JP5806885B2 - Resin composition - Google Patents

Description

  The present invention relates to a resin composition.

  Conventionally, polymer alloys made of polyamide resin / polyphenylene ether resin are excellent in mechanical strength, heat resistance, chemical resistance, etc., and thus have been used in many fields such as automobile parts, mechanical parts, and electrical / electronic parts. .

  In recent years, parts from various industrial fields have been converted from metals and thermosetting resins to thermoplastic resins from the viewpoint of weight reduction and productivity improvement by integral molding. As a molded article using a thermoplastic resin, a material having further excellent heat resistance, molding processability, impact resistance, and rigidity is required.

  From the above, studies have been conducted on the dispersion form (morphology) of the polymer alloy. For example, a thermoplastic resin composition (see, for example, Patent Document 1) having an excellent balance of heat resistance, impact resistance, and chemical resistance by using a polyphenylene ether resin as a domain phase has been proposed. There has been proposed a thermoplastic resin composition that controls the diameter and is excellent in toughness, light discoloration resistance, molding fluidity, appearance of a molded product, and impact resistance (see, for example, Patent Documents 2 and 3).

  However, the impact resistance improvement effect by these morphological controls is not sufficient.

  Therefore, the applicant of the present invention is a thermoplastic resin excellent in toughness and impact resistance, in which a mixture of a polyphenylene ether resin and an elastomer component is dispersed as a domain phase with a dispersed particle size of 1.2 μm or less in a polyamide resin matrix in order to improve toughness. The resin composition (for example, refer patent document 4) is proposed.

JP 2009-235282 A JP 2006-219563 A Japanese Patent Laid-Open No. 08-134347 JP 2004-256827 A

  However, in the resin composition composed of polyamide resin / polyphenylene ether resin added with elastomer described in Patent Document 4, toughness and impact resistance are improved by adding elastomer, but rigidity tends to decrease. There is room for improvement.

  Under such circumstances, there is a demand for materials having higher toughness and rigidity while maintaining the excellent mechanical properties of the polymer alloy composed of polyamide resin / polyphenylene ether resin, but the improvement regarding these is still insufficient. This is the actual situation.

  Therefore, an object of the present invention is a resin composition containing a polymer alloy composed of a polyamide resin and a polyphenylene ether resin, which is excellent in balance between toughness (impact strength) and rigidity, and excellent in molding fluidity. It is to provide a composition.

  In order to solve the above-mentioned problems, the present inventor has made a resin composition containing a polyamide resin, a polyphenylene ether resin and an elastomer, although the resin type is different, “impact resistance is improved by uniformly dispersing the elastomer” (for example, special Based on the knowledge of Kaihei 11-080497 (described in [0025]), a study was conducted to improve the impact resistance by uniformly dispersing the elastomer in the polyphenylene ether resin. However, the balance between the impact resistance and the rigidity was investigated. Satisfactory results were not obtained. Therefore, further investigations have been carried out, and surprisingly, in a resin composition containing a polyamide resin, a polyphenylene ether resin, a compatibilizing agent and an elastomer, the elastomer is non-uniformly dispersed in the polyphenylene ether resin particles, and the elastomer is non-uniform. It has been found that by taking a dispersed form in which the proportion of uniformly dispersed polyphenylene ether resin particles is within a specific range, a resin composition having excellent balance between toughness (impact strength) and rigidity and excellent molding fluidity can be obtained. It was. Furthermore, the present inventors have found a suitable production method for obtaining a resin composition having the above specific dispersion form, and have reached the present invention.

  That is, the present invention relates to the following.

[1]
(A) a polyamide resin, (b) a polyphenylene ether resin, (c) a compatibilizing agent and (d) an elastomer,
(B) the polyphenylene ether resin is present as the following particles 1 and the following particles 2, and (b) the polyphenylene ether resin particles have a morphology dispersed in the (a) polyamide resin,
The resin composition in which the ratio of the total cross-sectional area of the following particles 2 is 5 to 50% with respect to the total cross-sectional area of all (b) polyphenylene ether resin particles;
Particle 1: (b) In a cross-sectional area of one polyphenylene ether resin particle, (d) a particle in which the elastomer is dispersed at a ratio of 80 to 100%,
Particle 2: (b) Particle in which (d) elastomer is dispersed at a ratio of 0 to 20% in the cross-sectional area of one polyphenylene ether resin particle.

