JP2019183072A - Polyamide resin composition - Google Patents

Abstract

To provide a polyamide resin composition capable of sufficiently exhibiting long term durability such as repeat fatigue resistance and abrasion resistance in actual applications while adding sufficient mechanical properties to a resin molded body.SOLUTION: There is provided a polyamide resin composition containing 100 pts.mass of (A) a polyamide resin, (B) cellulose, and 0.01 to 5 pts.mass of (C) a surface modifier. The polyamide resin composition satisfies a relational expression (1):1≥10×W'/W (1), in which (C) surface modifier content in an insoluble component is W', (C) surface modifier content in a solution is W'' and total of W' and W'' is W, when the polyamide resin composition is dissolved in a polyamide resin soluble solvent.SELECTED DRAWING: None

Description

  The present invention relates to a polyamide resin composition containing cellulose.

  Thermoplastic resins are light and excellent in processing characteristics, and thus are widely used in various fields such as automobile parts, electric / electronic parts, office equipment housings, precision parts and the like. However, the resin alone often has insufficient mechanical properties, slidability, thermal stability, dimensional stability, etc., and a composite of resin and various inorganic materials is generally used.

A resin composition obtained by reinforcing a thermoplastic resin with a reinforcing material that is an inorganic filler such as glass fiber, carbon fiber, talc, or clay has a high specific gravity, so that there is a problem that the weight of the resulting resin molded body increases.
Therefore, in recent years, cellulose having a low environmental load has been used as a new reinforcing material for resins mainly in the automobile industry and the like.

  It is known that cellulose has a high elastic modulus comparable to an aramid fiber and a linear expansion coefficient lower than that of glass fiber as its simple substance properties. Further, the true density is as low as 1.56 g / cm 3, and glass (density 2.4 to 2.6 g / cm 3) or talc (density 2.7 g / cm 3) used as a reinforcing material for general thermoplastic resins. Compared to the lighter material.

Cellulose is not only made from trees, but also from hemp, cotton, kenaf, cassava and so on. Furthermore, bacterial cellulose represented by Nata de Coco is also known. After these materials are hydrolyzed and weakened, they are defibrated by a crushing method such as a high-pressure homogenizer, microfluidizer, ball mill, or disk mill. It is known that it can be formed. A large amount of natural resources as raw materials for cellulose exists on the earth, and for this effective use, a technology that utilizes cellulose as a filler in a resin is attracting attention.
Automobiles have been converted to HEV and EV in response to fuel efficiency regulations that are becoming stricter year by year. However, reduction of vehicle weight is one of the issues that must be promoted at the same time. As a solution, application of CNF (cellulose nanofiber) reinforced resin is attracting attention.

  However, in order to mix CNF in the resin, it is necessary to dry and powder CNF. However, CNF has a problem that it becomes a strong aggregate from a finely dispersed state in the process of separating from water and is difficult to redisperse. is there. This cohesive force is expressed by hydrogen bonding due to the hydroxyl group of cellulose, and is said to be very strong.

  Therefore, in order to develop sufficient performance, it is necessary to relax hydrogen bonds due to hydroxyl groups of cellulose. Even if the relaxation of hydrogen bonds can be sufficiently realized, it is difficult to maintain the defibrated state (nanometer size (ie, less than 1 μm)) in the resin.

  As described above, since it is difficult to finely disperse CNF in the resin, techniques for coexisting CNF during polymerization of the resin, techniques for modifying the CNF surface, and the like have been proposed as solutions.

  For example, Patent Document 1 introduces a technique for allowing cellulose to coexist during the polymerization of a thermoplastic resin. As in Patent Document 1, it is possible to increase the strength by finely dispersing CNF in the resin, expanding the range of applicable parts, and being applicable to parts that are directly attached to a vehicle and subjected to repeated stress. In recent years, it has been demanded.

International Publication No. 2011/126038

  However, in the conventional technology, the interfacial strength between the filler and the resin is still insufficient, and for example, a problem that the material breaks due to repeated stress has been revealed. This is because even when CNF is added during the polymerization of polyamide, CNF tends to continue to exist mainly in the aqueous phase, and thus it cannot be formed in a dispersed state or interface strength that can withstand repeated stress. Conceivable. Further, the conventional technology has revealed a problem that the processability at the time of extrusion and molding is still insufficient and it is difficult to mass-produce. This is considered to be caused by decomposition products due to frictional heat during melt kneading of cellulose and resin, lower molecular weight of the surface modifier in the resin, and further volatile components.

  The present invention provides a polyamide resin composition that solves the above-mentioned problems and can sufficiently exhibit long-term durability such as repeated fatigue resistance and wear resistance in practical applications while giving sufficient mechanical properties to a resin molded body. The purpose is to provide.

  In order to solve the above-mentioned problems, the present inventors have intensively studied, and as a result, in a resin composition containing a polyamide resin, cellulose, and a surface modifier, the amount is expressed by controlling the amount of the surface modifier. The inventors have found that the above problems can be solved, and have made the present invention.

That is, the present invention includes the following aspects.
[1] A polyamide resin composition comprising (A) 100 parts by mass of a polyamide resin, (B) cellulose, and (C) 0.01 to 5 parts by mass of a surface modifier.
[2] When the polyamide resin composition is dissolved in a polyamide resin-soluble solvent, the content of (C) the surface modifier in the insoluble portion is W ′, and the content of the (C) surface modifier in the solution Is W ″, and the sum of W ′ and W ″ is W, the following relational expression (1):
1 ≧ 10 × W ′ / W (1)
The polyamide resin composition according to the first aspect, which satisfies the above.
[3] The polyamide resin composition according to the above aspect 1 or 2, comprising 0.01 to 2 parts by mass of a surface modifier (C).
[4] The polyamide resin composition according to any one of the above aspects 1 to 3, wherein the number average molecular weight of the (C) surface modifier is 100 to 2000.
[5] (C) The surface modifier is selected from the group consisting of polyolefin resins, polyamide resins, polyester resins, polyacetal resins, polyacrylic resins, polyphenylene ether resins, polyphenylene sulfide resins, and modified products thereof. The polyamide resin composition according to any one of the above aspects 1 to 4, which is one or more selected oligomers.
[6] The polyamide resin composition according to any one of the above aspects 1 to 5, which includes (D) a metal ion component.
[7] (D) The group in which the metal ion component is made of copper iodide (CuI), cuprous bromide (CuBr), cupric bromide (CuBr ₂ ), cuprous chloride (CuCl), and copper acetate. The polyamide resin composition according to aspect 6, which is one or more selected from the group consisting of:
[8] The polyamide resin composition according to any one of the above aspects 1 to 7, comprising (E) a sliding agent component.
[9] (E) The sliding agent component is at least one selected from the group consisting of alcohol, amine, carboxylic acid, hydroxy acid, amide, ester, polyoxyalkylene glycol, silicone oil, wax, and lubricating oil. The polyamide resin composition according to aspect 8 above.
[10] (E) The polyamide resin composition according to the aspect 8 or 9, wherein the sliding agent component has a melting point of 40 to 150 ° C.
[11] The composition according to any one of the above aspects 1 to 10, which is obtained by mixing a raw material monomer of (A) a polyamide resin and an aqueous dispersion of (B) cellulose and performing a polymerization reaction. Polyamide resin composition.
[12] A molded article comprising the polyamide resin composition according to any one of the above aspects 1 to 11.

  ADVANTAGE OF THE INVENTION According to this invention, the polyamide resin composition which has the repetition fatigue resistance in an actual use and the outstanding workability is provided, giving sufficient mechanical characteristics to a resin molding.

  Illustrative aspects of the present invention will be specifically described below, but the present invention is not limited to these aspects.

  In one embodiment, the polyamide resin composition includes a polyamide resin, cellulose, and a predetermined amount of a surface modifier. Hereinafter, examples of each component of the polyamide resin composition will be further described.

≪ (A) Polyamide resin≫
Examples of the (A) polyamide resin that can be used in the present invention are not particularly limited, but polyamide 6, polyamide 11, polyamide 12, etc. obtained by polycondensation reaction of lactams; 1,6-hexanediamine, 2 -Methyl-1,5-pentanediamine, 1,7-heptanediamine, 2-methyl-1-6-hexanediamine, 1,8-octanediamine, 2-methyl-1,7-heptanediamine, 1,9- Nonanediamine, 2-methyl-1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, m-xylylenediamine, and the like, butanedioic acid, pentane Diacid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, benzene-1,2-di Obtained as a copolymer with dicarboxylic acids such as rubonic acid, benzene-1,3-dicarboxylic acid, benzene-1,4 dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, etc. Polyamide 6,6, Polyamide 6,10, Polyamide 6,11, Polyamide 6,12, Polyamide 6, T, Polyamide 6, I, Polyamide 9, T, Polyamide 10, T, Polyamide 2M5, T, Polyamide MXD, 6, Examples thereof include polyamide 6, C, polyamide 2M5, C, and the like; and copolymers obtained by copolymerizing them (polyamide 6, T / 6, I as an example).

  Among these polyamide resins, aliphatic polyamides such as polyamide 6, polyamide 11, polyamide 12, polyamide 6,6, polyamide 6,10, polyamide 6,11, polyamide 6,12, polyamide 6, C, polyamide 2M5, C, etc. An alicyclic polyamide is more preferable.

  Although there is no restriction | limiting in particular in the terminal carboxyl group density | concentration of a polyamide resin, A lower limit is preferable in it being 20 micromol / g, More preferably, it is 30 micromol / g. The upper limit of the terminal carboxyl group concentration is preferably 150 μmol / g, more preferably 100 μmol / g, and still more preferably 80 μmol / g.

  In the polyamide resin, the carboxyl end group ratio ([COOH] / [all end groups]) to all end groups is more preferably 0.30 to 0.95. The lower limit of the carboxyl end group ratio is more preferably 0.35, still more preferably 0.40, and most preferably 0.45. The upper limit of the carboxyl end group ratio is more preferably 0.90, even more preferably 0.85, and most preferably 0.80. The carboxyl end group ratio is desirably 0.30 or more from the viewpoint of dispersibility of the cellulose component in the composition, and desirably 0.95 or less from the viewpoint of the color tone of the resulting composition.

  As a method for adjusting the terminal group concentration of the polyamide resin, a known method can be used. For example, diamine compound, monoamine compound, dicarboxylic acid compound, monocarboxylic acid compound, acid anhydride, monoisocyanate, monoacid halide, monoester, monoalcohol, etc. The method of adding the terminal regulator which reacts with a terminal group to a polymerization liquid is mentioned.

  Examples of terminal regulators that react with terminal amino groups include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid. Aliphatic monocarboxylic acids such as cycloaliphatic carboxylic acids; aromatic monocarboxylic acids such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid Carboxylic acid; and a plurality of mixtures arbitrarily selected from these. Of these, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, in terms of reactivity, stability of the sealing end, price, etc. And one or more terminal regulators selected from the group consisting of benzoic acid and acetic acid is most preferred.

  Examples of the terminal regulator that reacts with the terminal carboxyl group include aliphatic amines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine. Examples include monoamines; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine, naphthylamine, and any mixture thereof. Among these, one or more terminals selected from the group consisting of butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine and aniline in terms of reactivity, boiling point, stability of the sealing end, price, etc. A modifier is preferred.

The concentration of the amino terminal group and the carboxyl terminal group is preferably determined from the integral value of the characteristic signal corresponding to each terminal group by ¹ H-NMR in terms of accuracy and simplicity. Specifically, the method described in Japanese Patent Application Laid-Open No. 7-228775 is recommended as a method for obtaining the concentration of these end groups. When this method is used, deuterated trifluoroacetic acid is useful as a measurement solvent. In addition, the number of ¹ H-NMR integrations is required to be at least 300 scans even when measured with an instrument having sufficient resolution. In addition, the concentration of end groups can be measured by a titration measurement method as described in JP-A-2003-055549. However, in order to reduce the influence of mixed additives, lubricants and the like as much as possible, quantification by ¹ H-NMR is more preferable.

  The polyamide resin preferably has an intrinsic viscosity [η] measured in concentrated sulfuric acid at 30 ° C. of 0.6 to 2.0 dL / g, and preferably 0.7 to 1.4 dL / g. More preferably, it is 0.7-1.2 dL / g, still more preferably 0.7-1.0 dL / g. Use of the above-mentioned polyamide resin having an intrinsic viscosity in a preferred range, particularly preferred range, can greatly increase the fluidity in the mold at the time of injection molding of the resin composition and give the effect of improving the appearance of the molded piece. Can do.

  In the present disclosure, the “intrinsic viscosity” is synonymous with a viscosity generally called an intrinsic viscosity. A specific method for determining this viscosity is to measure ηsp / c of several measuring solvents having different concentrations in 96% concentrated sulfuric acid under a temperature condition of 30 ° C., and determine the respective ηsp / c and concentration (c ) And extrapolating the concentration to zero. The value extrapolated to zero is the intrinsic viscosity. Details of these are described in, for example, pages 291 to 294 of Polymer Process Engineering (Prentice-Hall, Inc 1994).

  At this time, it is desirable from the viewpoint of accuracy that the number of points of some measurement solvents having different concentrations is at least 4. At this time, the recommended concentrations of the different viscosity measuring solutions are preferably at least four points of 0.05 g / dL, 0.1 g / dL, 0.2 g / dL, and 0.4 g / dL.

  The number average molecular weight of the polyamide resin is not particularly limited, but the lower limit value is preferably more than 2000, more preferably 3000, and most preferably 5000. The upper limit of the number average molecular weight is not particularly limited, but is preferably 50000 or less from the viewpoint of handleability. In order to ensure molding processability as a resin composition, the number average molecular weight is preferably within the above-mentioned range. The number average molecular weight is a value measured in terms of standard polymethyl methacrylate using GPC (gel permeation chromatography).

≪ (B) Cellulose≫
Next, (B) cellulose that can be used in the present invention will be described in detail. (B) Although the suitable example of a cellulose is not specifically limited, For example, it is 1 or more types of a cellulose pulp, a cellulose whisker, a cellulose fiber, or these modified substances of cellulose, and these are reactive (namely, when a cellulose is denatured). It is preferable in terms of reactivity, (B) reactivity of cellulose and (C) surface modifier), stability, price, and the like.

  In the present disclosure, “length” (L) and “diameter” (D) correspond to the major and minor diameters of cellulose whiskers, and the fiber length and fiber diameter of cellulose pulp and cellulose fibers, respectively.

  The method for producing the cellulose pulp is not particularly limited. For example, after the raw pulp is cut with hot water at 100 ° C. or higher, the hemicellulose portion is hydrolyzed and weakened, and then the high-pressure homogenizer, microfluidizer, ball mill, disk It can be obtained by defibration by a pulverization method using a mill or the like. In a typical embodiment, the cellulose pulp has an L / D ratio of 40 or more and an average fiber diameter exceeding 1000 nm.

  In the present disclosure, the cellulose whisker is a crystalline cellulose remaining after dissolving an amorphous part of cellulose in an acid such as hydrochloric acid or sulfuric acid after cutting the raw material using pulp or the like as a raw material. / The diameter ratio (L / D ratio) is less than 30.

