.
  • the polyamide resin composition of the present invention needs to have a tensile elastic modulus of more than 3.0 GPa, preferably 3.8 GPa or more, and more preferably 4.7 GPa or more.
  • the upper limit of the tensile elastic modulus is not particularly limited, and is usually 10 GPa, particularly 8 GPa.
  • the polyamide resin composition of the present invention also preferably has a flexural modulus of 4.0 GPa or more, more preferably 6.0 GPa or more, and even more preferably 8.0 GPa or more.
  • the upper limit of the flexural modulus is not particularly limited, and is usually 20 GPa, particularly 12 GPa.
  • the polyamide resin composition of the present invention also preferably has a coefficient of linear expansion of 40 ⁇ 10 -6 / ° C. or less, more preferably 15 ⁇ 10 -6 / ° C. or less, and 7 ⁇ 10 -6 / ° C. The following is more preferable.
  • the lower limit of the coefficient of linear expansion is not particularly limited, and is usually 1 ⁇ 10 -6 / ° C, particularly 2 ⁇ 10 -6 / ° C.
  • the tensile elastic modulus, flexural modulus and linear expansion modulus of the polyamide resin composition of the present invention refer to the tensile elastic modulus, bending elastic modulus and linear expansion coefficient in the molded product obtained by using the resin composition, respectively.
  • the molded body for measuring these characteristic values is the same as the molded body for measuring the average fiber diameter described above.
  • the tensile elastic modulus and the flexural modulus are the values measured in accordance with ISO527 and ISO178, respectively.
  • the coefficient of linear expansion is the coefficient of linear expansion in the injection direction (that is, the flow direction of the resin at the time of injection molding, also referred to as the MD direction) at the time of manufacturing the molded body, and is measured based on JIS K7197. The average value in the region of 20 to 150 ° C. is used.
  • the coefficient of linear expansion of the polyamide resin composition of the present invention is 30% or more, preferably 60% or more, based on the coefficient of linear expansion of the molded product obtained from the polyamide resin composition produced by the melt polymerization method. It preferably shows a reduction rate of 65% or more. The upper limit of the reduction rate is not particularly limited, and is usually 90%, particularly 80%.
  • the polyamide resin composition produced by the melt polymerization method is the same polyamide resin composition as the polyamide resin composition of the present invention except that it is produced by adopting the melt polymerization method, and is, for example, the present invention. It has the same composition and composition ratio as the polyamide resin composition.
  • the polyamide resin composition of the present invention has a significant reduction effect on the coefficient of linear expansion as compared with the polyamide resin composition by the melt polymerization method having the same composition and composition ratio as the polyamide resin composition.
  • the melt polymerization method is the same method as the above-mentioned melt polymerization method, and is a method in which a polyamide resin is obtained in a molten state by sufficiently carrying out polymerization by heating without using a solvent.
  • a polyamide resin composition containing a melted polyamide resin can be obtained.
  • water in the aqueous dispersion of cellulose fibers is removed at the time of polymerization, and therefore, it is not classified as a solvent.
  • the rate of decrease in the coefficient of linear expansion is determined by expressing the coefficient of linear expansion of the polyamide resin composition of the present invention and the coefficient of linear expansion of the polyamide resin composition by the melt polymerization method as "X" and "Y", respectively. It is a ratio expressed by X) / Y ⁇ ⁇ 100 (%).
  • the rate of decrease in the linear expansion coefficient is a characteristic value based on a comparison between the polyamide resin composition of the present invention and the polyamide resin composition obtained by the melt polymerization method and having the same content of the cellulose fibers. It is one characteristic value that often suggests uniform dispersibility. The larger the reduction rate, the better the uniform dispersibility of the cellulose fibers.
  • the polyamide resin composition of the present invention is also excellent in heat resistance.
  • the heat resistance includes the characteristic that the heat distortion temperature of the polyamide resin composition at a load of 1.8 MPa is within the range described later and the characteristic that the heat distortion temperature at a load of 0.45 MPa is within the range described later.
  • the polyamide resin composition of the present invention preferably has a heat distortion temperature of 50 ° C. or higher, more preferably 60 ° C. or higher, further preferably 70 ° C. or higher, and even more preferably 130 ° C. under a load of 1.8 MPa.
  • the above is particularly preferable, 170 ° C. or higher is sufficiently preferable, and 188 ° C. or higher is most preferable. If the heat distortion temperature under a load of 1.8 MPa is less than 50 ° C., it does not have sufficient heat resistance and is difficult to use for various purposes.
  • the heat distortion temperature under a load of 0.45 MPa is preferably 150 ° C. or higher, more preferably 170 ° C. or higher, still more preferably 180 ° C. or higher. It is particularly preferably 200 ° C. or higher, sufficiently preferably 207 ° C. or higher, and most preferably 217 ° C. or higher. If the heat distortion temperature under a load of 0.45 MPa is less than 150 ° C., it does not have sufficient heat resistance and is difficult to use for various purposes.
  • the heat distortion temperature of the polyamide resin composition of the present invention refers to the heat distortion temperature in the molded product obtained by using the resin composition.