[2]
The resin composition according to [1], wherein the total cross-sectional area of the particles 2 is 5 to 30% with respect to the total cross-sectional area of all (b) polyphenylene ether particles.

[3]
(A) The polyamide resin is at least one selected from the group consisting of polyamide 6, polyamide 6,6, polyamide 6 / 6,6, polyamide 6,12 and polyamide 6,6 / 6, I [1] or The resin composition as described in [2].

[4]
(B) The resin composition according to any one of [1] to [3], wherein the polyphenylene ether resin is 100% by mass of polyphenylene ether, or polyphenylene ether / styrene resin = 30 to 99% by mass / 70 to 1% by mass. object.

[5]
(C) The resin composition according to any one of [1] to [4], wherein the compatibilizer is at least one selected from the group consisting of citric acid, maleic acid, itaconic acid, and anhydrides thereof.

[6]
(D) a block copolymer in which the elastomer contains at least one block mainly composed of an aromatic vinyl compound and at least one block mainly composed of a conjugated diene compound, and / or the block copolymer The resin composition according to any one of [1] to [5], which is a hydrogenated product.

[7]
(A) Polyamide resin content is 40 to 90 parts by mass, (b) Polyphenylene ether resin content is 5 to 50 parts by mass, and (d) Elastomer content is 5 to 20 parts by mass. The content of the (c) compatibilizer is 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the total content of the components (a), (b) and (d) [1] to [6] The resin composition in any one of.

[8]
(A) polyamide resin, (b) polyphenylene ether resin, and (c) a step of melt-kneading the total amount of the compatibilizer above (a) the melting point of the polyamide resin;
The method for producing a resin composition according to any one of [1] to [7], further comprising: (d) supplying an elastomer and (a) performing melt kneading at or above the melting point of the polyamide resin.

[9]
(A) polyamide resin, (b) polyphenylene ether resin and (c) a step of obtaining pellets by melting and kneading the total amount of the compatibilizer at or above the melting point of the polyamide resin;
After the step, the obtained pellet and (d) the elastomer are mixed, and (a) a melt kneading step at or above the melting point of the polyamide resin, the resin composition according to any one of [1] to [7] Manufacturing method.

[10]
[1] A resin structural component obtained by molding the resin composition according to any one of [7].

[11]
1 selected from the group consisting of home appliance / OA equipment internal parts, optical equipment mechanism parts, light source lamp surrounding parts, optical fiber connector ferrule, printer parts, copier parts, automobile lamp parts, automobile engine compartment parts, and automobile interior parts The resin structural component according to [10], which is a seed or more.

  According to the present invention, in a resin composition containing a polyamide resin, a polyphenylene ether resin, a compatibilizing agent and an elastomer, by taking a specific dispersion form, the balance between toughness (impact strength) and rigidity is excellent, and molding fluidity is achieved. Can be obtained. The resin composition having such a specification is very useful industrially.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail.

  The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist.

≪Resin composition≫
The resin composition of the present embodiment includes (a) a polyamide resin, (b) a polyphenylene ether resin, (c) a compatibilizing agent, and (d) an elastomer.
(B) the polyphenylene ether resin is present as the following particles 1 and the following particles 2, and (b) the polyphenylene ether resin particles have a morphology dispersed in the (a) polyamide resin,
The ratio of the total cross-sectional area of the following particles 2 is 5 to 50% with respect to the total cross-sectional area of all (b) polyphenylene ether resin particles.
Particle 1: (b) Particle in which (d) elastomer is dispersed at a ratio of 80 to 100% in the cross-sectional area of one polyphenylene ether resin particle.
Particle 2: (b) Particle in which (d) elastomer is dispersed at a ratio of 0 to 20% in the cross-sectional area of one polyphenylene ether resin particle.

<(A) Polyamide resin>
The type of (a) polyamide resin that can be used in the present embodiment is not particularly limited as long as it has an amide bond {—NH—C (═O) —} in the repeating unit of the polymer main chain. .

  Polyamide resins are generally obtained by ring-opening polymerization of lactams, polycondensation of diamine and dicarboxylic acid, polycondensation of aminocarboxylic acid, and the like, but the method for obtaining the polyamide resin is not limited to these.

  The diamine is roughly classified into aliphatic, alicyclic and aromatic diamines, and specific examples include tetramethylene diamine, hexamethylene diamine, 1,9-nonamethylene diamine, 2-methyl-1,8-octa. Methylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecamethylene diamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 1,3- One or more kinds selected from bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, and p-xylylenediamine are exemplified.