  In the present disclosure, the cellulose fiber is treated with hot water or the like at 100 ° C. or higher, and the hemicellulose portion is hydrolyzed and weakened, and then a high-pressure homogenizer, a microfluidizer, a ball mill, a disk mill, etc. are used. Cellulose defibrated by a pulverization method and having an L / D ratio of 30 or more and not classified into cellulose pulp (that is, an L / D ratio of 40 or more and a fiber diameter exceeding 1000 nm). In a preferred embodiment, the cellulose fiber has an L / D ratio of 30 or more and a number average fiber diameter of 1000 nm or less.

  The L / D lower limit of the cellulose pulp is more preferably 50, even more preferably 80, and most preferably 100. The upper limit is not particularly limited, but is preferably 10,000 or less from the viewpoint of handleability. In order to develop good mechanical properties of the resin composition, the L / D ratio of the cellulose pulp is desirably within the above-mentioned range.

  The L / D upper limit of the cellulose whisker is preferably 25, more preferably 20, still more preferably 15, still more preferably 10, and most preferably 5. Although a minimum is not specifically limited, What is necessary is just to exceed one. In order to develop good slidability of the resin composition, it is desirable that the L / D ratio of the cellulose whisker is within the above range.

  The L / D lower limit of the cellulose fiber is preferably 50, more preferably 80, more preferably 100, still more preferably 120, and most preferably 150. The upper limit is not particularly limited, but is preferably 1000 or less from the viewpoint of handleability. The L / D ratio of the cellulose fiber is preferably within the above-mentioned range in order to exhibit the good mechanical properties of the resin molded body obtained using the resin composition of the present disclosure in a small amount.

  In the present disclosure, the length, diameter, and L / D ratio of each of the cellulose pulp, cellulose whisker, and cellulose fiber are determined based on the water dispersion of each of the cellulose pulp, cellulose whisker, and cellulose fiber. (Trade name “Excel Auto Homogenizer ED-7”, manufactured by Co., Ltd.), and processing conditions: water dispersion dispersed at a rotational speed of 15,000 rpm × 5 minutes is purified to 0.1 to 0.5 mass%. A measurement sample is diluted with water, cast on mica, and air-dried, and is obtained by measurement with an optical microscope, a high-resolution scanning microscope (SEM), or an atomic force microscope (AFM). Specifically, the length (L) and diameter (D) of 100 randomly selected celluloses were measured in an observation field whose magnification was adjusted so that at least 100 celluloses were observed, The ratio (L / D) is calculated. Those having a ratio (L / D) of less than 30 are classified as cellulose whiskers, and those having a ratio of 30 or more are classified as cellulose fibers. However, those whose fiber diameter exceeds 1000 nm and whose ratio (L / D) exceeds 40 are classified as cellulose pulp. For each of the cellulose pulp, cellulose whisker, and cellulose fiber, the number average value of the length (L), the number average value of the diameter (D), and the number average value of the ratio (L / D) are calculated. The length, diameter, and L / D ratio of each of cellulose pulp, cellulose whisker, and cellulose fiber. Moreover, the length and diameter of the cellulose component of the present disclosure are the number average values of the 100 celluloses.

  Alternatively, the length, diameter, and L / D ratio of each of the cellulose pulp, cellulose whisker, and cellulose fiber in the composition are confirmed by measuring the above-described measurement method using the solid composition as a measurement sample. be able to.

  Alternatively, the length, diameter, and L / D ratio of each of the cellulose pulp, cellulose whisker, and cellulose fiber in the composition are determined by adding the resin component in the composition to an organic or inorganic solvent that can dissolve the resin component in the composition. After dissolving and separating the cellulose and thoroughly washing with the solvent, an aqueous dispersion in which the solvent is replaced with pure water or a dispersible organic solvent is prepared, and the cellulose concentration is 0.1 to 0.5% by mass. It can be confirmed by diluting with pure water, casting on mica and air-drying as a measurement sample by the above-described measurement method. At this time, 100 or more randomly selected celluloses are measured.

  Examples of the modified cellulose in the present disclosure include those modified with one or more modifying agents selected from esterifying agents, silylating agents, isocyanate compounds, halogenated alkylating agents, alkylene oxides and / or glycidyl compounds. Can be mentioned.

  The esterifying agent as a modifying agent includes an organic compound having at least one functional group capable of reacting with a hydroxyl group on the surface of cellulose and esterifying it. The esterification can be carried out by the method described in paragraph [0108] of International Publication No. 2017/159823. The esterifying agent may be a commercially available reagent or product.

  Preferable examples of the esterifying agent are not particularly limited. For example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isochoric acid, Aliphatic monocarboxylic acids such as butyric acid; cycloaliphatic monocarboxylic acids such as cyclohexanecarboxylic acid; aromatics such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid A monocarboxylic acid; and a plurality of mixtures arbitrarily selected therefrom, and a symmetric anhydride (acetic anhydride, maleic anhydride, cyclohexane-carboxylic acid anhydride, benzene-sulfonic acid anhydride), optionally selected from these, Mixed acid anhydride (butyric acid-valeric acid anhydride), cyclic anhydride (succinic anhydride, phthalic anhydride) Acid, naphthalene-1,8: 4,5-tetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic acid 3,4-anhydride), ester anhydride (acetic acid 3- (ethoxy Carbonyl) propanoic anhydride, benzoylethyl carbonate) and the like.

  Among these, in terms of reactivity, stability, price, etc., acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, benzoic acid, Acetic anhydride, maleic anhydride, succinic anhydride, and phthalic anhydride are preferably used.

  The silylating agent as a modifier includes a Si-containing compound having at least one reactive group capable of reacting with a hydroxyl group on the surface of cellulose or a group after hydrolysis thereof. The silylating agent may be a commercially available reagent or product.

  Preferable examples of the silylating agent include, but are not limited to, chlorodimethylisopropylsilane, chlorodimethylbutylsilane, chlorodimethyloctylsilane, chlorodimethyldodecylsilane, chlorodimethyloctadecylsilane, chlorodimethylphenylsilane, chloro (1-hexenyl) Dimethylsilane, dichlorohexylmethylsilane, dichloroheptylmethylsilane, trichlorooctylsilane, hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,3 -Diphenyl-1,3-dimethyl-disilazane, 1,3-N-dioctyltetramethyl-disilazane, diisobutyltetramethyldisilazane, diethyltetramethyldisilazane, N-dipropyltetramethyldisilazane, N Dibutyltetramethyldisilazane or 1,3-di (para-t-butylphenethyl) tetramethyldisilazane, N-trimethylsilylacetamide, N-methyldiphenylsilylacetamide, N-triethylsilylacetamide, t-butyldiphenylmethoxysilane, octadecyl Examples include dimethylmethoxysilane, dimethyloctylmethoxysilane, octylmethyldimethoxysilane, octyltrimethoxysilane, trimethylethoxysilane, and octyltriethoxysilane.

  Among these, hexamethyldisilazane, octadecyldimethylmethoxysilane, dimethyloctylmethoxysilane, and trimethylethoxysilane are preferably used from the viewpoints of reactivity, stability, and price.

  The halogenated alkylating agent as a modifying agent includes an organic compound having at least one functional group capable of reacting with a hydroxyl group on the surface of cellulose and halogenating and alkylating it. The halogenated alkylating agent may be a commercially available reagent or product.

  Preferable examples of the halogenated alkylating agent are not particularly limited, and chloropropane, chlorobutane, bromopropane, bromohexane, bromoheptane, iodomethane, iodoethane, iodooctane, iodooctadecane, iodobenzene and the like can be used. Among these, bromohexane and iodooctane can be preferably used in terms of reactivity, stability, price, and the like.

  The isocyanate compound as a modifier includes an organic compound having at least one isocyanate group capable of reacting with a hydroxyl group on the surface of cellulose. Further, the isocyanate compound may be a blocked isocyanate compound that can regenerate the isocyanate group by elimination of the blocking group at a specific temperature, and also a diisocyanate or trimer of polyisocyanate, a burette isocyanate. Or a modified product such as polymethylene polyphenyl polyisocyanate (polymeric MDI). These may be commercially available reagents or products.

  Although it does not specifically limit as a suitable example of an isocyanate compound, Aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, araliphatic polyisocyanate, block isocyanate compound, polyisocyanate etc. are mentioned. For example, tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (isocyanate methyl) Cyclohexane), tolylene diisocyanate (TDI), 2,2'-diphenylmethane diisocyanate, 2,4'-diph Nylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate) , Dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, α, α, α, α-tetramethylxylylene diisocyanate, oxime block agent, phenol block agent, lactam block agent, alcohol block agent, active methylene Blocks that have been reacted with a system block agent, amine block agent, pyrazole block agent, bisulfite block agent, or imidazole block agent And socyanate compounds.

  Among these, TDI, MDI, hexamethylene diisocyanate, and blocked isocyanate using hexamethylene diisocyanate modified and hexamethylene diisocyanate as raw materials can be preferably used from the viewpoint of reactivity, stability, price, and the like.

  The upper limit of the dissociation temperature of the blocking group of the blocked isocyanate compound is preferably 210 ° C., more preferably 190 ° C., and even more preferably 150 ° C. from the viewpoints of reactivity and stability. The lower limit is preferably 70 ° C, more preferably 80 ° C, and even more preferably 110 ° C. Examples of the blocking agent whose block group dissociation temperature falls within this range include methyl ethyl ketone oxime, ortho-secondary butylphenol, caprolactam, sodium bisulfite, 3,5-dimethylpyrazole, 2-methylimidazole and the like.

  The alkylene oxide and / or glycidyl compound as a modifying agent includes an organic compound having at least one alkylene oxide group, glycidyl group and / or epoxy group capable of reacting with a hydroxyl group on the surface of cellulose. The alkylene oxide and / or glycidyl compound may be a commercially available reagent or product.

  Preferable examples of the alkylene oxide and / or glycidyl compound are not particularly limited. For example, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, phenyl glycidyl ether, p -Glycidyl ethers such as tertiary butylphenyl glycidyl ether, sec-butylphenyl glycidyl ether, n-butylphenyl glycidyl ether, phenylphenol glycidyl ether, cresyl glycidyl ether, dibromocresyl glycidyl ether; glycidyl acetate, glycidyl stearate, etc. Glycidyl ester; ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether 1,4-butanediol diglycidyl ether, hexamethylene glycol diglycidyl ether, resorcinol diglycidyl ether, bisphenol A diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polybutylene glycol diglycidyl ether, glycerol Examples thereof include polyhydric alcohol glycidyl ethers such as triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, polyglycerol polyglycidyl ether, and diglycerol polyglycidyl ether.

  Among these, 2-methyloctyl glycidyl ether, hexamethylene glycol diglycidyl ether, and pentaerythritol tetraglycidyl ether can be preferably used in terms of reactivity, stability, price, and the like.

(B) Cellulose is obtained by dissolving the resin component in the composition in an organic or inorganic solvent capable of dissolving the resin component of the composition, separating the cellulose, thoroughly washing with the solvent, and then thermally decomposing the separated cellulose. Or it can confirm by hydrolyzing. Alternatively, it can be confirmed by directly performing ¹ H-NMR and ¹³ C-NMR measurements.

  The blending amount of (B) cellulose with respect to 100 parts by mass of (A) polyamide resin is 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 from the viewpoints of good mechanical properties, thermal stability and durability. From the viewpoint of obtaining sufficient moldability, it is 200 parts by mass or less, preferably 100 parts by mass or less, and more preferably 20 parts by mass or less.

≪ (C) Surface modifier≫
Next, the surface modifier (C) that can be used in the present invention will be described in detail.
(C) The surface modifier is typically an oligomer (for example, an oligomer of a thermoplastic resin). In one embodiment, the oligomer is a polymer having a polymerization degree of 20 or less.

  Specific examples of thermoplastic resin oligomers include polyamide resins, polyester resins, polyacetal resins, polycarbonate resins, polyacrylic resins, polyphenylene ether resins (polyphenylene ether blended or graft polymerized with other resins). Modified polyphenylene ether), polyarylate resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyketone resin, polyphenylene ether ketone resin, polyimide resin, polyamideimide resin, poly Examples include etherimide resins, polyurethane resins, polyolefin resins (for example, α-olefin (co) polymers), and oligomers such as various ionomers.

  Preferred specific examples of the thermoplastic resin include high-density polyethylene, low-density polyethylene (for example, linear low-density polyethylene), polypropylene, polymethylpentene, cyclic olefin-based resin, poly-1-butene, poly-1-pentene, and polymethyl. Pentene, ethylene / α-olefin copolymer, ethylene / butene copolymer, EPR (ethylene-propylene copolymer), modified ethylene / butene copolymer, EEA (ethylene-ethyl acrylate copolymer), modified EEA, Modified EPR, modified EPDM (ethylene-propylene-diene terpolymer), ionomer, α-olefin copolymer, modified IR (isoprene rubber), modified SEBS (styrene-ethylene-butylene-styrene copolymer), halogen Isobutylene-paramethylstyrene copolymer, ethylene A len-acrylic acid-modified product, an ethylene-vinyl acetate copolymer, and an acid-modified product thereof, a copolymer of (ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester), ( Polyolefin, conjugated diene and vinyl aromatic hydrocarbon obtained by metallizing at least a part of the carboxyl group of a copolymer of (ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic ester) Block copolymers, hydrides of block copolymers of conjugated dienes and vinyl aromatic hydrocarbons, copolymers of other conjugated diene compounds and nonconjugated olefins, natural rubber, various butadiene rubbers, various styrene-butadiene copolymers Polymer rubber, isoprene rubber, butyl rubber, copolymer bromide of isobutylene and p-methylstyrene, halogen Butyl rubber, acrylonitrile butadiene rubber, chloroprene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene-butadiene copolymer rubber, isoprene-butadiene Copolymer rubber, chlorosulfonated polyethylene, acrylic rubber, epichlorohydrin rubber, polysulfide rubber, silicone rubber, fluorine rubber, urethane rubber, polyvinyl chloride, polystyrene, polyacrylic ester, polymethacrylic ester, acrylic, acrylonitrile Acrylonitrile copolymer as the main component, acrylonitrile / butanediene / styrene (ABS) resin, acrylonitrile / styrene (AS) resin, cellulose resin such as cellulose acetate, vinyl chloride Le / ethylene copolymer, vinyl chloride / vinyl acetate copolymer, ethylene / vinyl acetate copolymer, and ethylene / saponified like vinyl acetate copolymer.

  These may be used individually by 1 type and may use 2 or more types together. . Moreover, what modified | denatured the above-mentioned thermoplastic resin by the at least 1 sort (s) of compound chosen from unsaturated carboxylic acid, its acid anhydride, or its derivative (s) can also be used.

  Among these, from the viewpoint of heat resistance, moldability, designability and mechanical properties, polyolefin resin, polyamide resin, polyester resin, polyacetal resin, polyacrylic resin, polyphenylene ether resin, polyphenylene sulfide resin and A resin selected from the group consisting of a mixture of two or more of these is preferred.