  • the molded body for measuring this characteristic value is the same as the molded body for measuring the average fiber diameter described above.
  • the heat distortion temperature uses the value measured in accordance with ISO 75.
  • the polyamide resin composition of the present invention is also excellent in recyclability.
  • Recyclability is a property in which the initial values of the physical properties such as the tensile elastic modulus and the flexural modulus of the molded product obtained by using the polyamide resin composition are sufficiently maintained even after repeated pulverization and molding. That is.
  • As an index showing such recyclability there is a physical property retention rate at the time of recycling (for example, retention rate of bending elastic modulus and tensile elastic modulus).
  • the polyamide resin composition of the present invention preferably has a physical property retention rate of 85% or more, more preferably 90% or more, and further preferably 95% or more at the time of recycling. If the physical property retention rate at the time of recycling is less than 85%, the physical properties deteriorate due to recycling, so that the material does not have sufficient recyclability and it becomes difficult to recycle (that is, reuse).
  • the retention rate of physical properties of the polyamide resin composition of the present invention at the time of recycling is such that the physical properties (for example, bending elastic modulus and tensile elastic modulus) of the molded product obtained by using the resin composition are recycled three times (that is, pulverized). And molding), it refers to the retention rate after repeating.
  • the molded body for measuring this characteristic value is the same as the molded body for measuring the average fiber diameter described above.
  • the pulverization is performed until the average value of the maximum diameters of any 100 pulverized particles becomes 1 to 5 mm.
  • the flexural modulus and tensile modulus can be measured by the same method as described above.
  • the polyamide resin composition of the present invention can be made into a molded product by a known molding method.
  • Known molding methods include, for example, injection molding, blow molding, extrusion molding, inflation molding, vacuum molding after sheet processing, pneumatic molding, and vacuum pneumatic molding.
  • a molded product obtained by injection molding using the polyamide resin composition of the present invention a film or sheet obtained by extrusion molding (hereinafter referred to as “film or the like”), these films or the like, or a stretched film thereof.
  • injection molding is preferable as the molding method.
  • the injection molding machine used for injection molding is not particularly limited, and examples thereof include a screw in-line type injection molding machine and a plunger type injection molding machine.
  • the polyamide resin composition heated and melted in the cylinder of the injection molding machine is weighed for each shot, injected into the mold in a molten state, cooled and solidified in a predetermined shape, and then from the mold as a molded body. Taken out.
  • the resin temperature at the time of injection molding is preferably equal to or higher than the melting point of the polyamide resin composition, and preferably less than (melting point + 100 ° C.).
  • the polyamide resin composition to be subjected to injection molding is preferably sufficiently dried.
  • a polyamide resin composition having a high water content may foam in the cylinder of an injection molding machine, making it difficult to obtain an optimum molded product. Therefore, the water content of the polyamide resin composition used for injection molding is preferably less than 0.3% by mass, more preferably less than 0.1% by mass.
  • the polyamide resin composition of the present invention is excellent in mechanical properties, particularly excellent in both tensile elastic modulus and linear expansion coefficient. Therefore, the polyamide resin composition of the present invention can be suitably used for automobiles, electrical and electronic equipment, agriculture / fisheries, medical equipment, miscellaneous goods and the like.
  • the molded product obtained from the polyamide resin composition of the present invention can be used as a recycled material by crushing and / or repelletizing the molded product. That is, the sprue, scraps such as runners, crushed products such as non-standard molded products and used molded products, or the crushed products generated when the polyamide resin composition of the present invention is used for molding processing such as injection molding. Repelletized by an extruder or the like can be mixed with another polyamide resin (for example, the polyamide resin composition of the present invention and / or another polyamide resin different from the polyamide resin composition) and used again in the molding process. can.
  • another polyamide resin for example, the polyamide resin composition of the present invention and / or another polyamide resin different from the polyamide resin composition
  • Repelletization is the process of pulverizing, melting and kneading the molded product or offcuts obtained through the pellets to obtain pellets again. Further, the recycled material may be used alone for the molding process again. Since the polyamide resin composition of the present invention has good adhesion between the polyamide resin and the cellulose fibers, deterioration of mechanical properties and heat resistance is suppressed even when used as a recycled material.
  • body such as bumper, instrument panel, console box, garnish, door trim, ceiling, floor, lamp reflector, brush holder, fuel pump module parts, distributor, seat lead valve, wiper motor gear, speed.
  • Meter frame solenoid ignition coil, alternator, switch, sensor parts, tie lot end stabilizer, ECU cable, exhaust gas control valve, connector, solenoid valve of exhaust brake, engine valve, radiator fan, starter, injector, panel around engine, engine cover , Motor cover.
  • Applications for electrical and electronic equipment include, for example, personal computers, mobile phones, music players, car navigation systems, SMT connectors, IC card connectors, optical fiber connectors, microswitches, capacitors, chip carriers, coil encapsulation, transistor encapsulation, IC sockets, switches.