  Among these, preferable diamines are exemplified by one or more diamines selected from tetramethylene diamine, hexamethylene diamine, 1,9-nonamethylene diamine and 2-methyl-1,8-octamethylene diamine. It is done. Particularly preferred are hexamethylenediamine, 1,9-nonamethylenediamine, and a mixture of 1,9-nonamethylenediamine and 2-methyl-1,8-octamethylenediamine.

  Dicarboxylic acids are roughly classified into aliphatic, alicyclic and aromatic dicarboxylic acids. Specific examples include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,1,3-tridecane. One or more kinds selected from diacid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, dimer acid and the like can be mentioned.

  Specific examples of lactams include ε-caprolactam, enantolactam, and ω laurolactam.

  Specific examples of aminocarboxylic acids include ε-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminonanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and 13-aminotridecane. An acid etc. are mentioned.

  In the present embodiment, these lactams, diamines, dicarboxylic acids, and aminocarboxylic acids may be used alone or in combination of two or more. Any of the copolymer polyamides obtained by polycondensation of two or more of these as a mixture can be used as the (a) polyamide resin.

  In addition, these lactams, diamines, dicarboxylic acids, and aminocarboxylic acids are polymerized in a polymerization reactor up to the low molecular weight oligomer stage, and those having a high molecular weight by an extruder or the like are also preferably used as the (a) polyamide resin. Can do.

  In particular, (a) polyamide resin that can be usefully used in this embodiment includes polyamide 6, polyamide 6,6, polyamide 6, T, polyamide 4,6, polyamide 11, polyamide 12, polyamide 6,10, polyamide 6 , 12, polyamide 6 / 6,6, polyamide 6 / 6,12, polyamide MXD (m-xylylenediamine), 6, polyamide 9, T, polyamide 12, T, polyamide 6, I, polyamide 6/6, T , Polyamide 6/6, I, polyamide 6,6 / 6, T, polyamide 6,6 / 6, I, polyamide 6/6, T / 6, I, polyamide 6,6 / 6, T / 6, I, Polyamide 6/12/6, T, Polyamide 6, 6/12/6, T, Polyamide 6/12/6, I, Polyamide 6, 6/12/6, I and the like. Polyamides obtained by copolymerizing a plurality of polyamide resins with an extruder or the like can also be used as the (a) polyamide resin. Preferred (a) polyamide resins are polyamide 6, polyamide 6,6, polyamide 9, T, polyamide 6 / 6,6, polyamide 6,6 / 9, T, polyamide 6,12, polyamide 6,6 / 6, I , Polyamide MXD, 6, polyamide 4,6, polyamide 11 and polyamide 12. Among these, more preferable (a) polyamide resin is polyamide 6, polyamide 6,6, polyamide 6 / 6,6, polyamide 6,12, polyamide 6,6 / 6, I, polyamide 6, T, polyamide 9, T, And one or more selected from the group consisting of polyamide 12. Particularly preferred (a) polyamide resin is at least one selected from the group consisting of polyamide 6, polyamide 6,6, polyamide 6 / 6,6, polyamide 6,12 and polyamide 6,6 / 6, I.

  The viscosity number of the polyamide resin (a) used in the present embodiment is not particularly limited as long as the characteristics of the present embodiment are not impaired, but is measured with 96% sulfuric acid in accordance with ISO 307: 1994. ) As a preferable range of the viscosity number of the polyamide resin, for example, in use for injection molding, 50 ml / g to 100 ml / g or 50 ml / g to 150 ml / g is preferable. For example, blow molding, sheet molding, film molding, etc. In use, the range of 50 ml / g to 250 ml / g or 100 ml / g to 250 ml / g is preferable.

  The (a) polyamide resin that can be used in the resin composition of the present embodiment may be a mixture of a plurality of polyamide resins having different viscosity numbers. When a plurality of polyamide resins are used, the viscosity number of the polyamide resin mixture is preferably within the above-described range. In order to confirm that the polyamide resin mixture is within the above-mentioned range of the viscosity number, it can be easily confirmed by actually measuring the viscosity number of the polyamide mixture mixed at a desired mixing ratio.