  Among these, polyolefin resins, polyamide resins, polyester resins, polyacetal resins, and the like are more preferable resins from the viewpoint of handleability and cost.

  The polyolefin resin is a polymer obtained by polymerizing monomer units containing olefins (for example, α-olefins). Specific examples of the polyolefin resin are not particularly limited, but ethylene (co) heavy exemplified by low density polyethylene (for example, linear low density polyethylene), high density polyethylene, ultra low density polyethylene, ultra high molecular weight polyethylene and the like. Polypropylene (co) polymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene exemplified by polymer, polypropylene, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, etc. -Copolymers of α-olefins and other monomer units represented by glycidyl methacrylate copolymers and the like.

  Moreover, in order to improve the affinity with cellulose, an acid-modified polyolefin resin can also be suitably used. The acid can be appropriately selected from maleic acid, fumaric acid, succinic acid, phthalic acid and anhydrides thereof, and polycarboxylic acids such as citric acid. Among these, maleic acid or an anhydride thereof is preferable because it easily increases the modification rate. There are no particular restrictions on the modification method, but a method of melting and kneading the resin by heating it to the melting point or higher in the presence / absence of peroxide is common. As the polyolefin resin to be acid-modified, all of the above-mentioned polyolefin resins can be used, but polypropylene can be preferably used.

  The acid-modified polyolefin resin may be used alone, but is more preferably used by mixing with an unmodified polyolefin resin in order to adjust the modification rate of the composition. For example, when using a mixture of unmodified polypropylene and acid-modified polypropylene, the ratio of the acid-modified polypropylene to the total polypropylene is preferably 0.5% by mass to 50% by mass. A more preferred lower limit is 1% by mass, still more preferably 2% by mass, still more preferably 3% by mass, particularly preferably 4% by mass, and most preferably 5% by mass. A more preferred upper limit is 45% by mass, still more preferably 40% by mass, still more preferably 35% by mass, particularly preferably 30% by mass, and most preferably 20% by mass. In order to maintain the interfacial strength with cellulose, the lower limit is preferable, and in order to maintain the thermal stability as a resin, the upper limit is preferable.

  The polyamide-based resin preferable as the thermoplastic resin is not particularly limited, but polyamide 6, polyamide 11, polyamide 12, etc. obtained by polycondensation reaction of lactams; 1,6-hexanediamine, 2-methyl-1,5- Pentanediamine, 1,7-heptanediamine, 2-methyl-1-6-hexanediamine, 1,8-octanediamine, 2-methyl-1,7-heptanediamine, 1,9-nonanediamine, 2-methyl-1 , 8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, m-xylylenediamine, and the like, butanedioic acid, pentanedioic acid, hexanedioic acid, Heptanedioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, benzene-1,2-dicarboxylic acid, benze Polyamide 6, obtained as a copolymer with dicarboxylic acids such as -1,3-dicarboxylic acid, benzene-1,4 dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid, cyclohexane-1,4-dicarboxylic acid, etc. 6, polyamide 6,10, polyamide 6,11, polyamide 6,12, polyamide 6, T, polyamide 6, I, polyamide 9, T, polyamide 10, T, polyamide 2M5, T, polyamide MXD, 6, polyamide 6, C, polyamide 2M5, C and a copolymer obtained by copolymerizing them, and examples thereof include copolymers such as polyamide 6, T / 6, and I.

  Among these polyamide-based resins, aliphatic polyamides such as polyamide 6, polyamide 11, polyamide 12, polyamide 6,6, polyamide 6,10, polyamide 6,11, polyamide 6,12, polyamide 6, C, polyamide 2M5, C The alicyclic polyamide is more preferable.

  Although there is no restriction | limiting in particular in the terminal carboxyl group density | concentration of a polyamide-type resin, A lower limit is preferable in it being 20 micromol / g, More preferably, it is 30 micromol / g. The upper limit of the terminal carboxyl group concentration is preferably 150 μmol / g, more preferably 100 μmol / g, and still more preferably 80 μmol / g.

  In the polyamide-based resin, it is more preferable that the carboxyl end group ratio ([COOH] / [all end groups]) to the preferable all end groups is 0.30 to 0.95. The lower limit of the carboxyl end group ratio is more preferably 0.35, still more preferably 0.40, and most preferably 0.45. The upper limit of the carboxyl end group ratio is more preferably 0.90, even more preferably 0.85, and most preferably 0.80. The carboxyl end group ratio is desirably 0.30 or more from the viewpoint of dispersibility of the cellulose component in the composition, and desirably 0.95 or less from the viewpoint of the color tone of the resulting composition.

  As a method for adjusting the terminal group concentration of the polyamide-based resin, a known method can be used. For example, diamine compound, monoamine compound, dicarboxylic acid compound, monocarboxylic acid compound, acid anhydride, monoisocyanate, monoacid halide, monoester, monoalcohol, etc. The method of adding the terminal regulator which reacts with a terminal group to a polymerization liquid is mentioned.

  Examples of terminal regulators that react with terminal amino groups include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid. Aliphatic monocarboxylic acids such as cycloaliphatic carboxylic acids; aromatic monocarboxylic acids such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid Carboxylic acid; and a plurality of mixtures arbitrarily selected from these. Of these, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, in terms of reactivity, stability of the sealing end, price, etc. And one or more terminal regulators selected from the group consisting of benzoic acid and acetic acid is most preferred.

  Examples of the terminal regulator that reacts with the terminal carboxyl group include aliphatic amines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine. Examples include monoamines; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine, naphthylamine, and any mixture thereof. Among these, one or more terminals selected from the group consisting of butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine and aniline in terms of reactivity, boiling point, stability of the sealing end, price, etc. A modifier is preferred.

The concentration of the amino terminal group and the carboxyl terminal group is preferably determined from the integral value of the characteristic signal corresponding to each terminal group by ¹ H-NMR in terms of accuracy and simplicity. Specifically, the method described in Japanese Patent Application Laid-Open No. 7-228775 is recommended as a method for obtaining the concentration of these end groups. When this method is used, deuterated trifluoroacetic acid is useful as a measurement solvent. In addition, the number of ¹ H-NMR integrations is required to be at least 300 scans even when measured with an instrument having sufficient resolution. In addition, the concentration of end groups can be measured by a titration measurement method as described in JP-A-2003-055549. However, in order to reduce the influence of mixed additives, lubricants and the like as much as possible, quantification by ¹ H-NMR is more preferable.

  The polyamide resin preferably has an intrinsic viscosity [η] measured in concentrated sulfuric acid at 30 ° C. of 0.6 to 2.0 dL / g, preferably 0.7 to 1.4 dL / g. Is more preferably 0.7 to 1.2 dL / g, and particularly preferably 0.7 to 1.0 dL / g. Use of the above-mentioned polyamide-based resin having an intrinsic viscosity in a preferred range, particularly a preferred range, has the effect of greatly increasing the fluidity in the mold during injection molding of the resin composition and improving the appearance of the molded piece. be able to.

  Polyester resins preferred as thermoplastic resins are not particularly limited, but include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene succinate (PBS), polybutylene succinate adipate ( PBSA), polybutylene adipate terephthalate (PBAT), polyarylate (PAR), polyhydroxyalkanoic acid (PHA) (polyester resin comprising 3-hydroxyalkanoic acid), polylactic acid (PLA), polycarbonate (PC), etc. 1 type (s) or 2 or more types can be used. Among these, more preferable polyester resins include PET, PBS, PBSA, PBT, and PEN, and more preferably, PBS, PBSA, and PBT.

  In addition, the polyester resin can freely change the terminal group depending on the monomer ratio at the time of polymerization and the presence / absence and amount of the terminal stabilizer, but the carboxyl terminal group ratio to the total terminal groups of the polyester resin. ([COOH] / [all end groups]) is preferably 0.30 to 0.95. The lower limit of the carboxyl end group ratio is more preferably 0.35, still more preferably 0.40, and most preferably 0.45. Further, the upper limit of the carboxyl end group ratio is more preferably 0.90, still more preferably 0.85, and most preferably 0.80. The carboxyl end group ratio is desirably 0.30 or more from the viewpoint of dispersibility of the cellulose component in the composition, and desirably 0.95 or less from the viewpoint of the color tone of the resulting composition.

  Polyacetal resins that are preferable as thermoplastic resins are generally homopolyacetals that use formaldehyde as a raw material, and copolyacetals that contain trioxane as the main monomer, for example, 1,3-dioxolane as a comonomer component, and both can be used. However, from the viewpoint of thermal stability during processing, copolyacetal can be preferably used. In particular, the amount of comonomer component (for example, 1,3-dioxolane) is preferably in the range of 0.01 to 4 mol%. A more preferred lower limit of the comonomer component amount is 0.05 mol%, more preferably 0.1 mol%, and particularly preferably 0.2 mol%. A more preferable upper limit is 3.5 mol%, further preferably 3.0 mol%, particularly preferably 2.5 mol%, and most preferably 2.3 mol%. From the viewpoint of thermal stability during extrusion and molding, the lower limit is preferably within the above range, and from the viewpoint of interfacial adhesion, the upper limit is preferably within the above range.

  (C) The lower limit of the number average molecular weight of the surface modifier is preferably 100, more preferably 200, and most preferably 300. The upper limit of the number average molecular weight is not particularly limited, but is preferably 2000 or less from the viewpoint of handleability. In order to ensure sufficient affinity with (B) cellulose, it is desirable that the number average molecular weight of (C) the surface modifier is within the above-mentioned range.

  In addition, the method for adding the (C) surface modifier in preparing the resin composition is not particularly limited, but (A) a polyamide resin, (B) cellulose, (C) a surface modifier, and A method of mixing and polymerizing other components, a method of mixing and polymerizing (A) a polyamide resin, (B) cellulose, and (C) a surface modifier, and melt-kneading the obtained resin composition and other components, (A) a polyamide resin, (B) cellulose, and other components are mixed and polymerized, and the resulting resin composition and (C) a surface modifier are melt-kneaded, (A) the polyamide resin is polymerized, (B) A method of melt-kneading cellulose, (C) a surface modifier, and other components, (B) cellulose, and (C) a surface modifier are mixed and dried to prepare a cellulose preparation. Cellulose preparation, (A) polyamide resin and Method of melt kneading the other components are valid.

  (C) The surface modifier is a part or all of (A) an oligomer that is a decomposition product of a polyamide resin, or (A) an oligomer that is a low molecular weight component generated during polymerization from a raw material monomer of a polyamide resin. There may be.

<< (C) Amount of surface modifier >>
The amount of the (C) surface modifier in the polyamide resin composition is evaluated by the following method. That is,
(C) The surface modifier is W ′ for the content of (C) the surface modifier in the insoluble matter when the polyamide resin composition is dissolved in the polyamide resin-soluble solvent, and the (C) surface in the solution. When the modifier content is W ″ and the total of W ′ and W ″ is W, the following relational expression (1):
1 ≧ 10 × W ′ / W (1)
Meet.

W ′ is a value obtained by measuring (C) surface modifier content on the cellulose surface, which is a polyamide resin-soluble solvent-insoluble component, by pyrolysis GC-MS, ¹ H-NMR, or ¹³ C-NMR. is there. Specifically, (C) qualitative evaluation of the surface modifier component and (C) quantitative evaluation of the surface modifier adhesion amount are performed by pyrolysis GC-MS. The isolated cellulose is dissolved in a cellulose-soluble solvent and measured by ¹ H-NMR or ¹³ C-NMR, and (C) the molecular weight of the surface modifier is measured. In one embodiment, the polyamide resin-soluble solvent can be a solvent that is liquid at 23 ° C., for example, hexafluoro-2-propanol, water, ethylene glycol, benzyl alcohol, acetic acid, calcium chloride saturated methanol solution, concentrated formic acid. Examples include aqueous solution, concentrated sulfuric acid, concentrated nitric acid, concentrated hydrochloric acid and the like. In one embodiment, as the cellulose-soluble solvent, a solvent that is liquid at 23 ° C. can be used, and examples thereof include dimethylformamide and dimethylacetamide.
W ″ is a value obtained by direct GPC measurement of the content of (C) the surface modifier in the solution.
When the above relational expression is satisfied, the resin and cellulose exhibit good adhesion, and various physical properties such as fatigue resistance and wear resistance tend to be improved. On the other hand, when the above 10 × W ′ / W exceeds 1, the cellulose becomes poorly dispersed, and various physical properties such as fatigue resistance and workability tend to decrease.

  The above W, W ′, and W ″ can be controlled by performing various operations. For example, refining with hot water at 95 ° C. for a predetermined time, and vacuum drying at 80 ° C. after pelletizing for a predetermined time. Performing annealing (performing heat treatment at a temperature higher than the Tg of the (C) surface modifier), storing the pellets in a constant temperature and humidity environment, and absorbing a predetermined amount at a predetermined temperature. (C) Controlling the amount (ie, W) of the surface modifier in the resin composition by performing injection molding, reducing pressure when performing melt kneading with an extruder such as a twin screw, etc. It is possible to increase W ′ by distributing many (C) surface modifiers in the vicinity of the cellulose surface.

  In refining for a predetermined time with hot water of 95 ° C., it is considered that (C) the surface modifier moves together with water and escapes from the system because the resin swells with water. In vacuum drying at 80 ° C. after pelletizing, the surface modifier (C) present in the pellet is vaporized from the pellet surface by exposing it to a temperature higher than the Tg of the polyamide resin and in an ultra-high vacuum state for a predetermined time. It is thought that it goes out of the system. In the annealing, heat treatment is performed at a temperature higher than the Tg of the (C) surface modifier, and (C) the surface modifier molecules move in the composition to promote crystallization of the resin. It is considered that (C) the surface modifier that has lost its place from the portion that has been moved has moved to the cellulose surface with higher affinity in the resin. When pellets are stored in a constant temperature and humidity environment and a predetermined amount is absorbed and then injection molded at a predetermined temperature, moisture absorption occurs and the polymer is decomposed by being exposed to a higher temperature. It is thought that oligomer formation occurs due to lower molecular weight.

W ′ and W ″ in the polyamide resin composition can be obtained by an analysis method common to those skilled in the art by isolation using a polyamide resin-soluble solvent as described above. For example, 1 g 50 ml of hexafluoro-2-propanol is used to dissolve the resin component in the composition, and the cellulose that is insoluble is separated by centrifugation, filtration, etc. Wet obtained by the separation 2 ml of hexafluoro-2-propanol is added to the cake-like cellulose, washed for 3 seconds, and vacuum filtration is performed once.The cellulose obtained by this vacuum filtration is air-dried at 23 ° C. for 24 hours or more, The obtained dry cellulose and the internal standard substance are measured simultaneously or under different conditions, using pyrolysis GC-MS, ¹ H-NMR, ¹³ C- It may be NMR measurement etc. Thereby, it is possible to calculate W ′ of the (C) surface modifier.

  On the other hand, it is possible to calculate W ″ of the surface modifier (C) by directly measuring the solution (that is, the filtrate in which the polyamide resin is dissolved) after separating the insoluble matter.