  • Relay parts Capacitor housings, Thermistas, Various coil bobbins, FDD main chassis, Tape coder head mounts, Stepping motors, Bearings, Shaver blades, LCD projection TV lamp housings, Microwave parts, Electromagnetic cooker coil bases, Dryers Nozzle, steam dryer parts, steam iron parts, DVD pickup base, rectifier base, circuit board, IC, liquid crystal jig, hood cutter, DAT cylinder base, copy machine gear, printer fixing unit parts, liquid crystal panel light guide plate, communication Equipment (antenna), sealing material for semiconductors, power module, fuse holder, water pump impeller, pipe for semiconductor manufacturing equipment, connector for game machines, drain pan for air conditioner, container in food waste disposer, motor fan guide for vacuum cleaner, electronic Examples include roller stay rings for ranges, cap stun motor bearings, street lights, submersible pumps, motor insulators, motor brush holders, breaker parts, personal computer housings, mobile phone housings, OA equipment housing parts, and gas meters.
  • Examples of agricultural and fishery applications include containers, cultivation containers, and floats.
  • Examples of medical device applications include syringes and drip containers.
  • miscellaneous goods examples include plates, cups, spoons, flower pots, cooler boxes, fan, toys, ballpoint pens, rulers, clips, drain materials, fences, storage boxes, construction switchboards, hot water supply equipment pump casings, impellers, joints, valves, etc.
  • Examples include faucet appliances
  • the polyamide resin composition of the present invention can be molded into a film or sheet by a known film forming method such as T-die extrusion or inflation molding.
  • the film or sheet obtained by molding the polyamide resin composition of the present invention can be used, for example, as a film capacitor, a release film for FPD, or an in-vehicle motor insulating film.
  • the polyamide resin composition of the present invention can be molded into a foam by a method using a chemical foaming agent or a method using a supercritical gas or an inert gas.
  • the foam obtained by molding the polyamide resin composition of the present invention can be used in the fields of electrical and electronic equipment and the field of automobiles.
  • the polyamide resin composition of the present invention can be molded into various fibers and various non-woven fabrics by known spinning methods such as a melt spinning method, a flash spinning method, an electrospinning method, and a melt blow method.
  • the fiber or non-woven fabric obtained by molding the polyamide resin composition of the present invention can be used as a bag filter for electrostatic precipitators, a motor binding yarn, a core material for clothing, a dry non-woven fabric, and felt.
  • the polyamide resin composition was evaluated by the following method.
  • (1) Average Fiber Diameter and Average Fiber Length of Cellulose Fibers in Polyamide Resin Composition A sufficiently dried resin composition is injection-molded using an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd .: NEX110-12E) and ISO.
  • the dumbbell test piece (test portion 80 mm ⁇ 10 mm ⁇ 4 mm) described in Standard 3167 was prepared.
  • the polyamide resin was polyamide 6, the conditions for injection molding were a resin temperature of 250 ° C., a mold temperature of 70 ° C., an injection time of 12 seconds, and a cooling time of 20 seconds.
  • the injection molding conditions were a resin temperature of 290 ° C., a mold temperature of 80 ° C., an injection time of 12 seconds, and a cooling time of 20 seconds.
  • the conditions for injection molding were a resin temperature of 200 ° C., a mold temperature of 80 ° C., an injection time of 12 seconds, and a cooling time of 20 seconds.
  • a section having a thickness of 100 nm was taken from an injection-molded piece using a frozen ultramicrotome, and after section staining, observation was performed using a transmission electron microscope (JEM-1230 manufactured by JEOL Ltd.).
  • the length in the direction perpendicular to the longitudinal direction and the length in the longitudinal direction of the cellulose fiber (single fiber) were measured. At this time, the maximum length in the vertical direction was defined as the fiber diameter, and the length in the longitudinal direction was defined as the fiber length.
  • the fiber diameter and fiber length of 10 cellulose fibers (single fibers) were measured, and the average value of 10 fibers was calculated and used as the average fiber diameter and average fiber length.
  • a section having a thickness of 10 ⁇ m cut out by a microtome was cut out using a stereoscopic microscope (SZ-40 manufactured by OLYMPUS). Observation was performed, and the fiber diameter was measured from the obtained image in the same manner as above, and the average fiber diameter was obtained.
  • the flexural modulus of the test piece obtained in (1) is determined by the ISO178-compliant three-point support bending method (distance between fulcrums: 64 mm, test speed: 2 mm / min, test atmosphere: 23 ° C, 50). % RH, in an absolutely dry state).
  • the flexural modulus was evaluated according to the following criteria. ⁇ : 8.0 GPa ⁇ flexural modulus (best); ⁇ : 6.0 GPa ⁇ flexural modulus ⁇ 8.0 GPa (good); ⁇ : 4.0 GPa ⁇ flexural modulus ⁇ 6.0 GPa (no problem in practical use); X: flexural modulus ⁇ 4.0 GPa (there is a problem in practical use).
  • the coefficient of linear expansion The test piece obtained in (1) was cut into 10 mm ⁇ 4 mm ⁇ 4 mmt so that the flow direction (MD direction) of the resin at the time of injection molding was the longitudinal direction.