  (A) The terminal group of the polyamide resin is involved in the reaction with polyphenylene ether. Polyamide resins generally have an amino group or a carboxyl group as a terminal group. However, when the carboxyl group concentration is generally high, impact resistance is reduced, fluidity is improved, and conversely the amino group concentration is high. If it becomes, impact resistance will improve and fluidity | liquidity will fall.

  In the (a) polyamide resin used in the present embodiment, a preferable ratio of these terminal groups is an amino group / carboxyl group concentration ratio, which is 9/1 to 1/9, more preferably 6/4 to 1/9, More preferably, it is 5/5 to 1/9.

The terminal amino group concentration is preferably 10 to 80 μmol / g. More preferably, it is 15-65 micromol / g, More preferably, it is 20-40 micromol / g. By setting the concentration of the terminal amino group within these ranges, it is possible to prevent a significant decrease in the fluidity in the mold of the resin composition. In addition, the density | concentration of a terminal amino group can be calculated | required from the integral value of the characteristic signal corresponding to an amino group by < ¹ > H-NMR.

  As a method for adjusting the end groups of these (a) polyamide resins, a known method that will be apparent to those skilled in the art can be used. For example, (a) a method of adding one or more selected from a diamine compound, a monoamine compound, a dicarboxylic acid compound, a monocarboxylic acid compound and the like so as to have a predetermined terminal concentration at the time of polymerization of the polyamide resin is exemplified.

  Moreover, in this embodiment, you may add a transition metal and / or a halogen in a resin composition in order to further improve the heat-resistant stability provided to a resin composition by (a) polyamide resin. Although there is no restriction | limiting in particular regarding the kind of transition metal, Copper, cerium, nickel, and cobalt are preferable, and copper is especially preferable. Of the halogens, bromine or iodine can be preferably used.

  A preferable addition amount of the transition metal is 10 ppm or more and less than 200 ppm, more preferably 10 ppm or more and less than 100 ppm in the resin composition. Moreover, the preferable addition amount of a halogen is 500 ppm or more and less than 1500 ppm in a resin composition, More preferably, it is 700 ppm or more and less than 1200 ppm.

  As a method for adding these transition metals and / or halogens to the resin composition, for example, a method of adding (a) a polyamide resin / (b) a resin composition containing a polyphenylene ether resin as a powder when melt kneading, ( Examples include a) a method of adding at the time of polymerization of the polyamide resin, (a) a method of adding a master pellet added to the polyamide resin at a high concentration, and then adding this master pellet to the resin composition. It doesn't matter. Among these methods, a preferable method is (a) a method of adding at the time of polymerization of the polyamide resin, or (a) a method of adding after preparing a master pellet added to the polyamide resin at a high concentration.

  Furthermore, in addition to the above, (a) known additives that can be added to the polyamide resin may be added in an amount of less than 10 parts by mass with respect to 100 parts by mass of the (a) polyamide resin.

<(B) Polyphenylene ether resin>
The (b) polyphenylene ether resin (hereinafter also abbreviated as “PPE”) used in the present embodiment is a homopolymer and / or copolymer polyphenylene comprising repeating units represented by the following bond units (formula 1). Ether resins or those in which these polyphenylene ether resins and styrene resins are mixed at an arbitrary ratio are preferable. The number average molecular weight of the (b) polyphenylene ether resin in terms of polystyrene measured using GPC (gel permeation chromatography) is preferably 1000 or more, more preferably 1500 to 50000, and still more preferably 1500 to 30000. .

(Where R1, R2, R3 and R4 are each a hydrogen atom, a halogen atom, a primary or secondary lower alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, A hydrogenoxy group or a halohydrocarbonoxy group in which at least two carbon atoms separate a halogen atom and an oxygen atom, which may be the same or different.
Specific examples of this PPE include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-6- 6). Phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols (for example, 2, 3, 6). Also included are polyphenylene ether copolymers such as copolymers with -trimethylphenol and 2-methyl-6-butylphenol). Of these, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1 , 4-phenylene ether).

  A method for producing such PPE is not particularly limited as long as it can be obtained by a known method. For example, a complex of cuprous salt and amine by Hay described in US Pat. No. 3,306,874 is used as a catalyst. For example, there is a method of producing PPE by oxidative polymerization of 2,6-xylenol. As other methods for producing PPE, U.S. Pat. No. 3,306,875, U.S. Pat. No. 3,257,357, U.S. Pat. No. 3,257,358, JP-B-52-17880, and JP-A-50-51197 are disclosed. And the method described in JP-A No. 63-152628.