  (A) The amount of the (C) surface modifier with respect to 100 parts by mass of the polyamide resin is 0.01 parts by mass or more, preferably 0.1 parts by mass or more, more preferably from the viewpoint of obtaining good performance of the resin molding. Is 0.5 parts by mass or more, and 5 parts by mass or less, preferably 4 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less, particularly from the viewpoint of improving the wear properties of the resin molded body. Preferably it is less than 2 parts by mass.

≪ (D) Metal ion component≫
Next, the (D) metal ion component that can be used in the present invention will be described in detail.
The polyamide resin composition can contain (D) a metal ion component as an optional component. (D) A commercially available reagent or product may be sufficient as a metal ion component.

  (D) Examples of the metal ion component include copper compounds and metal halides (other than copper or copper).

Copper compounds include copper halides such as copper chloride, copper bromide, copper iodide; copper acetate, copper propionate, copper benzoate, copper adipate, copper terephthalate, copper isophthalate, copper salicylate, copper nicotinate And carboxylic acid copper salts such as copper stearate; copper complex salts in which copper is coordinated to a chelating agent such as ethylenediamine and ethylenediaminetetraacetic acid. A copper compound may be used by 1 type and may be used in combination of 2 or more types. As copper compounds, copper iodide (CuI) is more excellent in heat aging resistance, and can suppress metal corrosion (hereinafter also simply referred to as “metal corrosion”) of screws and cylinders during extrusion. Cuprous bromide (CuBr), cupric bromide (CuBr ₂ ), cuprous chloride (CuCl), and copper acetate are preferred, and copper iodide and copper acetate are more preferred.

  It is preferable that content of the said copper compound in a polyamide resin composition is 0.005-0.6 mass part with respect to 100 mass parts of (A) polyamide resin, and is 0.005-0.4 mass part. More preferably, it is 0.01 to 0.4 parts by mass. Surprisingly, when the amount of the metal ion component (D) is within the above range, the number of breaks in the fatigue test of the polyamide resin composition is further improved. The cause of such excellent repeated fatigue resistance is not yet elucidated, but (B) the interface between the surface of cellulose and (C) the surface modifier, or (B) the surface of cellulose and (A) the polyamide resin. It is presumed that (D) a metal ion component is present at the interface with the surface, increasing adhesion. In addition, when the content of the copper compound is within the above range, the heat aging property, which is one of the thermal stability indexes, can be further improved, and copper precipitation and metal corrosion can be further suppressed.

  It is preferable that content of the copper element in the copper compound in a polyamide resin composition is 0.005-0.2 mass part with respect to 100 mass parts of said (A) polyamide resin, 0.005-0.00. The amount is more preferably 15 parts by mass, and further preferably 0.006 to 0.1 parts by mass. When the content of the copper element is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be further suppressed.

  The polyamide resin composition may further contain at least one metal halide selected from the group consisting of alkali metal halides and alkaline earth metal halides. A metal halide may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the metal halide include potassium iodide, potassium bromide, potassium chloride, sodium iodide, sodium chloride and the like. As the metal halide, potassium iodide and potassium bromide are preferable, and potassium iodide is more preferable in that the heat aging resistance of the polyamide resin composition is further improved and metal corrosion is further suppressed.

  The content of the metal halide in the polyamide resin composition is preferably 0.05 to 20 parts by mass, and 0.05 to 10 parts by mass with respect to 100 parts by mass of the (A) polyamide resin. More preferably, it is 0.07-5 mass parts. When the content of the metal halide is within the above range, the heat aging resistance is further improved, and copper precipitation and metal corrosion can be further suppressed.

  The metal halide is preferably blended so that the molar ratio C3 / C4 of the halogen element content C3 and the copper element content C4 is 2/1 to 50/1. It is more preferable to mix | blend so that it may become 1, and it is further more preferable to mix | blend so that it may become 5 / 1-30 / 1. By setting the molar ratio C3 / C4 to 2/1 or more, copper precipitation and metal corrosion can be further suppressed. By setting the molar ratio to 50/1 or less, the metal properties are not impaired without impairing mechanical properties such as toughness and rigidity. Corrosion can be further suppressed.

Examples of the method of incorporating a copper compound in the polyamide resin composition include, for example, a method of blending a copper compound (and, if necessary, a metal halide) at the time of polyamide polymerization (Production Method 1), and a polyamide resin using melt kneading. The method (manufacturing method 2) which mix | blends a copper compound (it is further a metal halide as needed) is mentioned.
In the method for producing the polyamide resin composition of the present embodiment, the copper compound may be added in a solid state, for example, in the form of an aqueous solution. The time of polyamide polymerization in the production method 1 may be any stage from the raw material monomer to the completion of the polymerization of the polyamide. The apparatus for melt kneading in production method 2 is not particularly limited, and a known apparatus such as a single- or twin-screw extruder, a Banbury mixer, and a mixing kneader such as a mixing roll can be used. Of these, a twin screw extruder is preferably used.

The temperature of the melt kneading is preferably a temperature that is about 1 to 100 ° C. higher than the melting point of the polyamide resin, and more preferably a temperature that is about 10 to 50 ° C. higher. The shear rate in the kneader is preferably about 100 sec ⁻¹ or more, and the average residence time during kneading is preferably about 0.5 to 5 minutes.

≪ (E) Sliding agent component≫
Next, the (E) sliding agent component that can be used in the present invention will be described in detail. The polyamide resin composition can contain (E) a sliding agent component as an optional component. (E) The sliding agent component may be a commercially available reagent or product.

  (E) The preferable minimum amount of a sliding agent component is 0.01 mass part with respect to 100 mass parts of (A) polyamide resin, More preferably, it is 0.5 mass part, Especially preferably, 1. 0 parts by mass. Moreover, the preferable upper limit of (E) sliding agent component is 5 mass parts with respect to 100 mass parts of (A) polyamide resin, More preferably, it is 4 mass parts, Most preferably, it is 3 mass parts. (E) By making the quantity of a sliding agent component into the said range, the frequency | count of a fracture | rupture in a fatigue test improves. When ordinary fillers (for example, glass fibers) are used, (E) the sliding agent component is unevenly distributed on the glass fiber surface, and a structure in which a large number of sliding agent molecules are laminated makes it easy for the filler to fall off. There may be a problem that the effect is reduced in a fatigue test or the like. However, when (B) cellulose is used, the surface area of cellulose is greatly different from that of glass fiber and the like, and therefore, (E) the sliding agent component is not unevenly distributed on the cellulose surface, and the sliding agent molecules are not easily laminated. . As a result, it is presumed that the number of breaks in the fatigue test is improved and the wear resistance is also maintained.

  (E) When the amount of the sliding agent component is 5 parts by mass or less with respect to 100 parts by mass of (A) the polyamide resin, delamination and generation of silver streaks in the resin molded body are more effectively suppressed. Further, when the amount of the (E) sliding agent component is 0.01 parts by mass or more with respect to 100 parts by mass of the (A) polyamide resin, a more remarkable effect of reducing the amount of wear can be obtained.

(E) Although it is not limited to these as a sliding agent component, For example, the compound which has a structure represented by following General formula (2), (3) or (4) is mentioned.
[R11- (A1-R12) x-A2-R13] y (2)
A3-R11-A4 (3)
R14-A5 (4)
Here, in formulas (2) and (3), R11, R12 and R13 are each independently at least one of an alkylene group having 1 to 7000 carbon atoms and a substituted or unsubstituted alkylene group having 1 to 7000 carbon atoms. At least one hydrogen atom in the substituted alkylene group in which 6 hydrogen atoms are substituted with an aryl group having 6 to 7000 carbon atoms, an arylene group having 6 to 7000 carbon atoms, or an arylene group having 6 to 7000 carbon atoms is 1 carbon atom A substituted arylene group substituted with ˜7000 substituted or unsubstituted alkyl groups.

  In Formula (4), R14 is an alkyl group having 1 to 7000 carbon atoms or an aryl group in which at least one hydrogen atom of a substituted or unsubstituted alkyl group having 1 to 7000 carbon atoms is 6 to 7000 carbon atoms. At least one hydrogen atom in the substituted alkyl group, the aryl group having 6 to 7000 carbon atoms, or the aryl group having 6 to 7000 carbon atoms is substituted with a substituted or unsubstituted alkyl group having 1 to 7000 carbon atoms A substituted aryl group;

  These groups may be groups containing a double bond, a triple bond, or a cyclic structure.

  In formula (2), A1 and A2 are each independently an ester bond, a thioester bond, an amide bond, a thioamide bond, an imide bond, a ureido bond, an imine bond, a urea bond, a ketoxime bond, an azo bond, or an ether bond. A thioether bond, a urethane bond, a thiourethane bond, a sulfide bond, a disulfide bond, or a trisulfide bond.

In formulas (3) and (4), A3, A4 and A5 are each independently a hydroxyl group, an acyl group (for example, acetyl group), an aldehyde group, a carboxyl group, an amino group, a sulfo group, an amidine group, An azide group, a cyano group, a thiol group, a sulfenic acid group, an isocyanide group, a ketene group, an isocyanate group, a thioisocyanate group, a nitro group, or a thiol group.
From the viewpoint of wear characteristics during sliding under a minute load, the structure represented by the above general formula (2), (3) or (4) in the (E) sliding agent component is preferably within the following range.

  That is, the carbon number in R11, R12, R13, and R14 is preferably 2 to 7000, more preferably 3 to 6800, and further preferably 4 to 6500.

  In formula (2), x represents an integer of 1 to 1000, and an integer of 1 to 100 is preferable. y shows the integer of 1-1000, and the integer of 1-200 is preferable.

  In formula (2), preferable A1 and A2 are each independently an ester bond, a thioester bond, an amide bond, an imide bond, a ureido bond, an imine bond, a urea bond, a ketoxime bond, an ether bond, and a urethane bond. More preferable A1 and A2 are each independently an ester bond, an amide bond, an imide bond, a ureido bond, an imine bond, a urea bond, a ketoxime bond, an ether bond, and a urethane bond.

  In formulas (3) and (4), preferred A3, A4 and A5 are each independently a hydroxyl group, an acyl group (for example, acetyl group), an aldehyde group, a carboxyl group, an amino group, an azide group, a cyano group, or a thiol. Group, isocyanide group, ketene group, isocyanate group, and thioisocyanate group, and more preferable A3, A4 and A5 are each independently a hydroxyl group, an acyl group (for example, acetyl group), an aldehyde group, a carboxyl group, an amino group. A group, a cyano group, an isocyanide group, a ketene group, and an isocyanate group.

  Specifically, the (E) sliding agent component is not particularly limited, and includes, for example, alcohol, amine, carboxylic acid, hydroxy acid, amide, ester, polyoxyalkylene glycol, silicone oil, wax, and lubricating oil. Examples include at least one compound selected from the group.

  The alcohol is preferably a saturated or unsaturated monovalent or polyhydric alcohol having 6 to 7000 carbon atoms. Specific examples are not particularly limited, for example, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, Oleyl alcohol, linoleyl alcohol, nonadecyl alcohol, eicosyl alcohol, ceryl alcohol, behenyl alcohol, melyl alcohol, hexyl decyl alcohol, octyldodecyl alcohol, decyl myristyl alcohol, decyl stearyl alcohol, uniline alcohol, ethylene glycol, diethylene glycol, tri Ethylene glycol, propylene glycol, dipropylene glycol, butane Ol, pentanediol, hexanediol, glycerol, diglycerol, triglycerol, threitol, erythritol, pentaerythritol, arabitol, ribitol, xylitol, sorbite, sorbitan, sorbitol, mannitol.

  Among these, alcohols having 11 or more carbon atoms are preferable from the viewpoint of slidability efficiency. More preferred is an alcohol having 12 or more carbon atoms, and still more preferred is an alcohol having 13 or more carbon atoms. Particularly preferred among these are saturated alcohols.

  Among these, stearyl alcohol, oleyl alcohol, linolyl alcohol, behenyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, and triethylene glycol are preferably used, and behenyl alcohol, diethylene glycol, and triethylene glycol are particularly preferably used.

  Examples of amines include, but are not limited to, primary amines, secondary amines, and tertiary amines.

  The primary amine is not particularly limited. For example, methylamine, ethylamine, propanamine, butaneamine, pentaneamine, hexaneamine, heptaneamine, octaneamine, cyclohexylamine, ethylenediamine, aniline, mensendiamine, isophoronediamine, xylenediamine. , Metaphenylenediamine, diaminodiphenylamine and the like.

  The secondary amine is not particularly limited, and examples thereof include dimethylamine, diethylamine, N-methylethylamine, diphenylamine, tetramethylethylenediamine, piperidine, N, N-dimethylpiperazine and the like.

  The tertiary amine is not particularly limited, and examples thereof include trimethylamine, triethylamine, hexamethylenediamine, N, N-diisopropylethylamine, pyridine, N, N-dimethyl-4-aminopyridine, triethylenediamine, and benzyldimethylamine. It is done.

  Although it does not specifically limit as a special amine, For example, a diethylenetriamine, a triethylenetetramine, a tetraethylenepentamine, a diethylamino propylamine, N-aminoethyl piperazine etc. are mentioned. Among these, hexaneamine, heptaneamine, octaneamine, tetramethylethylenediamine, N, N-dimethylpiperazine, and hexamethylenediamine can be more preferably used. Among these, heptaneamine, octaneamine, tetramethylethylenediamine, hexa Methylenediamine is particularly preferably usable.

  The carboxylic acid is preferably a saturated or unsaturated monovalent or polyvalent aliphatic carboxylic acid having 6 to 7000 carbon atoms. Specific examples are not particularly limited, but, for example, caproic acid, enanthic acid, caprylic acid, undecyl acid, pelargonic acid, lauric acid, tridecyl acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nanodecane Acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptaconic acid, montanic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, melicic acid, laccelic acid, undecylenic acid, elaidic acid, cetreic acid, Examples include brassic acid, sorbic acid, palmitoleic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, eleostearic acid, arachidonic acid, nervonic acid, erucic acid, propiolic acid, stearolic acid and the like.

  Among these, fatty acids having 10 or more carbon atoms are preferable from the viewpoint of slidability efficiency. More preferred are fatty acids having 11 or more carbon atoms, and even more preferred are fatty acids having 12 or more carbon atoms. Of these, saturated fatty acids are particularly preferred. Among the saturated fatty acids, palmitic acid, stearic acid, behenic acid, montanic acid, adipic acid, sebacic acid and the like are easily available industrially, and more preferable.

  Further, it may be a naturally occurring fatty acid containing these components or a mixture thereof. These fatty acids may be substituted with hydroxy groups, or may be synthetic fatty acids obtained by carboxyl-modifying the end of uniline alcohol, which is a synthetic aliphatic alcohol.