  • the coefficient of linear expansion in the MD direction of the sample was measured based on JIS K7197, and the average value in the region of 20 to 150 ° C. was calculated.
  • the coefficient of linear expansion was evaluated according to the following criteria.
  • the rate of decrease in the coefficient of linear expansion is a significant characteristic value when comparing polyamide resin compositions having the same content of cellulose fibers. ⁇ : 65% ⁇ reduction rate (best); ⁇ : 60% ⁇ decrease rate ⁇ 65% (good); ⁇ : 30% ⁇ reduction rate ⁇ 60% (no problem in practical use).
  • Heat resistance heat distortion temperature
  • the heat distortion temperature of the test piece obtained in (1) was measured based on ISO 75. At this time, the loads were measured at 1.8 MPa and 0.45 MPa.
  • the heat distortion temperature was evaluated according to the following criteria. ⁇ Heat distortion temperature (load 1.8 MPa) ⁇ : 188 ° C ⁇ heat distortion temperature (best); ⁇ : 170 ° C ⁇ heat distortion temperature ⁇ 188 ° C (good); ⁇ : 130 ° C ⁇ ⁇ heat distortion temperature ⁇ 170 ° C (no problem in practical use); X: Heat distortion temperature ⁇ 130 ° C (there is a problem in practical use).
  • Physical property retention rate (%) ⁇ (recycled value) / (initial value) ⁇ x 100
  • the retention rate of physical properties after recycling three times was evaluated according to the following criteria. ⁇ : 95% ⁇ retention rate of physical properties (best); ⁇ : 90% ⁇ Physical property retention rate ⁇ 95% (good); ⁇ : 85 ⁇ Physical property retention rate ⁇ 90% (no problem in practical use); X: Physical characteristic retention rate ⁇ 85% (there is a problem in practical use).
  • Raw materials (1) Polyamide resin monomer component ⁇ ⁇ -caprolactam ⁇ 6-aminocaproic acid ⁇ Polyamide 66 salt (a salt of the raw material monomer constituting the polyamide 66, specifically, an isomorphic salt of hexamethylenediamine-adipic acid) ⁇ ⁇ -Laurolactam ⁇ 12-Aminododecanoic acid
  • A-1 KY110N (Selish KY110N manufactured by Daicel FineChem Co., Ltd., containing 15% by mass of cellulose fiber having an average fiber diameter of 125 nm (unmodified).
  • A-2 KY100G (Selish KY100G manufactured by Daicel FineChem Co., Ltd., containing 10% by mass of cellulose fibers having an average fiber diameter of 125 nm (unmodified).
  • A-3 KY100S (Selish KY100S manufactured by Daicel FineChem Co., Ltd., containing 25% by mass of cellulose fibers having an average fiber diameter of 140 nm (unmodified).
  • Bacterial cellulose fiber (undenatured) 50 mL of a medium having a composition of 0.5% by mass glucose, 0.5% by mass polypeptone, 0.5% by mass yeast extract, and 0.1% by mass magnesium sulfate heptahydrate was dispensed into a 200 mL Erlenmeyer flask. It was sterilized by steam at 120 ° C. for 20 minutes in an autoclave.
  • Gluconacetobacter xylinus (NBRC 16670) grown on a test tube slope agar medium was inoculated into one loop loop and statically cultured at 30 ° C. for 7 days.
  • A-6 TEMPO-catalyzed cellulose oxide fiber (cellulose fiber in which a part of the hydroxyl group derived from cellulose is modified with a hydrophilic substituent): 500 g (absolutely dry) of unbeaten kraft pulp (whiteness 85%) derived from bleached softwood was added to 500 mL of an aqueous solution containing 780 mg of TEMPO and 75.5 g of sodium bromide, and the mixture was stirred until the pulp was uniformly dispersed. .. The oxidation reaction was started by adding an aqueous sodium hypochlorite solution to the solution so as to have a concentration of 6.0 mmol / g.
  • Ether-modified cellulose fiber (cellulose fiber in which a part of the hydroxyl group derived from cellulose is modified with a hydrophobic substituent): 19.94 kg of water was added to 600 g of softwood bleached kraft pulp (manufactured by Oji Paper Co., Ltd., solid content 25%) to prepare an aqueous suspension having a solid content concentration of 0.75% by mass.
  • the obtained slurry was mechanically defibrated using a bead mill (NVM-2 manufactured by IMEX) to obtain cellulose fibers (zirconia bead diameter 1 mm, bead filling amount 70%, rotation speed 2000 rpm, number of treatments 2). times).
  • NMP N-methyl-2-pyrrolidone
  • toluene 500 mL of N-methyl-2-pyrrolidone (NMP) and 250 mL of toluene were added, and the cellulose fibers were dispersed in NMP / toluene with stirring.
  • a cooler was attached, and the dispersion was heated to 150 ° C. under a nitrogen atmosphere, and acetone and water contained in the dispersion were distilled off together with toluene. Then, the dispersion was cooled to 40 ° C., 15 mL of pyridine and 25 g of hexamethyldisilazane (silyl etherifying agent) were added and reacted under a nitrogen atmosphere for 90 minutes to prepare an NMP dispersion of ether-modified cellulose fibers.