  In addition, the polyphenylene ether resin (b) that can be used in the present embodiment may be a polyphenylene ether resin modified in whole or in part. The modified polyphenylene ether resin here means at least one carbon-carbon double bond or triple bond in the molecular structure, and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group or glycidyl. A polyphenylene ether resin modified with at least one modifying compound having a group.

  The modified polyphenylene ether resin can be produced by (1) melting the polyphenylene ether resin in the temperature range of 100 ° C. or higher and lower than the glass transition temperature of the polyphenylene ether resin in the presence or absence of a radical initiator. (2) A method in which the compound is melt kneaded and reacted with the modifying compound in a temperature range of not less than 360 ° C. and (3) a temperature lower than the glass transition temperature of the polyphenylene ether resin. Examples thereof include a method of reacting a polyphenylene ether resin and a modifying compound in a solution, and any of these methods may be used, but the method (1) or (2) is preferred.

  Next, at least one modified compound having at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group or glycidyl group in the molecular structure. This will be specifically described.

  Examples of the modified compound having a carbon-carbon double bond and a carboxylic acid group or an acid anhydride group in the molecule include maleic acid, fumaric acid, chloromaleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid and These acid anhydrides are mentioned. Fumaric acid, maleic acid, and maleic anhydride are particularly preferable, and fumaric acid and maleic anhydride are particularly preferable. In addition, one in which one or two of the two carboxyl groups of the unsaturated dicarboxylic acid is an ester can be used.

  Examples of the modified compound having a carbon-carbon double bond and a glycidyl group in the molecule include allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and epoxidized natural oil. Among these, glycidyl acrylate and glycidyl methacrylate are particularly preferable.

Examples of the modified compound having a carbon-carbon double bond and a hydroxyl group in the molecule include general formula C _n H _2n-3 OH such as allyl alcohol, 4-penten-1-ol, and 1,4-pentadien-3-ol. (N is a positive integer) unsaturated alcohol, and unsaturated alcohols such as general formulas C _n H _2n-5 OH and CnH _2n-7 OH (n is a positive integer).

  The above-described modifying compounds may be used alone or in combination of two or more.

  0.1-10 mass parts is preferable with respect to 100 mass parts of polyphenylene ether resins, and, as for the addition amount of the modification compound at the time of manufacturing modified polyphenylene ether resin, More preferably, it is 0.3-5 mass parts.

  A preferable amount of the radical initiator in producing the polyphenylene ether resin modified with the radical initiator is 0.001 to 1 part by mass with respect to 100 parts by mass of the polyphenylene ether resin.

  Further, the addition ratio of the modifying compound to the modified polyphenylene ether resin is preferably 0.01 to 5% by mass. More preferably, it is 0.1-3 mass%.

  In the modified polyphenylene ether resin, an unreacted modified compound and / or polymer of the modified compound may remain if it is less than 1% by mass.

  Furthermore, you may add the well-known additive etc. which can be added to polyphenylene ether resin in the quantity of less than 10 mass parts with respect to 100 mass parts of polyphenylene ether resin.

  The polyphenylene ether resin of the component (b) used in the present embodiment can be used even with 100% by mass of the polyphenylene ether described above, but in this embodiment, polyphenylene ether / styrene resin = 1 to 99% by mass / 99 to 1%. What was comprised by the ratio of the mass% can be used preferably. Among these, in the resin composition of the present embodiment, the ratio of polyphenylene ether / styrene-based resin is more preferably 20 to 99% by mass / 80 to 1% by mass in order to improve the molding fluidity. It is more preferable that it is 99 mass% / 70-1 mass%, and it is especially preferable that it is 30-80 mass% / 70-20 mass%.

  Such a styrene resin is a rubber polymer dispersed in a matrix made of a homopolymer of a styrene compound, a copolymer of two or more styrene compounds, and a polymer of styrene compounds. Examples thereof include rubber-modified styrene resin (high impact polystyrene). Examples of the styrenic compound that gives these polymers include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, α-methylstyrene, ethylstyrene, α-methyl-p-methylstyrene, 2,4- Examples thereof include dimethyl styrene, monochloro styrene, and p-tert-butyl styrene.

  These styrenic compounds may be a copolymer obtained by using two or more kinds in combination, but among them, polystyrene obtained by polymerization using styrene alone is preferable. As these polymers, polystyrene having a stereoregular structure such as atactic polystyrene and syndiotactic polystyrene can be effectively used.