  Although it does not specifically limit as a hydroxy acid, For example, aliphatic hydroxy acid and aromatic hydroxy acid are mentioned. The aliphatic hydroxy acid is not particularly limited. For example, glycolic acid, hydroxypropionic acid, hydroxybutanoic acid, hydroxypentanoic acid, hydroxyhexanoic acid, hydroxyheptanoic acid, hydroxynonanoic acid, hydroxydecanoic acid, hydroxyundecanoic acid, hydroxy Dodecanoic acid, hydroxytridecanoic acid, hydroxytetradecanoic acid, hydroxypentadecanoic acid, hydroxyhexadecanoic acid, hydroxyheptadecanoic acid, hydroxyoctadecanoic acid, hydroxynonadecanoic acid, hydroxyicosanoic acid, hydroxydocosanoic acid, hydroxytetradocosanoic acid, Hydroxyhexadocosanoic acid, hydroxyoctadocosanoic acid, lactic acid, tartronic acid, glyceric acid, hydroxybutyric acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, γ- Examples include droxybutyric acid, malic acid, tartaric acid, citramalic acid, citric acid, isocitric acid, leucine acid, mevalonic acid, pantoic acid, ricinoleic acid, ricinaleic acid, cerebronic acid, quinic acid, shikimic acid, etc., and their isomers It may be.

  The aromatic hydroxy acid is not particularly limited. For example, salicylic acid, creosote acid (homosalicylic acid, hydroxy (methyl) benzoic acid), vanillic acid, silling acid, and pyrocatechuic acid as dihydroxybenzoic acid derivatives, as monohydroxybenzoic acid derivatives, Resorcylic acid, protocatechuic acid, gentisic acid, orceric acid, trihydroxybenzoic acid derivative, gallic acid, phenylacetic acid derivative, mandelic acid, benzylic acid, atrolactic acid, cinnamic acid and hydrocinnamic acid derivative, mellitoic acid, phloretic acid , Coumaric acid, umbelic acid, caffeic acid, ferulic acid, and sinapinic acid, and these isomers may be used. Among these, aliphatic hydroxy acids are more preferable, and among the aliphatic hydroxy acids, aliphatic hydroxy acids having 5 to 30 carbon atoms are more preferable, and aliphatic hydroxy acids having 8 to 28 carbon atoms are particularly preferable.

  The amide is preferably a saturated or unsaturated monovalent or polyvalent aliphatic amide having 6 to 7000 carbon atoms. Although it does not specifically limit as a specific example, For example, heptane amide, octane amide, nonane amide, decan amide, undecan amide, lauryl amide, tridecyl amide, myristyl amide, pentadecyl amide, cetyl amide, heptadecyl amide as primary amide, Stearylamide, oleylamide, nonadecylamide, eicosylamide, serylamide, behenylamide, melylamide, hexyldecylamide, octyldodecylamide, lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, oleic acid Examples thereof include saturated or unsaturated amides such as amide and erucic acid amide.

  Examples of secondary amides include, but are not limited to, for example, N-oleyl palmitic acid amide, N-stearyl stearic acid amide, N-stearyl oleic acid amide, N-oleyl stearic acid amide, N- Stearyl erucic acid amide, methylene bis stearic acid amide, ethylene bis capric acid amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene bishydroxy stearic acid amide, ethylene bis behenic acid amide, ethylene bis oleic acid amide, ethylene bis Saturated or unsaturated amides such as erucic acid amide, hexamethylene bis stearic acid amide, hexamethylene bis behenic acid amide, hexamethylene bis oleic acid amide, hexamethylene hydroxy stearic acid amide, etc. That.

  Examples of tertiary amides include, but are not limited to, N, N-distearyl adipic acid amide, N, N-distearyl sebacic acid amide, N, N-dioleyl adipic acid amide, Examples thereof include saturated or unsaturated amides such as N, N-dioleyl sebacic acid amide and N, N-distearylisophthalic acid amide.

  Among these, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxystearic acid amide, oleic acid amide, erucic acid amide, and N-stearyl stearic acid amide can be more preferably used.

  Among these, methylene bis stearic acid amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, and ethylene bis behenic acid amide are preferably used. Among these, amides having 10 or more carbon atoms are preferable from the viewpoint of sliding efficiency. More preferred is an amide having 11 or more carbon atoms, and still more preferred is an amide having 13 or more carbon atoms. Particularly preferred among these are saturated aliphatic amides.

  The ester is preferably a reaction product in which the above-mentioned alcohol and carboxylic acid or hydroxy acid react to form an ester bond.

  Specific examples include, but are not limited to, for example, butyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, monoglyceride behenate, cetyl 2-ethylhexanoate, isopropyl myristate, isopropyl palmitate, Cholesteryl isostearate, methyl laurate, methyl oleate, methyl stearate, cetyl myristate, myristyl myristate, octyldodecyl myristate pentaerythritol monooleate, pentaerythritol monostearate, pentaerythritol tetrapalmitate, stearyl stearate, Isotridecyl stearate, 2-ethylhexanoic acid triglyceride, diisodecyl adipate, ethylene glycol monolaurate, ethylene Recall dilaurate, ethylene glycol monostearate, ethylene glycol distearate, triethylene glycol monostearate, triethylene glycol distearate, ethylene glycol monooleate, ethylene glycol dioleate, polyethylene glycol monolaurate, polyethylene glycol mono Examples include stearate, polyethylene glycol distearate, polyethylene glycol monooleate, glycerol monostearate, glycerol distearate, glycerol monolaurate, glycerol dilaurate, glycerol monooleate, and glycerol dioleate.

  Among these, cetyl myristate, diisodecyl adipate, ethylene glycol monostearate, ethylene glycol distearate, triethylene glycol monostearate, triethylene glycol distearate, polyethylene glycol monostearate, polyethylene glycol distearate are preferred. Among them, cetyl myristate, diisodecyl adipate, and ethylene glycol distearate can be particularly preferably used.

  The polyoxyalkylene glycol is not limited to the following, and examples thereof include the following three types.

  The first polyoxyalkylene glycol is a polycondensate having alkylene glycol as a monomer. Examples of such polycondensates include, but are not limited to, polyethylene glycol, polypropylene glycol, block copolymers of ethylene glycol and propylene glycol, random copolymers, and the like. A preferable range of the polymerization degree of these polycondensates is 5 to 2500, and a more preferable range is 10 to 2300.

  The second polyoxyalkylene glycol is an ether compound of the polycondensate mentioned in the first polyoxyalkylene glycol and an aliphatic alcohol. Examples of such ether compounds include, but are not limited to, polyethylene glycol oleyl ether (ethylene oxide polymerization degree 5 to 500), polyethylene glycol cetyl ether (ethylene oxide polymerization degree 5 to 500), polyethylene glycol, and the like. Stearyl ether (ethylene oxide polymerization degree 5 to 300), polyethylene glycol lauryl ether (ethylene oxide polymerization degree 5 to 300), polyethylene glycol tridecyl ether (ethylene oxide polymerization degree 5 to 300), polyethylene glycol nonylphenyl ether (ethylene oxide polymerization) Degree 2 to 1000), polyethylene glycol octylphenyl ether (ethylene oxide polymerization degree 4 to 500), and the like.

  The third polyoxyalkylene glycol is an ester compound of the polycondensate mentioned in the first polyoxyalkylene glycol and a higher fatty acid. Examples of such ester compounds include, but are not limited to, polyethylene glycol monolaurate (ethylene oxide polymerization degree 2 to 300), polyethylene glycol monostearate (ethylene oxide polymerization degree 2 to 500), Examples include polyethylene glycol monooleate (ethylene oxide polymerization degree 2 to 500).

  Examples of the wax include, but are not limited to, for example, shellac wax, beeswax, whale wax, shellac wax, wool wax, carbana wax, wood wax, rice wax, candelilla wax, shellfish wax, paraffin wax, microcrystalline wax. , Montan wax, Fischer-Tropsch wax, polyethylene wax, polypropylene wax, and high density polymerization type, low density polymerization type, oxidation type, acid modification type, and special monomer modification type thereof.

  Among these, carnauba wax, rice wax, candelilla wax, paraffin wax, montan wax, polyethylene wax and their high-density polymerization type, low-density polymerization type, oxidation type, acid-modified type, and special monomer-modified type can be used more preferably. Carnauba wax, rice wax, candelilla wax, paraffin wax, polyethylene wax and their high-density polymerization type, low-density polymerization type, oxidation type, acid-modified type, and special monomer-modified type are particularly preferably usable.

  Among these, as the (E) sliding agent component, at least one selected from the group consisting of alcohol, amine, carboxylic acid, ester, amide compound composed of monovalent or divalent amine and carboxylic acid, and wax. A compound is preferred.

  The (E) sliding agent component paraffin wax, polyethylene wax and their high-density polymerization type, low-density polymerization type, oxidation type, acid-modified type, and special monomer-modified type used in the polyamide resin composition of the present embodiment are particularly Although not limited, an acidic group is introduced by an oxidation reaction of a polyolefin wax, a polyolefin is oxidatively decomposed, an inorganic acid, an organic acid, an unsaturated carboxylic acid, or the like is reacted with the polyolefin wax to generate a carboxyl group or a sulfonic acid group. It can be obtained by a method of introducing a polar group or a monomer having an acidic group at the time of polyolefin wax polymerization.

  These are commercially available under names such as oxidation-modified or acid-modified polyolefin waxes and can be easily obtained.

  Examples of the polyolefin wax include, but are not limited to, for example, paraffin wax, microcrystalline wax, montan wax, Fischer-Tropsch wax, polyethylene wax, polypropylene wax, and their high-density polymerization type, low-density polymerization type, special Monomer modified type and the like.

  Examples of the polyolefin include polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, polypropylene-butene copolymer, polybutene, hydrogenated polybutadiene, and ethylene-acrylic acid. Examples thereof include an ester copolymer, an ethylene-methacrylic acid ester copolymer, an ethylene-acrylic acid copolymer, and an ethylene-vinyl acetate copolymer.

  (E) As a sliding agent component, paraffin wax, polyethylene wax, acid modified product of polypropylene wax, polyethylene (high pressure method low density polyethylene, linear low density polyethylene, ultra low density polyethylene) from the viewpoint of improving sliding properties Polypropylene, an ethylene-propylene copolymer, and an acid-modified product of an ethylene-butene copolymer are preferable.

  (E) The sliding agent component is particularly preferably a modified wax containing acid-modified polyethylene and / or acid-modified polypropylene.

The (E) sliding agent component may be used alone or in combination of two or more.
In this embodiment, the (E) sliding agent component can be calculated from the molecular structure, molecular weight, melting point, acid value, viscosity, and the like by separating from the polyamide resin molded body.

The (E) sliding agent component in the molded article containing the polyamide resin composition of the present embodiment is isolated by performing operations such as dissolving the polyamide resin molded article or the composition, and then (E) the sliding agent. The components can be purified by operations such as recrystallization and reprecipitation. (E) By performing various measurements such as ¹ H-NMR, ¹³ C-NMR, two-dimensional NMR, and MALDI-TOF MS on the sliding agent component, molecular structures such as repetitive structures, branched structures, and positional information of various functional groups Can be determined.

  (E) When the sliding agent component is acid-modified polyethylene and / or acid-modified polypropylene, the acid value is preferably in the range of 0 to 85 mg-KOH / g. There is no particular lower limit for the acid value, but it is preferably 0 mg-KOH / g or more. The upper limit of the acid value is more preferably 83 mg-KOH / g, still more preferably 80 mg-KOH / g, and still more preferably 75 mg-KOH / g. By setting the acid value within the above-mentioned range, discoloration at the time of drying is suppressed, and wear resistance at the time of high-temperature sliding with a minute load tends to be good. (E) The acid value of the sliding agent component can be measured by a method based on JIS K0070.

  (E) The acid value of the sliding agent component is, for example, the method described in Example 1 or 2 of JP-A No. 2004-75749, the method described in Example 1 of JP-A No. 62-167308, or commercially available. This high-density polyethylene can be controlled by a method of adjusting or controlling the introduction amount of acidic groups and / or the introduction amount of polar groups by thermally decomposing in an oxygen atmosphere. In addition, when the (E) sliding agent component is acid-modified polyethylene and / or acid-modified polypropylene, a commercially available product can be used.

  (E) When the sliding agent component is acid-modified polyethylene and / or acid-modified polypropylene, the melt viscosity at 140 ° C. is preferably in the range of 1 to 3000 mPa · s. The lower limit is not particularly limited, but is preferably 1 mPa · s, more preferably 20 mPa · s, and even more preferably 25 mPa · s from the viewpoint of workability during melt kneading of the polyamide resin composition of the present embodiment. Yes, even more preferably 30 mPa · s, even more preferably 50 mPa · s. The upper limit of the 140 ° C. melt viscosity is preferably 2850 mPa · s, more preferably 2800 mPa · s, still more preferably 2700 mPa · s, even more preferably 2650 mPa · s, and even more preferably. 2000 mPa · s.

  (E) When the sliding agent component is acid-modified polyethylene and / or acid-modified polypropylene, the melt viscosity at 180 ° C. is preferably in the range of 100 to 2900 mPa · s. (E) The lower limit of the 180 ° C. melt viscosity when the sliding agent component is acid-modified polyethylene and / or acid-modified polypropylene is preferably 110 mPa · s, more preferably 140 mPa · s, and even more preferably 160 mPa · s. · S, even more preferably 300 mPa · s. In addition, when the (E) sliding agent component is acid-modified polyethylene and / or acid-modified polypropylene, the preferable upper limit of the 180 ° C. melt viscosity is 2850 mPa · s, more preferably 2800 mPa · s, still more preferably 2700 mPa S, even more preferably 2650 mPa · s, even more preferably 2000 mPa · s, and particularly preferably 1600 mPa · s.

  (E) When the sliding agent component is acid-modified polyethylene and / or acid-modified polypropylene, the resin pellets are completely melted when the polyamide resin composition of the present embodiment is melt-kneaded by setting the melt viscosity within the above range. Thus, the kneading tends to be sufficiently performed.

  (E) When the sliding agent component is acid-modified polyethylene and / or acid-modified polypropylene, the melt viscosity at 140 ° C. and 180 ° C. can be measured with a Brookfield viscometer.

  (E) The lubricating oil that can be used as the sliding agent component is not limited to the following, but may be any material that can improve the friction and wear characteristics of the resin molded body, such as engine oil and cylinder. Natural oils such as oils; paraffinic oils (Diana Process Oil PS32, etc., manufactured by Idemitsu Kosan Co., Ltd.), naphthenic oils (Diana Process Oil, NS90S, etc., manufactured by Idemitsu Kosan Co., Ltd.) Synthetic hydrocarbon oils such as AC12; silicone greases such as G30 series manufactured by Shin-Etsu Chemical Co., Ltd., silicone oils such as silicone oil represented by polydimethylsiloxane, silicone gum, and modified silicone gum; Available and generally available on the market It is appropriately selected from among Namerayu, as it is or may be used appropriately in the formulation if desired. Among these, paraffinic oil and silicone oil are preferable from the viewpoint of slidability and easily available industrially. These lubricating oils may be used alone or in combination.