  • the obtained NMP dispersion of the ether-modified cellulose fiber was replaced with water by precipitating the cellulose fiber by a centrifuge. This was repeated 3 times to prepare an aqueous dispersion containing 1.0% by mass of ether-modified cellulose fibers having an average fiber diameter of 100 nm.
  • the ether-modified cellulose fiber was analyzed by 1 H-NMR, 13 C-NMR, and FT-IR, it was confirmed that a part of the hydroxyl group derived from cellulose was replaced with a hydrophobic silyl ether group.
  • Example 1 Polymerization method A: Low temperature polymerization
  • Serish KY110N manufactured by Daicel FineChem: containing 15% by mass of cellulose fibers having an average fiber diameter of 125 nm
  • 83 parts by mass of ⁇ -caprolactam and 17 parts by mass of 6-aminocaproic acid are stirred and mixed with a mixer until a uniform dispersion is obtained, and a paste-like mixed dispersion is prepared. Obtained.
  • This mixed dispersion was gradually heated under a nitrogen stream, the temperature was raised to 190 ° C.
  • Examples 2 to 13 (Polymerization method A: Low temperature polymerization) A polyamide resin composition was obtained in the same manner as in Example 1 except that the type of cellulose fiber and the content of cellulose fiber were changed as shown in Table 1.
  • Example 14 Polymerization method A: Low temperature polymerization
  • Serish KY110N manufactured by Daicel FineChem: containing 15% by mass of cellulose fibers having an average fiber diameter of 125 nm
  • 167 parts by mass of the aqueous dispersion of the cellulose fibers and 100 parts by mass of ⁇ -caprolactam were stirred and mixed with a mixer until a uniform dispersion was obtained, and a paste-like mixed dispersion was obtained.
  • the mixed dispersion was heated to 190 ° C. while stirring, and the pressure was increased to 0.7 MPa while gradually releasing water vapor.
  • Example 15 Polymerization method A: Low temperature polymerization
  • 33 parts by mass of the aqueous dispersion of cellulose fibers and 100 parts by mass of the polyamide 66 salt were stirred and mixed with a mixer until a uniform dispersion was obtained to obtain a paste-like mixed dispersion.
  • This mixed dispersion was gradually heated under a nitrogen stream, the temperature was raised to 240 ° C. while discharging water vapor during the heating, and the mixture was allowed to stand at 240 ° C. for 12 hours to carry out a polymerization reaction (). Low temperature polymerization). At this time, stirring was not performed.
  • the polyamide 66 salt was in a liquid state (ie, a molten state).
  • the obtained polymerization reaction product was pulverized to obtain a flake-shaped resin composition.
  • the obtained flake-shaped resin composition was smelted with hot water at 95 ° C. and then dried.
  • Examples 16 and 17 (Polymerization method A: Low temperature polymerization) A polyamide resin composition was obtained in the same manner as in Example 15 except that the content of the cellulose fibers and the polymerization temperature were changed as shown in Table 1.
  • the polyamide 66 salt was in a liquid state (ie, a molten state) at the polymerization temperature (ie 240 ° C.).
  • the polyamide 66 salt was in a solid state at the polymerization temperature (ie, 195 ° C.).
  • Example 18 Polymerization method A: Low temperature polymerization
  • 33 parts by mass of the aqueous dispersion of cellulose fibers, 83 parts by mass of ⁇ -laurolactam and 17 parts by mass of 12-aminododecanoic acid are stirred and mixed with a mixer until a uniform dispersion is obtained, and the paste is used.
  • a mixed dispersion in the form of a mixture was obtained.
  • This mixed dispersion was gradually heated under a nitrogen stream, the temperature was raised to 160 ° C. while discharging water vapor during the heating, and the mixture was allowed to stand at 160 ° C. for 12 hours to carry out a polymerization reaction (). Low temperature polymerization). At this time, stirring was not performed.
  • ⁇ -laurolactam was in the liquid state (ie, in the molten state) and 12-aminododecanoic acid was in the solid state.
  • the obtained polymerization reaction product was pulverized to obtain a flake-shaped resin composition.
  • the obtained flake-shaped resin composition was smelted with hot water at 95 ° C. and then dried.
  • Example 19 (Polymerization method A: Low temperature polymerization) A polyamide resin composition was obtained in the same manner as in Example 18 except that the content of the cellulose fibers was changed as shown in Table 1.
  • Example 20 By adjusting the polymerization time in Comparative Example 1, a polyamide 6 resin (number average molecular weight 20100, molecular weight distribution 2.8) was obtained. 50 parts by mass of the polyamide 6 resin and 50 parts by mass of the resin composition obtained in Example 6 were dry-blended and supplied to the main hopper of a twin-screw extruder (TEM26SS manufactured by Toshiba Machine Co., Ltd., screw diameter 26 m). It was sufficiently melt-kneaded at 260 ° C., dispensed into strands, and cut to obtain pellets of the resin composition.