  The styrene resin used in combination with the polyphenylene ether includes a block copolymer obtained by copolymerizing an aromatic vinyl compound corresponding to the component (d) shown below and a conjugated diene compound, and / or Block copolymer hydrogenation is not included.

<(C) Compatibilizer>
The (c) compatibilizer used in the present embodiment acts as an emulsifying dispersant when mixing the (a) polyamide resin and the (b) polyphenylene ether resin, and has excellent toughness ( Impact strength) and rigidity.

  The (c) compatibilizing agent that can be used in the present embodiment refers to a polyfunctional compound that interacts with (a) a polyamide resin, (b) a polyphenylene ether resin, or both. This interaction may be chemical (eg, grafting) or physical (eg, changing the surface properties of the dispersed phase). In any case, the resulting polyamide resin-polyphenylene ether resin mixture exhibits improved compatibility.

  Such (c) compatibilizers are described in detail in JP-A-8-48869 and JP-A-9-124926, and all of these known compatibilizers can be used. Is possible.

  Among these various compatibilizers, particularly preferred (c) compatibilizer is at least one selected from the group consisting of citric acid, maleic acid, itaconic acid and anhydrides thereof. Of these, maleic anhydride and citric acid are more preferable. By including such a (c) compatibilizing agent, the resulting resin composition tends to further improve the balance between toughness (impact strength) and rigidity.

<(D) Elastomer>
The (d) elastomer used in this embodiment is a component that is usually contained in the resin composition for the purpose of imparting impact strength. Examples of the elastomer (d) include a block copolymer obtained by copolymerizing a vinyl aromatic compound and a conjugated diene compound, and a hydrogenated block copolymer obtained by further hydrogenating the block copolymer. In addition to these block copolymers and hydrogenated block copolymers, at least one functional group selected from a hydroxyl group, a carboxyl group, an acid anhydride group, an ester group, an epoxy group, an oxazolyl group, and an amino group Can be used. Further, (d) as an elastomer, an ethylene / α-olefin copolymer or this ethylene / α-olefin copolymer may be added to a hydroxyl group, a carboxyl group, an acid anhydride group, an ester group, an epoxy group, an oxazolyl group, or an amino group. A copolymer provided with a functional group obtained by graft reaction of an unsaturated compound having at least one functional group selected from the above in the presence or absence of a radical initiator, ethylene and / or other α -Copolymerizing an olefin with a functional group-containing unsaturated compound having at least one functional group selected from a hydroxyl group, a carboxyl group, an acid anhydride group, an ester group, an epoxy group, an oxazolyl group, and an amino group. Examples thereof include a functional group-containing copolymer. At least one selected from (d) elastomers can be used according to the purpose.

  In particular, as the elastomer (d), a block copolymer obtained by copolymerizing a vinyl aromatic compound and a conjugated diene compound and / or a hydrogenated block copolymer obtained by further hydrogenating the block copolymer. Is particularly preferable from the viewpoints of heat resistance, heat deterioration resistance, and (b) miscibility with polyphenylene ether resin.

  Specifically, as the elastomer (d), a block copolymer containing at least one polymer block mainly composed of an aromatic vinyl compound and at least one polymer block mainly composed of a conjugated diene compound. And / or a hydrogenated product of the block copolymer. Specific examples of the aromatic vinyl compound constituting a part of the block copolymer include styrene, α-methylstyrene, vinyltoluene and the like, but are not limited thereto. Two or more of these aromatic vinyl compounds may be used in combination. Styrene is particularly preferred.

  Specific examples of the conjugated diene compound constituting a part of the block copolymer include butadiene, isoprene, piperylene, 1,3-pentadiene and the like, but are not limited thereto. Two or more of these conjugated diene compounds may be used in combination. Butadiene, isoprene or combinations thereof are preferred.

  Here, “mainly” in a block mainly composed of an aromatic vinyl compound and a block mainly composed of a conjugated diene compound means that at least 50% by mass of the block is an aromatic vinyl compound or a conjugated diene compound. Means. More preferably, it is 70 mass% or more.