  The lower limit of the molecular weight of the lubricating oil is preferably 100, more preferably 400, and even more preferably 500. The upper limit is preferably 5 million, more preferably 2 million, and even more preferably 1 million. The lower limit of the melting point of the lubricating oil is preferably −50 ° C., more preferably −30 ° C., and further preferably −20 ° C. The upper limit of the melting point of the lubricating oil is preferably 50 ° C, more preferably 30 ° C, and even more preferably 20 ° C. When the molecular weight is 100 or more, the slidability of the lubricating oil tends to be good. Further, when the molecular weight is 5 million or less, particularly 1 million or less, the dispersion of the lubricating oil becomes good and the wear resistance tends to be improved. Further, by setting the melting point to −50 ° C. or higher, the fluidity of the lubricating oil existing on the surface of the resin molded body is maintained, and by suppressing the abrasive wear, the wear resistance of the resin molded body tends to be improved. . Further, by setting the melting point to 50 ° C. or less, the lubricating oil can be easily kneaded with the polyamide resin, and the dispersibility of the lubricating oil tends to be improved. From the above viewpoint, the molecular weight and melting point of the lubricating oil are preferably within the above ranges. In addition, the said melting | fusing point means the temperature 2.5 degreeC lower than the pour point of lubricating oil, and the said pour point is a value measured based on JISK2269.

  (A) The lower limit of the content of the lubricating oil with respect to 100 parts by mass of the polyamide resin is not particularly limited, but is preferably 0.1 parts by mass, more preferably 0.2 parts by mass, and even more preferably 0.3 parts by mass. . Moreover, although the upper limit of the said content is not specifically limited, 5.0 mass part is preferable, 4.5 mass part is more preferable, and 4.2 mass part is further more preferable. When the content of the lubricating oil is in the above range, the wear resistance of the polyamide resin composition tends to be improved. In particular, when the content of the lubricating oil is 0.1 parts by mass or more, good slidability can be secured and wear resistance tends to be improved. In addition, when the content of the lubricating oil is 5.0 parts by mass or less, the softening of the resin can be suppressed, and the strength of the polyamide resin composition that can withstand uses such as gears tends to be ensured. Therefore, when the range of the content of the lubricating oil in the polyamide resin composition is adjusted as described above, it is preferable from the viewpoint of improving the wear characteristics during sliding and further having excellent stable slidability.

  In the resin molding, since the dispersion state of the sliding agent component in the vicinity of the surface layer has a great influence on the sliding characteristics, the weight average molecular weight of the (E) sliding agent component is important. (E) The minimum with a preferable weight average molecular weight of a sliding agent component is 500, More preferably, it is 600, Most preferably, it is 700. Moreover, although there is no preferable upper limit of the weight average molecular weight of (E) sliding agent component, 100,000 is a standard from the ease of handling. (E) By making the weight average molecular weight of a sliding agent component into the above-mentioned range, for example, the resin molded body can achieve maintenance of wear resistance at sliding times exceeding 10,000 times.

  (E) Although there is no particular lower limit of the molecular weight distribution of the sliding agent component, it is a guideline that is close to 1.0 from the viewpoint of the stability of the friction coefficient during sliding. Moreover, the upper limit with preferable molecular weight distribution of (E) sliding agent component is 9.0, More preferably, it is 8.5, More preferably, it is 8.0, More preferably, it is 7.5.

  (E) The weight average molecular weight of the sliding agent component is measured by liquid chromatography / mass spectrometry when the weight average molecular weight is 1000 or less, and measured by gel permeation chromatography when the weight average molecular weight exceeds 1000. It is represented by a weight average molecular weight in terms of converted standard polystyrene or the like.

  (E) As for a sliding agent component, it is preferable that the melting | fusing point is 40-150 degreeC. (E) By making melting | fusing point of a sliding agent component 40 degreeC or more, it exists in the tendency which becomes possible to improve the abrasion resistance of the resin molding in higher temperature, (E) By setting the melting point to 150 ° C. or less, it becomes easy to achieve good dispersion of the (E) sliding agent component in the resin during processing. (E) The minimum with more preferable melting | fusing point of a sliding agent component is 45 degreeC, Furthermore, a preferable minimum is 50 degreeC and a especially preferable minimum is 80 degreeC. Further, the more preferable upper limit of the melting point of the (E) sliding agent component is 140 ° C., more preferably 135 ° C., and particularly preferably 130 ° C. (E) Melting | fusing point of a sliding agent component can be measured by the method (DSC method) based on JISK7121.

≪Other ingredients≫
The polyamide resin composition of the present embodiment can contain various stabilizers conventionally used in thermoplastic resins within a range that does not impair the purpose of the present embodiment. Examples of the stabilizer include, but are not limited to, the following inorganic fillers and heat stabilizers. These may be used alone or in combination of two or more. These may be commercially available reagents or products.

  The inorganic filler is not limited to the following, but is, for example, at least one compound selected from the group consisting of fibrous particles, plate-like particles, and inorganic pigments. The fibrous particles and plate-like particles herein are particles having an average aspect ratio of 5 or more.

  Although it does not specifically limit as fibrous particle, For example, glass fiber, carbon fiber, potassium titanate fiber, asbestos fiber, silicon carbide fiber, silicon nitride fiber, calcium metasilicate fiber, aramid fiber, etc. are mentioned.

  Further, the plate-like particles are not particularly limited, and examples thereof include talc, mica, kaolin, glass flakes, bentonite and the like. Among these, talc, mica, and glass fiber are preferable. By using these, the mechanical strength tends to be excellent and economical.

  Further, the inorganic pigment is not particularly limited. For example, zinc sulfide, titanium oxide, zinc oxide, iron oxide, barium sulfate, titanium dioxide, barium sulfate, hydrous chromium oxide, chromium oxide, cobalt aluminate, barite powder, zinc yellow 1 type, 2 types of zinc yellow, ferric iron ferric kalkaolin, titanium yellow, cobalt blue, ultramarine blue, cadmium, nickel titanium, lithopone, strontium, amber, shenna, azurite, malachite, azuro malachite, opiment, real gar, cinnabar, Turquoise, rhodochrosite, yellow ocher, tail belt, rhosenna, rhomber, cassel earth, chalk, plaster, burnt senna, burnt amber, lapis lazuli, azurite, malachite, coral powder, white mica, cobalt blue, se Lian Blue, Cobalt Violet, Cobalt Green, Zinc White, Titanium White, Light Red, Chromium Oxide Green, Mars Black, Billijan, Yellow Ocher, Alumina White, Cadmium Yellow, Cadmium Red, Vermilion, Talc, White Carbon, Clay, Mineral Bio red, rose cobalt violet, silver white, gold powder, bronze powder, aluminum powder, Prussian blue, aureolin, mica titanium, carbon black, acetylene black, lamp black, furnace black, vegetable black, bone charcoal, calcium carbonate, bitumen, etc. Can be mentioned.

  Among these, zinc sulfide, zinc oxide, iron oxide, titanium dioxide, titanium yellow, cobalt blue, and carbonate are preferable from the viewpoint of imparting higher wear resistance, and zinc oxide and titanium yellow have sufficient Mohs hardness. Is more preferable from the viewpoint of imparting high wear resistance.

  Although the addition amount of the inorganic filler mentioned above is not specifically limited, It is preferable in the range of 0.002-50 mass parts of inorganic fillers with respect to 100 mass parts of (A) polyamide resin. The handling property of a resin composition can be improved by making the addition amount of an inorganic filler into the above-mentioned range.

  Examples of the heat stabilizer include various heat stabilizers such as a hindered phenol heat stabilizer, a phosphorus heat stabilizer, and an amine heat stabilizer from the viewpoint of improving the heat stability of the resin molded body. Of these, hindered phenol antioxidants are preferred.

  Examples of the hindered phenol antioxidant include, but are not limited to, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3′-methyl-5′-t-butyl-4′-hydroxyphenyl) -propionate, n-tetradecyl-3- (3 ′, 5′-di-t-butyl-4′- Hydroxyphenyl) -propionate, 1,6-hexanediol-bis- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate), 1,4-butanediol-bis- (3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate), triethylene glycol-bis- (3- (3-t-butyl-5-methyl-4-hydroxy) Phenyl) - propionate), and the like.

  In addition, the hindered phenol-based antioxidant is not limited to the following. For example, tetrakis- (methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) pro Pionate methane, 3,9-bis (2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8,10 -Tetraoxaspiro (5,5) undecane, N, N'-bis-3- (3 ', 5'-di-t-butyl-4-hydroxyphenol) priionyl hexamethylenediamine, N, N'- Tetramethylenebis-3- (3′-methyl-5′-t-butyl-4-hydroxyphenol) propionyldiamine, N, N′-bis- (3- (3,5-di-t-butyl-4- Hydroxy Enol) propionyl) hydrazine, N-salicyloyl-N′-salicylidenehydrazine, 3- (N-salicyloyl) amino-1,2,4-triazole, N, N′-bis (2- (3- (3 Also included are 5-di-butyl-4-hydroxyphenyl) propionyloxy) ethyl) oxyamide and the like.

  Among the above-mentioned hindered phenol-based antioxidants, triethylene glycol-bis- (3- (3-t-butyl-5-methyl-4-hydroxyphenyl)-from the viewpoint of improving the thermal stability of the resin molded body. Propionate), and tetrakis- (methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate) methane are preferred.

  Although it does not specifically limit as a phosphorus heat stabilizer, For example, a pentaerythritol type | mold phosphite compound, a trioctyl phosphite, a trilauryl phosphite, a tridecyl phosphite, an octyl diphenyl phosphite, a tris isodecyl phosphite, a phenyl diisodecyl Phosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenylisodecylphosphite, diphenyl (tridecyl) phosphite, triphenylphosphite, tris (nonylphenyl) phosphite, tris (2,4-di-) t-butylphenyl) phosphite, tris (2,4-di-t-butyl-5-methylphenyl) phosphite, tris (butoxyethyl) phosphite, 4,4′-butylidene-bis (3- Til-6-tert-butylphenyl-tetra-tridecyl) diphosphite, tetra (C12-C15 mixed alkyl) -4,4′-isopropylidene diphenyldiphosphite, 4,4′-isopropylidenebis (2-tert-butyl) Phenyl) di (nonylphenyl) phosphite, tris (biphenyl) phosphite, tetra (tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphosphite, Tetra (tridecyl) -4,4′-butylidenebis (3-methyl-6-tert-butylphenyl) diphosphite, tetra (C1-C15 mixed alkyl) -4,4′-isopropylidene diphenyldiphosphite, tris (mono, Dimixed nonylphenyl) phosphite, 9,10-di-hydro-9-oxy -9-oxa-10-phosphaphenanthrene-10-oxide, tris (3,5-di-t-butyl-4-hydroxyphenyl) phosphite, hydrogenated-4,4'-isopropylidenediphenyl polyphos Phyto, bis (octylphenyl) bis (4,4′-butylidenebis (3-methyl-6-tert-butylphenyl)) 1,6-hexanol diphosphite, hexatridecyl-1,1,3-tris (2 -Methyl-4-hydroxy-5-t-butylphenyl) diphosphite, tris (4,4'-isopropylidenebis (2-t-butylphenyl)) phosphite, tris (1,3-stearoyloxyisopropyl) phosphite 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 2,2-methylenebi (3-methyl-4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene diphosphite And tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene diphosphite. These may be used alone or in combination of two or more.

  Among those listed above, pentaerythritol phosphite compounds and tris (2,4-di-t-butylphenyl) phosphite from the viewpoint of further improving the heat aging resistance of the composition and reducing the amount of gas generated. Is preferred. The pentaerythritol type phosphite compound is not particularly limited. For example, (2,6-di-t-butyl-4-methylphenyl) phenylpentaerythritol diphosphite, (2,6-di-t-butyl) -4-methylphenyl) methylpentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) 2-ethylhexylpentaerythritol diphosphite, (2,6-di-t-butyl-4) -Methylphenyl) isodecylpentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) laurylpentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) ) Isotridecyl pentaerythritol diphosphite, (2,6-di-t-butyl-4) Methylphenyl) stearylpentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) cyclohexylpentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) benzyl Pentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) ethyl cellosolve pentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) butyl carbitol penta Erythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) octylphenyl pentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) nonylphenyl pentaerythritol di Phosphite, bis (2,6-di-t-butyl 4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, (2,6-di-t-butyl-4-methyl) Phenyl) (2,6-di-t-butylphenyl) pentaerythritol diphosphite, (2,6-di-t-butyl-4-methylphenyl) (2,4-di-t-butylphenyl) pentaerythritol Diphosphite, (2,6-di-t-butyl-4-methylphenyl) (2,4-di-t-octylphenyl) pentaerythritol diphosphite, (2,6-di-t-butyl-4 -Methylphenyl) (2-cyclohexylphenyl) pentaerythritol diphosphite, (2,6-di-t-amyl-4-methylphenyl) phenylpen Taerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2,6-di-t-octyl-4-methylphenyl) penta An example is erythritol diphosphite. These may be used alone or in combination of two or more.

  Among the pentaerythritol type phosphite compounds listed above, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis, from the viewpoint of reducing the gas generation amount of the polyamide composition. (2,6-di-t-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-amyl-4-methylphenyl) pentaerythritol diphosphite, and bis (2, 6-di-t-octyl-4-methylphenyl) pentaerythritol diphosphite is preferred, and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite is preferred. Phosphite is more preferred.

  The amine heat stabilizer is not particularly limited, and examples thereof include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4- Acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, -(Ethylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2 , 6,6-tetramethylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) -carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -oxalate, bis (2,2,6,6-tetramethyl-4-piperidyl) -malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -sebacate, bis (2,2,6,6-tetra Methyl-4-piperidyl) -adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) -terephthalate, 1,2-bis (2,2,6,6- Tramethyl-4-piperidyloxy) -ethane, α, α′-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene, bis (2,2,6,6-tetramethyl) -4-piperidyltolylene-2,4-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene-1,6-dicarbamate, tris (2,2,6, 6-tetramethyl-4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,4-tricarboxy 1- [2- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} butyl] -4- [3- (3,5-di-t-butyl-4- Hydroxyphenyl) pro Onyloxy] 2,2,6,6-tetramethylpiperidine, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′ , Β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethanol. These may be used alone or in combination of two or more.

  Although the addition amount of the heat stabilizer mentioned above is not specifically limited, It is preferable in the range of 0.1-2 mass parts of heat stabilizers with respect to 100 mass parts of (A) polyamide resin. By making the addition amount of a heat stabilizer into the above-mentioned range, the handleability of the polyamide resin composition can be improved and the heat aging resistance can be further improved.

≪Method for manufacturing resin molded article≫
The resin molded body of the present embodiment includes, for example, the above-described (A) polyamide resin, (B) cellulose, and (C) a surface modifier, and W, W ′, and W ″ have a relational expression (1 The polyamide resin composition of the present embodiment satisfying the above can be manufactured by melt-kneading and molding into a specific shape.

  The apparatus for producing the polyamide resin composition of the present embodiment is not particularly limited, and a generally used kneader can be applied. The kneading machine is not limited to the following, and for example, a uniaxial or multi-axial kneading extruder, a roll, a Banbury mixer or the like may be used. Among these, a twin-screw extruder equipped with a decompression device and side feeder equipment is preferable.