  • TEM26SS twin-screw extruder
  • Example 21 By adjusting the polymerization time in Comparative Example 1, a polyamide 6 resin (number average molecular weight 21000, molecular weight distribution 3.6) was obtained. 50 parts by mass of the polyamide 6 resin and 50 parts by mass of the resin composition obtained in Example 6 were dry-blended and supplied to the main hopper of a twin-screw extruder (a twin-screw extruder similar to Example 20). It was sufficiently melt-kneaded at 260 ° C., dispensed into strands, and cut to obtain pellets of the resin composition.
  • a twin-screw extruder a twin-screw extruder similar to Example 20
  • Example 22 By adjusting the polymerization time in Comparative Example 1, a polyamide 6 resin (number average molecular weight 24200, molecular weight distribution 3.7) was obtained. 50 parts by mass of the polyamide 6 resin and 50 parts by mass of the resin composition obtained in Example 6 were dry-blended and supplied to the main hopper of a twin-screw extruder (a twin-screw extruder similar to Example 20). It was sufficiently melt-kneaded at 260 ° C., dispensed into strands, and cut to obtain pellets of the resin composition.
  • a twin-screw extruder a twin-screw extruder similar to Example 20
  • Comparative Example 1 (Polymerization method A: Low temperature polymerization) A polyamide resin composition was obtained in the same manner as in Example 1 except that an aqueous dispersion of cellulose fibers was not added.
  • Comparative Example 2 (Polymerization method A: Low temperature polymerization) A polyamide resin composition was obtained in the same manner as in Example 15 except that an aqueous dispersion of cellulose fibers was not added.
  • Comparative Example 3 (Polymerization method A: Low temperature polymerization) A polyamide resin composition was obtained in the same manner as in Example 18 except that an aqueous dispersion of cellulose fibers was not added.
  • Comparative Example 4 Polymerization method B: melt polymerization + solid phase polymerization
  • Serish KY110N manufactured by Daicel FineChem: containing 15% by mass of cellulose fibers having an average fiber diameter of 125 nm
  • Purified water was added to this aqueous dispersion and stirred with a mixer to prepare an aqueous dispersion having a cellulose fiber content of 3% by mass.
  • 70 parts by mass of the aqueous dispersion of the cellulose fibers and 100 parts by mass of ⁇ -caprolactam were further stirred and mixed with a mixer until a uniform dispersion was obtained.
  • the mixed dispersion was heated to 240 ° C.
  • melt polymerization was carried out at 240 ° C. for 1 hour.
  • the resin composition (pellets) obtained at the time of dispensing was smelted with hot water at 95 ° C. and then dried. The dried pellets were subjected to solid phase polymerization at 170 ° C. for 15 hours under a nitrogen stream.
  • Comparative Example 5 (Polymerization method C: Melt polymerization) A mixed dispersion of 70 parts by mass of an aqueous cellulose fiber dispersion and 100 parts by mass of ⁇ -caprolactum prepared in the same manner as in Comparative Example 4 was heated to 240 ° C. with stirring, and while gradually releasing water vapor, 0. The pressure was increased to 7 MPa. After that, the pressure was released to atmospheric pressure, and melt polymerization was carried out at 240 ° C. for 1 hour. The obtained resin composition (pellet) was smelted with hot water at 95 ° C. and then dried.
  • Comparative Example 30 (Polymerization method B: melt polymerization + solid phase polymerization) 167 parts by mass of the cellulose fiber aqueous dispersion and 100 parts by mass of the polyamide 66 salt prepared in the same manner as in Comparative Example 4 were further stirred and mixed with a mixer until a uniform dispersion was obtained.
  • the mixed dispersion was heated at 230 ° C. until the internal pressure reached 1.5 MPa. After reaching that pressure, heating was continued to maintain that pressure while gradually releasing water vapor. When the temperature reached 280 ° C., the pressure was released to normal pressure, and melt polymerization was carried out for 1 hour.
  • the resin composition (pellets) obtained at the time of dispensing was smelted with hot water at 95 ° C. and then dried. The dried pellets were subjected to solid phase polymerization at 220 ° C. for 15 hours under a nitrogen stream.
  • Comparative Example 31 (Polymerization method C: Melt polymerization) 167 parts by mass of the cellulose fiber aqueous dispersion and 100 parts by mass of the polyamide 66 salt prepared in the same manner as in Comparative Example 4 were further stirred and mixed with a mixer until a uniform dispersion was obtained.
  • the mixed dispersion was heated at 230 ° C. until the internal pressure reached 1.5 MPa. After reaching that pressure, heating was continued to maintain that pressure while gradually releasing water vapor. When the temperature reached 280 ° C., the pressure was released to normal pressure, and melt polymerization was carried out for 1 hour.
  • the resin composition (pellets) obtained at the time of dispensing was smelted with hot water at 95 ° C. and then dried.