  When butadiene is used as the conjugated diene compound of the block copolymer, the microstructure of the polybutadiene block portion is such that the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is 5 to 80%. Preferably, 10 to 50% is more preferable, and 15 to 40% is still more preferable. Usually, there are 1,2-vinyl bond, 3,4-vinyl bond, and 1,4-vinyl bond as the bond form of the conjugated diene compound. The vinyl bond amount referred to here is the conjugated diene compound at the time of polymerization. The ratio of the bonding form is shown. For example, the amount of 1,2-vinyl bond means the ratio of 1,2-vinyl bond in the above three bond forms and can be easily known by an infrared spectrophotometer, a nuclear magnetic resonance apparatus, or the like. be able to.

  Furthermore, the bonding form of the polymer block (S) mainly composed of an aromatic vinyl compound and the polymer block (B) mainly composed of a conjugated diene compound is as follows: SB type, SBS type, S Examples include a bonding form selected from among -B-S-B types. (D) The elastomer is preferably a block copolymer having such a bonding form. Among these, the SBS type and the SBS type are more preferable, and the SBS type is more preferable. Of course, these may be a mixture.

  In the present embodiment, a hydrogenated block copolymer of an aromatic vinyl compound and a conjugated diene compound can also be used as the (d) elastomer. In other words, this hydrogenated block copolymer is a mixture of the above-described aromatic vinyl compound and conjugated diene compound in a block copolymer that is hydrogenated by hydrogenating the aliphatic double bond to exceed 100. Controlled by the rate of hydrogenation treatment for double bonds within the range up to%. A preferable hydrogenation rate of the hydrogenated block copolymer is 50% or more, more preferably 80% or more, and still more preferably 95% or more.

  In this embodiment, the block copolymer (optionally hydrogenated) of an aromatic vinyl compound and a conjugated diene compound is preferably a block copolymer having a number average molecular weight of 50,000 or more. More preferred is a block copolymer having a number average molecular weight of 65,000 or more.

  The number average molecular weight as used in the present embodiment refers to the number average molecular weight measured with an ultraviolet spectroscopic detector using a gel permeation chromatography measuring device and converted to standard polystyrene. At this time, a low molecular weight component resulting from catalyst deactivation during polymerization may be detected. In this case, the low molecular weight component is not included in the molecular weight calculation. Usually, the calculated correct molecular weight distribution (weight average molecular weight / number average molecular weight) is preferably in the range of 1.0 to 1.1.

  In the present embodiment, the number average molecular weight of one polymer block mainly composed of an aromatic vinyl compound is preferably 15,000 or more. More preferably, it is 20,000 or more and 300,000 or less. By setting the number average molecular weight of one polymer block mainly composed of an aromatic vinyl compound to 15,000 or more and 300,000 or less, the miscibility with the component (b) is improved, and the resin composition of this embodiment This is preferable because it is effective for imparting impact resistance to objects.

  In addition, the number average molecular weight of one polymer block mainly composed of an aromatic vinyl compound can be obtained by the following equation using the number average molecular weight of the block copolymer described above.

Mn (a) = {Mn × a / (a + b)} / N
[In the above formula, Mn (a) is the number average molecular weight of one polymer block mainly composed of an aromatic vinyl compound, Mn is at least one polymer block mainly composed of an aromatic vinyl compound, and a conjugated diene. The number average molecular weight of a block copolymer containing at least one polymer block mainly composed of a compound, a is the weight percent of the polymer block mainly composed of all aromatic vinyl compounds in the block copolymer, b Represents the weight percentage of the polymer block mainly composed of all conjugated diene compounds in the block copolymer, and N represents the number of polymer blocks mainly composed of the aromatic vinyl compound in the block copolymer. ]
These block copolymers that can be used in the present embodiment are those having different bonding types, different aromatic vinyl compound types, different conjugated diene compound types, unless contrary to the spirit of the present embodiment, Each of 1,2-bond vinyl content or 1,2-bond vinyl content and 3,4-bond vinyl content different, aromatic vinyl compound component content different, hydrogenation rate different, etc. You may mix and use 2 or more types about.

  In addition, these block copolymers used in the present embodiment may be block copolymers in which all or part of the block copolymers are modified.

  The modified block copolymer here means at least one carbon-carbon double bond or triple bond in the molecular structure, and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group or It refers to a block copolymer modified with at least one modifying compound having a glycidyl group.

  The modified block copolymer can be produced by (1) melt-kneading with the modified compound at a temperature in the range of the softening point temperature of the block copolymer to 250 ° C. in the presence or absence of a radical initiator. (2) a method of reacting the block copolymer and the modifying compound in a solution at a temperature below the softening point of the block copolymer, and (3) a temperature below the softening point of the block copolymer, Examples include a method of reacting the block copolymer and the modifying compound without melting them, and any of these methods may be used, but the method (1) is preferable, and among the methods (1), in the presence of a radical initiator. The method of performing is more preferable.