  The polyamide resin composition of this embodiment can be provided in various shapes. Specific examples include a resin pellet shape, a sheet shape, a fiber shape, a plate shape, and a rod shape, and the resin pellet shape is more preferable from the viewpoint of ease of post-processing and ease of transportation. Preferable pellet shapes at this time include a round shape, an elliptical shape, a cylindrical shape, and the like, and these differ depending on a cutting method at the time of extrusion. Pellets cut by a cutting method called underwater cut are often round, and pellets cut by a cutting method called hot cut are often round or oval, and are called strand cuts. The pellets cut by the method are often cylindrical. In the case of round pellets, the preferred size is 1 mm or more and 3 mm or less as the pellet diameter. Moreover, the preferable diameter in the case of a cylindrical pellet is 1 mm or more and 3 mm or less, and a preferable length is 2 mm or more and 10 mm or less. The above diameter and length are preferably set to the lower limit or more from the viewpoint of operational stability during extrusion, and are preferably set to the upper limit or less from the viewpoint of biting into the molding machine in post-processing.

The following method is mentioned as a specific example of the manufacturing method of a polyamide resin composition.
(1) Using a single-screw or twin-screw extruder, a mixture of (A) polyamide resin, (B) cellulose, and (C) surface modifier is melt-kneaded, extruded into a strand, and cooled and solidified in a water bath. To obtain a pellet-shaped molded body.
(2) Using a single or twin screw extruder, a mixture of (A) polyamide resin, (B) cellulose, and (C) surface modifier is melted and kneaded, extruded into a rod or cylinder, cooled and extruded. Method to obtain as a molded body.
(3) Using a single screw or twin screw extruder, a mixture of (A) polyamide resin, (B) cellulose, and (C) surface modifier is melt-kneaded, extruded from a T-die, or film-like A method for obtaining a molded body.
(4) Using a single or twin screw extruder, a mixture of (A) polyamide resin, (B) cellulose, and (C) surface modifier is melt kneaded, extruded into a strand, and cooled and solidified in a water bath. To obtain a pellet-shaped molded body.

Moreover, the following method is mentioned as a specific example of the melt-kneading method of (A) polyamide resin, (B) cellulose, and (C) surface modifier.
(1) After mixing (A) polyamide resin and (B) cellulose and (C) surface modifier mixed in a desired ratio in the presence / absence of a surfactant component, Melting and kneading method.
(2) (B) Cellulose, (C) Surface modifier mixed powder, and optionally surfactant component mixed in a desired ratio after melt-kneading (A) polyamide resin and optionally surfactant A method of adding and further melt-kneading.
(3) (A) Polyamide resin, (B) cellulose mixed in a desired ratio, (C) Surface modifier mixed powder, and water and, if necessary, a surfactant are mixed and then melt-kneaded in a lump. Method.
(4) (B) Cellulose, (C) Surface modifier mixed powder, water, and, if necessary, surfactant, after kneading and kneading (A) polyamide resin and surfactant if necessary A method of adding an agent and further melt-kneading.

  In another preferred embodiment, the polyamide resin composition may be produced by a method in which (A) a raw material monomer of a polyamide resin and (B) an aqueous dispersion of cellulose are mixed and a polymerization reaction of the raw material monomer is performed. Good. In this embodiment, the (C) surface modifier may be a low molecular weight component (that is, an oligomer) generated during the polymerization of the raw material monomer of the (A) polyamide resin, and instead of or in addition to this, before the polymerization, A separate (C) surface modifier may be added to the system during or after the polymerization.

≪Members≫
The polyamide resin composition of the present embodiment can be formed into the following member forms. The method for molding the polyamide resin composition is not particularly limited, and a known molding method can be applied. For example, extrusion molding, injection molding, vacuum molding, blow molding, injection compression molding, decorative molding, other material molding, gas assist injection molding, foam injection molding, low pressure molding, ultra thin injection molding (ultra high speed injection molding), Molding can be performed by any of molding methods such as in-mold composite molding (insert molding, outsert molding).

  As a use of the member of this embodiment obtained from the above-mentioned polyamide resin composition, a use that is excellent in appearance after molding and requires long-term durability such as low dimensional change, wear resistance, and repeated fatigue resistance is suitable. is there.

  The use of the member of the present embodiment is not limited to the following, but for example, cam, slider, lever, arm, clutch, felt clutch, idler gear, pulley, roller, roller, key stem, key top, shutter Offices represented by mechanical parts such as reels, shafts, joints, shafts, bearings, and guides, resin parts for outsert molding, resin parts for insert molding, chassis, trays, side plates, printers, and copiers Parts for automation equipment, VTR (Video tape recorder), video movies, digital video cameras, cameras, and parts for cameras or video equipment represented by digital cameras, cassette players, DAT, LD (Laser disk), MD (Mini disk) , D (Compact disk) (including CD-ROM (Read only memory), CD-R (Recordable), CD-RW (Rewriteable)), DVD (Digital versatile disk) [DVD-ROM, DVD-R, DVD + R, DVD -RW, DVD + RW, DVD-R DL, DVD + R DL, DVD-RAM (including Random access memory), DVD-Audio], Blu-ray Disc, HD-DVD, and other optical disk drives; MFD (Multi Function Display) Music, video or information equipment represented by MO (Magneto-Optical Disk), navigation system and mobile personal computer, Parts for communication equipment typified by band telephone and facsimile; parts for electrical equipment, electronic equipment components, and the like.

  In addition, as members of the present embodiment, automobile parts such as gasoline tanks, fuel pump modules, valves, fuel tank parts such as gasoline tank flanges, door locks, door handles, window regulators, speaker grills, etc. Parts around doors, seat belt slip rings, seat belt peripheral parts such as press buttons, combination switch parts, switches, clips, etc., bumper bodies, instrument panels, console boxes , Garnish, door trim, ceiling, floor, lamp reflector, brush holder, fuel pump module parts, distributor, seat lead valve, wiper motor gear, speedometer frame, solenoid ignition co , Alternator, switch, sensor parts, tie rod end stabilizer, ECU cable, exhaust gas control valve, connector, exhaust brake solenoid valve, engine valve, radiator fan, starter, injector, engine surrounding panel, engine cover, motor cover, EPS Gears and the like.

  In addition, the members of the present embodiment include mechanical pencils as industrial parts and miscellaneous goods, mechanical parts for inserting and removing the cores of mechanical pencils, washstands, drain outlets, drain valve opening / closing mechanism parts, and opening / closing of vending machines. Part lock mechanism, product discharge mechanism parts, cord stopper for clothing, adjuster, button, nozzle for watering, sprinkling hose connection joint, dish, cup, spoon, flower pot, cooler box, fan, toy, ballpoint pen, ruler, clip, Drain materials, fences, storage boxes, construction switchboards, hot water supply equipment pump casings, impellers, joints, valves, faucet fixtures, stair railings, and building materials that support floor materials, disposable cameras, toys, fasteners, chains, Conveyors, buckles, sporting goods, vending machines, furniture, musical instruments, industrial machine parts (eg Electromagnetic equipment casings, roll materials, transport arms, medical equipment members, etc.), general machine parts, automobile / railway / vehicle parts (eg outer plates, chassis, aerodynamic members, seats, friction materials inside transmissions, etc.), ships Parts (eg, hulls, seats, etc.), aviation related parts (eg, fuselage, main wings, tail wings, moving wings, fairings, cowls, doors, seats, interior materials, etc.), spacecrafts, satellite members (motor cases, wings, Structures, antennas, etc.), electronic / electrical parts (for example, personal computer housings, mobile phone housings, OA equipment, AV equipment, telephones, facsimiles, home appliances, toy supplies, etc.), construction / civil engineering materials (eg, reinforcing steel substitute materials) , Truss structure, cable for suspension bridge, etc.), household goods, sports / leisure goods (eg golf club shaft, fishing rod, tennis and batmin) Such emissions racquet), wind power for the housing member or the like, also containers and packaging member, for example, can be a material for the high pressure container for filling and hydrogen gas as used in a fuel cell.

  Moreover, when the member of this embodiment is a resin composite film, it is suitable for the laminated board reinforcement in a printed wiring board. Others, for example, generators, transformers, rectifiers, circuit breakers, controller insulation cylinders, insulation levers, arc extinguishing plates, operation rods, insulation spacers, cases, wind tunnels, end bells, wind sinks, switch boxes for standard electrical products , Case, crossbar, insulation shaft, fan blade, mechanism parts, transparent resin substrate, speaker diaphragm, eta diaphragm, television screen, fluorescent cover, antenna for communication equipment / aerospace, horn cover, radome, case, Mechanical parts, wiring boards, aircraft, rockets, satellite electronic equipment parts, railway parts, marine parts, bathtubs, septic tanks, corrosion-resistant equipment, chairs, safety caps, pipes, tank trucks, cooling towers, floating breakwaters, underground It can also be suitably used as an industrial part typified by a buried tank and container housing equipment.

≪Linear expansion coefficient≫
Since the polyamide resin composition of this embodiment contains a cellulose, it becomes possible to show a lower linear expansion than the conventional resin composition. Specifically, the linear expansion coefficient in the temperature range of 0 ° C. to 60 ° C. of the resin composition is preferably 50 ppm / K or less. More preferably, the linear expansion coefficient of the composition is 45 ppm / K or less, even more preferably 40 ppm / K or less, and most preferably 35 ppm / K or less. The lower limit of the linear expansion coefficient is not particularly limited, but is preferably 5 ppm / K, and more preferably 10 ppm / K, from the viewpoint of ease of manufacture.

  The present invention will be further described based on examples, but the present invention is not limited to these examples.

≪Raw materials and evaluation method≫
Below, the used raw material and the evaluation method are demonstrated.

≪ (A) Polyamide resin≫
(A-1) Ube Industries, Ltd. product name ε-caprolactam (as a raw material monomer of (A) polyamide resin)
(A-2) PA6 Ube Industries, Ltd. product name 1013B

≪ (B) Cellulose≫
(B-1)
After cutting the linter pulp, it is heated in hot water at 120 ° C. or higher for 3 hours using an autoclave, and the purified pulp from which the hemicellulose portion has been removed is pressed and the solid content becomes 1.5% by weight in pure water. In this way, the fiber was highly shortened and fibrillated by beating treatment, and then defibrated cellulose was obtained by defibration with a high-pressure homogenizer (operating pressure: treated 10 times at 85 MPa) at the same concentration. Here, in the beating process, a disc refiner is used, and a beating blade having a high defibrating function (hereinafter referred to as a defibrating blade) is processed for 2.5 hours with a beating blade having a high cutting function (hereinafter referred to as a cutting blade). Using this, beating was further performed for 2 hours to obtain b-1. The obtained cellulose was dehydrated and concentrated to 3 wt%. Thereafter, various evaluations described below were performed, and the following results were obtained. Crystallinity: 80%, average fiber diameter: 90 nm, crystal form: type I crystal, L / D: 450

<Degree of polymerization of cellulose component>
It was measured by a reduced specific viscosity method using a copper ethylenediamine solution specified in the crystalline cellulose confirmation test (3) of “14th revised Japanese pharmacopoeia” (published by Yodogawa Shoten).

<Crystal form and crystallinity of cellulose component>
Using an X-ray diffractometer (manufactured by Rigaku Corporation, multipurpose X-ray diffractometer), a diffraction image was measured by a powder method (at room temperature), and a crystallinity was calculated by a Segal method. The crystal form was also measured from the obtained X-ray diffraction image.

<L / D of cellulose component>
The cellulose component was made into a pure water suspension at a concentration of 1% by mass, and a high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7”, treatment condition: 15,000 rpm × 5 minutes) Obtained by diluting the water dispersion dispersed in with pure water to 0.1-0.5% by mass, casting on mica, and air-drying, as measured with an atomic force microscope (AFM). The ratio (L / D) when the major axis (L) and minor axis (D) of the obtained particle image were determined was calculated and calculated as the average value of 100 to 150 particles.

<Average diameter of cellulose component>
In a planetary mixer (manufactured by Shinagawa Kogyo Co., Ltd., trade name “5DM-03-R”, stirring blade is a hook type) with a cellulose content of 40% by mass, it is 126 rpm at room temperature and normal pressure for 30 minutes. Kneaded. Subsequently, a pure water suspension having a solid content of 0.5% by mass was prepared, and a high shear homogenizer (manufactured by Nippon Seiki Co., Ltd., trade name “Excel Auto Homogenizer ED-7”, treatment condition: 15,000 rpm × 5 minutes), centrifuged (Kubota Shoji Co., Ltd., trade name “6800 type centrifuge”, rotor type RA-400 type, processing conditions: supernatant centrifuged at a centrifugal force of 39200 m ² / s for 10 minutes The supernatant was further centrifuged at 116000 m ² / s for 45 minutes.) Volume obtained by laser diffraction / scattering particle size distribution analyzer (manufactured by Horiba, Ltd., trade name “LA-910”, ultrasonic treatment for 1 minute, refractive index 1.20) using the supernatant after centrifugation. An integrated 50% particle diameter (volume average particle diameter) in the frequency particle size distribution was measured, and this value was defined as the average diameter.

≪ (C) Surface modifier≫
(C-1) Polymerization was performed using ε-caprolactam manufactured by Ube Industries, Ltd., and purification was performed.
170 parts by mass of water, 216 parts by mass of ε-caprolactam, 44 parts by mass of aminocaproic acid, and 0.59 parts by mass of phosphorous acid were stirred and mixed with a mixer until a uniform dispersion was obtained. Subsequently, the mixed dispersion was gradually heated, and the temperature was raised to 240 ° C. while discharging water vapor in the middle of heating, followed by stirring at 240 ° C. for 1 hour to perform a polymerization reaction. When the polymerization was completed, the resin composition obtained was dispensed and cut into pellets. The obtained pellets were treated with hot water at 95 ° C., scoured and dried.
The hot water portion was cooled to evaporate the water, thereby obtaining a surface modifier.
The obtained surface modifier was Mw1138 and Mw / Mn1.15.

≪ (D) Metal ion component≫
(D-1) Copper iodide (I) Wako Pure Chemical Industries, Ltd. Trade name Copper iodide (I)
(D-2) Potassium iodide Wako Pure Chemical Industries, Ltd. Product name Potassium iodide

≪ (E) Sliding agent component≫
(E-1) Wax Baker Petrolite Co., Ltd. Product name Uniside 700 (Mn819, Mw1100, Mw / Mn1.2, melting point 110 ° C.)
(E-2) Ethylene bisstearylamide Lion product name Armo wax EBS (molecular weight 593, melting point 145 ° C.)

≪Mechanical properties≫
A multipurpose test piece based on ISO294-3 was molded using an injection molding machine. The obtained multipurpose test piece was measured for tensile yield strength and tensile elongation at break according to ISO 527 and bending elastic modulus according to ISO 179.