  • Comparative Example 32 (Polymerization method B: melt polymerization + solid phase polymerization) 167 parts by mass of the cellulose fiber aqueous dispersion, 83 parts by mass of ⁇ -laurolactam and 17 parts by mass of 12-aminododecanoic acid prepared in the same manner as in Comparative Example 4 were further stirred and mixed with a mixer until a uniform dispersion was obtained. .. This mixed dispersion was gradually heated under a nitrogen stream, the temperature was raised to 200 ° C. while discharging water vapor during the heating, and the mixture was stirred at 230 ° C. for 1 hour to carry out a polymerization reaction. The resin composition (pellets) obtained at the time of dispensing was smelted with hot water at 95 ° C. and then dried. The dried pellets were subjected to solid phase polymerization at 150 ° C. for 15 hours under a nitrogen stream.
  • Comparative Example 33 (Polymerization method C: Melt polymerization) 167 parts by mass of the cellulose fiber aqueous dispersion, 83 parts by mass of ⁇ -laurolactam and 17 parts by mass of 12-aminododecanoic acid prepared in the same manner as in Comparative Example 4 were further stirred and mixed with a mixer until a uniform dispersion was obtained. .. This mixed dispersion was gradually heated under a nitrogen stream, the temperature was raised to 200 ° C. while discharging water vapor during the heating, and the mixture was stirred at 230 ° C. for 1 hour to carry out a polymerization reaction. The resin composition (pellets) obtained at the time of dispensing was smelted with hot water at 95 ° C. and then dried.
  • a polyamide resin (PA6) was obtained in the same manner as in Comparative Example 5 except that an aqueous dispersion of cellulose fibers was not added. This operation was performed 10 times to obtain 10 kinds of polyamide resins (PA6).
  • the melting points of 10 kinds of polyamide resins (PA6) were measured by a differential scanning calorimeter, and the average value of these measured values was used as the melting point of the polyamide resin (PA6).
  • the melting point of the polyamide resin (PA6) was 220 ° C.
  • Reference example 4 100 parts by mass of the polyamide resin obtained in Comparative Example 1 was supplied to the main hopper of the twin-screw extruder, and 43 parts by mass of glass fibers were supplied from the side feeder on the way. It was sufficiently melt-kneaded at 260 ° C., dispensed into strands, and cut to obtain pellets of the resin composition.
  • Tables 1 to 4 show the results of measuring the characteristic values of the polyamide resin compositions obtained in Examples 1 to 22, Comparative Examples 1 to 33, and Reference Examples 1 to 4.
  • Polymerization method A Low temperature polymerization
  • Polymerization method B melt polymerization + subsequent solid phase polymerization
  • Polymerization method C Melt polymerization.
  • the polymerization temperature of the polymerization method B is the temperature at the time of melt polymerization.
  • the reduction rates of the linear expansion coefficients of Examples 1 to 4, 6 to 15 and 18, respectively, are Comparative Examples 5,7,9,11,15,17,19,21,23,25,27,29, respectively. The rate of decrease from the coefficient of linear expansion of 11, 31 and 33 is shown.
  • the melting point of the polyamide obtained in Reference Example 1 220 ° C.
  • the melting point of the polyamide obtained in Reference Example 2 270 ° C.
  • the melting point of the polyamide obtained in Reference Example 3 175 ° C.
  • All of the polyamide resin compositions of Examples 1 to 22 have a tensile elastic modulus of 3.2 GPa or more, preferably 3.8 GPa or more, more preferably 4.7 GPa or more, and a linear expansion coefficient of 40 ⁇ in the MD direction. It was 10-6 (1 / ° C.) or less, preferably 15.0 ⁇ 10-6 (1 / ° C.) or less, and more preferably 7.0 ⁇ 10-6 (1 / ° C.) or less.
  • the coefficient of linear expansion of the examples in which the low temperature polymerization method was adopted was the same as that of each example except that the melt polymerization method was adopted instead of the low temperature polymerization method.
  • 30% or more based on the coefficient of linear expansion of similar comparative examples Comparative Examples 5, 7, 9, 11, 15, 17, 19, 21, 23, 25, 27, 29, 11, 31 and 33, respectively. The rate of decline was shown. Comparative examples in which the melt polymerization method and the solid phase polymerization method were used in combination (for details, Comparative Examples 4, 6, 8, 10, 14, 16, 18, 20, 22, 24, 26, 28, 30 and 32).
  • the coefficient of linear expansion of is the same as that of each comparative example except that only the melt polymerization method is adopted (comparative examples 5, 7, 9, 11, 15, 17, 19, 21, 23, 25, 27, respectively). , 29, 31 and 33) were similar in value to the coefficient of linear expansion.
  • Examples 1 to 19 since it is not necessary to hold the obtained polyamide resin composition in a molten state at the time of producing the polyamide resin composition, the polyamide resin composition is extremely easy to handle, and the yield is 99% by mass. That was all. In the yields of Examples 1 to 19, when the polymerization reaction product was taken out from the reaction vessel for refining after low temperature polymerization, the proportion of the polymerization reaction product adhering to the reaction vessel and difficult to recover was reduced from 100% by mass. Value. In Comparative Examples 4 to 33, the polyamide resin composition must be held in a molten state at the time of producing the polyamide resin composition, and as the polymerization progresses, the melt viscosity becomes high and it becomes difficult to dispense, and the yield is high.
  • the physical property retention rate (retention rate of bending elastic modulus and tensile elastic modulus) after recycling three times was 95% or more.
  • the retention rate of physical properties after recycling three times was low.
  • the content of the cellulose fiber is 8 to 100 parts by mass (particularly 8 to 80 parts by mass) with respect to 100 parts by mass of the polyamide resin, and the polyamide resin contains a monomer in a liquid state at the polymerization temperature as a monomer component.
  • the evaluation result of the mechanical properties is " ⁇ " or " ⁇ ".
  • Method the evaluation results of heat resistance and recyclability were also " ⁇ " or " ⁇ ".
  • PA6 in which the content of the cellulose fiber is 22 to 100 parts by mass (particularly 22 to 80 parts by mass) with respect to 100 parts by mass of the polyamide resin, and the polyamide resin contains a monomer in a liquid state at the polymerization temperature as a monomer component.
  • the evaluation result of the mechanical properties for example, bending elastic modulus, tensile elastic modulus and linear expansion coefficient (and its reduction rate)
  • ⁇ bending elastic modulus
  • the polyamide resin composition of the present invention can be suitably used for automobiles, electrical and electronic equipment, agriculture / fisheries, medical equipment, miscellaneous goods, and the like.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention concerne une composition de résine polyamide qui améliore sensiblement les propriétés mécaniques telles que le module d'élasticité en flexion, le module d'élasticité en traction et le coefficient de dilatation linéaire (et en particulier à la fois le module d'élasticité en traction et le coefficient de dilatation linéaire). La présente invention concerne une composition de résine de polyamide qui contient de 0,01 à 200 parties en masse de fibres de celluloses pour 100 parties en masse d'une résine de polyamide. La composition de résine de polyamide est caractérisée en ce que le module d'élasticité en traction des corps moulés obtenus à partir de la composition de résine de polyamide est supérieur à 3,0 GPa.
PCT/JP2021/036587 2020-10-06 2021-10-04 Composition de résine polyamide et procédé de production d'une composition de résine polyamide WO2022075249A1 (fr)

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Cited By (1)

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JP7294715B1 (ja) 2022-04-01 2023-06-20 ユニチカ株式会社 ポリアミド樹脂組成物およびポリアミド樹脂組成物の製造方法

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JP2002003599A (ja) * 2000-06-19 2002-01-09 Toray Ind Inc ポリアミドの製造方法、それから得られるポリアミドおよびポリアミド成形体
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WO2011126038A1 (fr) * 2010-04-06 2011-10-13 ユニチカ株式会社 Composition de résine polyamide et procédé de production d'une composition de résine polyamide
JP2012031271A (ja) * 2010-07-30 2012-02-16 Unitika Ltd ポリアミドの製造方法
JP2012180486A (ja) * 2011-03-03 2012-09-20 Unitika Ltd ポリアミド低重合体の製造方法
JP2012188557A (ja) * 2011-03-11 2012-10-04 Unitika Ltd ポリアミドの製造方法
JP2014136745A (ja) * 2013-01-17 2014-07-28 Unitika Ltd ポリアミド樹脂成形体
JP2020125563A (ja) * 2019-02-06 2020-08-20 株式会社スギノマシン セルロース繊維乾燥体、セルロース繊維樹脂複合体、成形体

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JPS5863723A (ja) * 1981-10-13 1983-04-15 Ube Ind Ltd ポリアミドの製法
JP2002003599A (ja) * 2000-06-19 2002-01-09 Toray Ind Inc ポリアミドの製造方法、それから得られるポリアミドおよびポリアミド成形体
US20040122133A1 (en) * 2002-11-07 2004-06-24 Board Of Trustees Of Michigan State University Filler reinforced thermoplastic compositions and process for manufacture
WO2011126038A1 (fr) * 2010-04-06 2011-10-13 ユニチカ株式会社 Composition de résine polyamide et procédé de production d'une composition de résine polyamide
JP2012031271A (ja) * 2010-07-30 2012-02-16 Unitika Ltd ポリアミドの製造方法
JP2012180486A (ja) * 2011-03-03 2012-09-20 Unitika Ltd ポリアミド低重合体の製造方法
JP2012188557A (ja) * 2011-03-11 2012-10-04 Unitika Ltd ポリアミドの製造方法
JP2014136745A (ja) * 2013-01-17 2014-07-28 Unitika Ltd ポリアミド樹脂成形体
JP2020125563A (ja) * 2019-02-06 2020-08-20 株式会社スギノマシン セルロース繊維乾燥体、セルロース繊維樹脂複合体、成形体

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7294715B1 (ja) 2022-04-01 2023-06-20 ユニチカ株式会社 ポリアミド樹脂組成物およびポリアミド樹脂組成物の製造方法
WO2023190039A1 (fr) * 2022-04-01 2023-10-05 ユニチカ株式会社 Composition de résine de polyamide et procédé de production de composition de résine de polyamide
JP2023152040A (ja) * 2022-04-01 2023-10-16 ユニチカ株式会社 ポリアミド樹脂組成物およびポリアミド樹脂組成物の製造方法

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