≪Aging test≫
The exposure test of the multipurpose test piece was implemented in 150 degreeC atmosphere using GPH-102 by ESPEC Corporation. The exposed sample was stored in an aluminum bag, and the tensile yield strength was measured according to ISO527. The strength retention at this time was evaluated based on the number of days in which the tensile yield strength was maintained at 80% based on the multipurpose test piece on the day of exposure 0 (100%).

≪Cantilever bending fatigue characteristics≫
A resin molded body of a test piece (thickness 6 mm type III test piece) based on ISO294-3 was obtained from the pellet of the obtained resin composition using an EC-75NII molding machine manufactured by Toshiba Machine Co., Ltd. Using this test piece, a cantilever bending fatigue test was measured under a condition in accordance with JIS-K7119, at a repetition rate of 35 Hz, a temperature of 23 ± 1 ° C., and a humidity of RH 60 ± 5%. The number of times to break was calculated from the intersection of the stress-life curve obtained at this time and the stress of 30 MPa.

≪Linear expansion coefficient≫
A cube sample having a length of 4 mm, a width of 4 mm, and a length of 4 mm was cut out from the center of the multi-purpose test piece with a precision cut-and-saw and measured in accordance with ISO 11359-2 at a measurement temperature range of −10 to 80 ° C. The expansion coefficient between 60 ° C. was calculated.

<< Calculation of W, W ', W ">>
W ′ = (A) Adhered to the residue (ie, cellulose after extraction) when the resin composition is dissolved in the polyamide resin-soluble solvent (hexafluoro-2-propanol) (C) The surface modifier Amount [g / g of resin composition]
W ″ = (A) Amount of (C) surface modifier in the solution when the resin composition is dissolved in the polyamide resin-soluble solvent (hexafluoro-2-propanol) [g / g of resin composition]
W = W ′ + W ″: (C) Amount of surface modifier of the entire resin composition [g / g of resin composition]
1 g of the resin composition was added to 50 ml of hexafluoro-2-propanol to dissolve the polyamide resin in the composition, and the solution was centrifuged and filtered to separate the cellulose. 2 ml of hexafluoro-2-propanol was added to the wet cake-like cellulose obtained by the separation, washed for 3 seconds, and filtered under reduced pressure once. The cellulose obtained by this vacuum filtration was air-dried at 23 ° C. for 24 hours or more to obtain dry cellulose. Toluene was added as an internal standard substance to 20 mg of the obtained dry cellulose, and ¹ H-NMR measurement was performed using 1 ml of d-hexafluoro-2-propanol. W ′ was quantified from the intensity ratio between the signal of the internal standard substance and the signal of (C) the surface modifier.

The filtrate in which the polyamide resin obtained in the previous separation was dissolved was air-dried at 23 ° C. for 24 hours or more, and further vacuum-dried at 23 ° C. for 24 hours. Using the obtained dried polyamide, a solution was prepared so as to be a hexafluoro-2-propanol solution having a polyamide concentration of 3 mg / ml, and GPC measurement was performed using the solution under the following conditions.
Equipment: Eco Sec manufactured by Tosoh Corporation
Column: 2 TSKgel Super GMH-M, TSKgel Super G1000H
Oven: 40 ° C
Eluent: HFIP (TFANa 4.848 g / kg)
Flow rate: Sample: 0.50 mL / min, ref: 0.25 mL / min
Sample volume: 25 μl 3 mg / ml
Detector: RI
Calibration curve: PMMA (polymethyl methacrylate)
The chromatogram obtained by GPC measurement was vertically divided into a component having a molecular weight of more than 2000 and a component having a molecular weight of 2000 or less, and the respective area ratios, Mn and Mw were calculated. W ″ was calculated from the area ratio of signals having a molecular weight of 2000 or less.

≪Formability≫
Separately from the multi-purpose test piece conforming to ISO294-3 using the previous injection molding machine, the cylinder temperature was set to 250 ° C. using an injection molding machine (EC-75NII, manufactured by Toshiba Machine Co., Ltd.). Was set under the injection conditions of an injection time of 35 seconds and a cooling time of 15 seconds to obtain a flat plate having a thickness of 2 mm, a length of 120 mm, and a width of 80 mm. The mold temperature at this time was 70 degreeC. At this time, molding was repeated until silver streaks were generated in the molded piece. The number of occurrences is listed in each table. Further, the extruder body was moved after molding 30 times, and the amount of resin adhering to the nozzle part was weighed. The amount of adhered resin at this time is shown in each table.

≪Extrusibility≫
Using an extruder (Toshiki Machine Co., Ltd. TEM-26SS extruder (L / D = 48, with vent), all cylinder temperatures were set to 260 ° C., and mixing was performed based on each table. Feeded from the feeder at the top main throat alone, optionally added and mixed with additional ingredients, extruded the resin kneaded material into strands under conditions of an extrusion rate of 10 kg / hour and a screw speed of 250 rpm, After quenching with a strand bath and cutting with a strand cutter, a pellet-shaped molded body was obtained, the main extrusion was continued for 3 hours, the closed state of the vent portion was visually confirmed, and the blocked state was evaluated in three stages.
○: No blockade △: Slight blockage ×: Blockage confirmed

  W, W ′, and W ″ are derived from the amount of the component (c-1), (A) an oligomer that is a decomposition product of the polyamide resin, and / or (A) a raw material monomer of the polyamide resin (that is, from the raw material monomer). The sum of the amount of oligomers produced) during polymerization.

≪Comparative example 1≫
170 parts by mass of water, 216 parts by mass of a-1, 44 parts by mass of aminocaproic acid, and 0.59 parts by mass of phosphorous acid were stirred and mixed with a mixer until a uniform dispersion was obtained. Subsequently, the mixed dispersion was gradually heated, and the temperature was raised to 240 ° C. while discharging water vapor in the middle of heating, followed by stirring at 240 ° C. for 1 hour to perform a polymerization reaction. When the polymerization was completed, the resin composition obtained was dispensed and cut into pellets. The obtained pellets were refined with hot water at 95 ° C. for 180 minutes and dried. The injection molding conditions were a cylinder temperature of 250 ° C. and a mold temperature of 70 ° C. Various evaluations were performed. The results are shown in Tables 1 and 2.

«Comparative Examples 2-5, Examples 1-10»
340 parts by mass of b-1, 216 parts by mass of a-1, 44 parts by mass of aminocaproic acid, and 0.59 parts by mass of phosphorous acid were stirred and mixed with a mixer until a uniform dispersion was obtained. Subsequently, the mixed dispersion was gradually heated, and the temperature was raised to 240 ° C. while discharging water vapor in the middle of heating, followed by stirring at 240 ° C. for 1 hour to perform a polymerization reaction. In Examples 2 to 10 and Comparative Examples 4 and 5, d-1 was added in advance to 0.0324 parts by mass during polymerization, and polymerization was performed. When the polymerization was completed, the resin composition obtained was dispensed and cut into pellets. The obtained pellets were refined with hot water at 95 ° C. for the time shown in Tables 1 and 2 and dried. In Comparative Example 2, after the polymerization, the state of 80 ° C. and 100 Pa or less was maintained, and vacuum drying was performed for 24 hours. In Comparative Examples 4 and 5, annealing was performed at 130 ° C. for 6 hours after polymerization. In Comparative Example 5, the injection molding was performed after the humidity was adjusted in an environment of 23 ° C. and 50% so that the moisture in the pellets after polymerization was 3000 ppm. The injection molding conditions were a cylinder temperature of 250 ° C. and a mold temperature of 70 ° C. Various evaluations were performed. The results are shown in Tables 1 and 2.

<< Examples 11 to 18, Comparative Example 6 >>
Uniform dispersion of 340 parts by weight of b-1, 216 parts by weight of a-1, 44 parts by weight of aminocaproic acid, 0.59 parts by weight of phosphorous acid, and 0.0324 parts by weight of d-1 It stirred and mixed with the mixer until it became a liquid. Subsequently, the mixed dispersion was gradually heated, and the temperature was raised to 240 ° C. while discharging water vapor in the middle of heating, followed by stirring at 240 ° C. for 1 hour to perform a polymerization reaction. When the polymerization was completed, the resin composition obtained was dispensed and cut into pellets. The obtained pellets were refined with hot water at 95 ° C. for the time shown in Tables 3 and 4 and dried. The operations after polymerization are described in Tables 3 and 4, and were performed in the same manner as in the previous comparative examples and examples. The injection molding conditions were a cylinder temperature of 250 ° C. and a mold temperature of 70 ° C. Various evaluations were performed. The results are shown in Tables 3 and 4.

<< Examples 19 to 20, Comparative Example 6 >>
Uniform dispersion of 340 parts by weight of b-1, 216 parts by weight of a-1, 44 parts by weight of aminocaproic acid, 0.59 parts by weight of phosphorous acid, and 0.0324 parts by weight of d-1 It stirred and mixed with the mixer until it became a liquid. Subsequently, the mixed dispersion was gradually heated, and the temperature was raised to 240 ° C. while discharging water vapor in the middle of heating, followed by stirring at 240 ° C. for 1 hour to perform a polymerization reaction. When the polymerization was completed, the resin composition obtained was dispensed and cut into pellets. The obtained pellets were refined with hot water at 95 ° C. for the time shown in Tables 3 and 4 and dried. The operations after polymerization are described in Tables 3 and 4, and were performed in the same manner as in the previous comparative examples and examples. 100 parts by mass of the obtained composition and other components were melt-kneaded at a ratio shown in Tables 3 and 4 using a twin screw extruder and dried to obtain a composition. Various evaluations were performed. The results are shown in Tables 3 and 4.

<< Examples 21 and 22 >>
Using 100 parts by mass of a-2, refining was carried out with hot water at 95 ° C. for the time shown in Tables 3 and 4, and dried. The pellet, 157.4 parts by mass of b-1, and other components were melt-kneaded at a ratio shown in Tables 3 and 4 using a twin screw extruder and dried to obtain a composition. The injection molding conditions were a cylinder temperature of 250 ° C. and a mold temperature of 70 ° C. Various evaluations were performed. The results are shown in Tables 3 and 4.

<< Examples 23 to 35 >>
Uniform dispersion of 340 parts by weight of b-1, 216 parts by weight of a-1, 44 parts by weight of aminocaproic acid, 0.59 parts by weight of phosphorous acid, and 0.0324 parts by weight of d-1 It stirred and mixed with the mixer until it became a liquid. Subsequently, the mixed dispersion was gradually heated, and the temperature was raised to 240 ° C. while discharging water vapor in the middle of heating, followed by stirring at 240 ° C. for 1 hour to perform a polymerization reaction. When the polymerization was completed, the resin composition obtained was dispensed and cut into pellets. The obtained pellets were refined with hot water at 95 ° C. for the time shown in Tables 5 and 6 and dried. The operations after polymerization are shown in Tables 5 and 6, and were carried out in the same manner as the previous comparative examples and examples.

  100 parts by mass of the obtained composition and other components were melt-kneaded using a biaxial extruder at the ratios shown in Tables 5 and 6 and dried to obtain a composition. The injection molding conditions were a cylinder temperature of 250 ° C. and a mold temperature of 70 ° C. Various evaluations were performed. The results are shown in Tables 5 and 6.

<< Comparative Example 7 >>
Polymerization was carried out by the method described in Example 1 of WO 2011/1226038 except that 170 parts by mass of b-1 was used as an aqueous dispersion of cellulose fiber instead of serisch KY100G. The obtained pellets were refined with hot water at 95 ° C. for 120 min and dried. The injection molding conditions were a cylinder temperature of 250 ° C. and a mold temperature of 70 ° C. Various evaluations were performed. The results are shown in Tables 5 and 6.

Example 36
170 parts by mass of b-1, 216 parts by mass of a-1, 44 parts by mass of aminocaproic acid, and 0.59 parts by mass of phosphorous acid were stirred and mixed with a mixer until a uniform dispersion was obtained. Subsequently, this mixed dispersion was gradually heated, and the temperature was raised to 240 ° C. while discharging water vapor in the middle of heating, and the mixture was stirred at 240 ° C. for 1 hour to carry out a polymerization reaction. When the polymerization was completed, the resin composition obtained was dispensed and cut into pellets. The obtained pellets were refined for the times shown in Tables 5 and 6. Furthermore, the state of 80 ° C. and 100 Pa or less was maintained, and vacuum drying was performed for 24 hours. The injection molding conditions were a cylinder temperature of 250 ° C. and a mold temperature of 70 ° C. Various evaluations were performed. The results are shown in Tables 5 and 6.

  The polyamide resin composition of the present invention is a sliding part mechanism part represented by gears, cams, sliders, shafts, bearings, guides, etc .; outsert molded resin parts, insert molded resin parts, door locks, doors Door parts represented by handles, window regulators, speaker grills, etc .; seat belt peripheral parts represented by slip rings for seat belts, press buttons, etc .; parts such as combination switch parts, switches, clips, etc. The present invention can be applied to various uses such as uses, electrical materials, and automotive exterior materials.

Claims (12)

  (A) A polyamide resin composition comprising 100 parts by mass of a polyamide resin, (B) cellulose, and (C) 0.01 to 5 parts by mass of a surface modifier. When the polyamide resin composition is dissolved in a polyamide resin-soluble solvent, the content of (C) surface modifier in the insoluble component is W ′, and the content of (C) surface modifier in the solution is W ″. , Where W ′ and W ″ are the sum of W, the following relational expression (1):
1 ≧ 10 × W ′ / W (1)
The polyamide resin composition according to claim 1, wherein   (C) The polyamide resin composition of Claim 1 or 2 containing 0.01-2 mass parts of surface modifiers.   (C) The polyamide resin composition as described in any one of Claims 1-3 whose number average molecular weights of a surface modifier are 100-2000.   (C) The surface modifier is selected from the group consisting of polyolefin resins, polyamide resins, polyester resins, polyacetal resins, polyacrylic resins, polyphenylene ether resins, polyphenylene sulfide resins, and modified products thereof. The polyamide resin composition according to any one of claims 1 to 4, which is an oligomer of more than one species.   (D) The polyamide resin composition as described in any one of Claims 1-5 containing a metal ion component. (D) The metal ion component is selected from the group consisting of copper iodide (CuI), cuprous bromide (CuBr), cupric bromide (CuBr ₂ ), cuprous chloride (CuCl), and copper acetate. The polyamide resin composition according to claim 6, wherein the polyamide resin composition is one or more.   (E) The polyamide resin composition as described in any one of Claims 1-7 containing a sliding agent component.   (E) The sliding agent component is one or more selected from the group consisting of alcohol, amine, carboxylic acid, hydroxy acid, amide, ester, polyoxyalkylene glycol, silicone oil, wax, and lubricating oil. 9. The polyamide resin composition according to 8.   (E) Polyamide resin composition of Claim 8 or 9 whose melting | fusing point of a sliding agent component is 40-150 degreeC.   (A) It is obtained by mixing the raw material monomer of a polyamide resin, and (B) the aqueous dispersion liquid of a cellulose, and performing a polymerization reaction, It is described in any one of Claims 1-10. Polyamide resin composition.   The molded object containing the polyamide resin composition as described in any one of Claims 1-11.