  At least one modified compound having at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group or glycidyl group in the molecular structure referred to herein. Can be the same as the modified compound described for the modified polyphenylene ether resin.

<Other ingredients>
In addition to the above components, the resin composition of the present embodiment may contain an inorganic filler as necessary within a range that does not impair the characteristics and effects of the resin composition of the present embodiment.

  Examples of inorganic fillers include glass fiber, potassium titanate fiber, gypsum fiber, brass fiber, stainless steel fiber, steel fiber, ceramic fiber, boron whisker fiber, mica, talc, graphite, silica, calcium carbonate, kaolin, calcined kaolin, and wollast. Fibrous, granular, plate-like, or needle-like inorganic reinforcing materials such as knight, zonotlite, apatite, glass beads, glass flakes, titanium oxide, and carbon black for coloring can be used. Two or more of these inorganic fillers may be used in combination. Among these, more preferable inorganic fillers include talc, wollastonite, and glass fiber. In addition, the inorganic filler may be a material that has been surface-treated by a known method using a surface treatment agent such as a silane coupling agent.

  The resin composition of the present embodiment includes other stabilizers such as heat stabilizers, antioxidants, ultraviolet absorbers, crystal nucleating agents, conductivity imparting agents, antistatic agents, flame retardants, pigments, dyes, and the like. Known mold release agents such as agents, polyethylene wax, polypropylene wax, montanate wax, stearate wax and the like can be added as appropriate.

<Morphology>
The resin composition of the present embodiment has a morphology in which (b) the polyphenylene ether resin exists as the following particles 1 and 2 and (b) the polyphenylene ether resin particles are dispersed in (a) the polyamide resin. Have
The ratio of the total cross-sectional area of the following particles 2 is 5 to 50% with respect to the total cross-sectional area of all (b) polyphenylene ether resin particles.
Particle 1: (b) Particle in which (d) elastomer is dispersed at a ratio of 80 to 100% in the cross-sectional area of one polyphenylene ether resin particle.
Particle 2: (b) Particle in which (d) elastomer is dispersed at a ratio of 0 to 20% in the cross-sectional area of one polyphenylene ether resin particle.

  The resin composition of the present embodiment can exhibit excellent molding fluidity and impact resistance without impairing heat resistance and rigidity by taking the above-described morphology (dispersed form).

  Furthermore, it is more preferable that the total cross-sectional area of the particles 2 is 5 to 30% with respect to the total cross-sectional area of all the (b) polyphenylene ether resin particles because the above-described effects are remarkably exhibited.

  The resin composition having the morphology (dispersed form) as described above can be obtained by, for example, a method for producing a resin composition described later.

  These morphologies (dispersed forms) can be easily confirmed by transmission electron micrographs. Specifically, it can be confirmed by the following method.

  First, from a molded piece obtained by molding the resin composition, a test piece for length 10 mm × width 5 mm × thickness 3 to 4 mm is cut out, and a plane for section cutting is formed on the end of the dye test piece with an ultramicrotome. create. Next, this test piece for dyeing is immersed in a 10% by mass phosphotungstic acid aqueous solution in a heat-resistant container, poured into a water bath at 80 ° C. for 4 hours, then pulled up, and cooled to room temperature. Thereafter, the test piece for dyeing is taken out from the heat-resistant container, washed with water and dried. By this dyeing operation, (a) the polyamide resin is dyed and observed as a black matrix phase when observed with a transmission electron microscope (TEM).

  Next, when the resin composition contains (d) an aromatic vinyl compound-conjugated diene compound copolymer as an elastomer, the test piece for dyeing is immersed in a 2% by mass osmium tetrachloride aqueous solution placed in a heat-resistant container, Water bath at 80 ° C. for 30 minutes in a water bath, then pull up and cool to room temperature. Thereafter, the test piece for dyeing is taken out from the heat-resistant container, washed with water and dried.

  By this dyeing operation, (d) an elastomeric aromatic vinyl compound-conjugated diene compound copolymer is dyed and observed as black dispersed particles in (b) polyphenylene ether resin particles when observed with a transmission electron microscope.

  Further, when the resin composition contains (d) a hydrogenated aromatic vinyl compound-conjugated diene compound copolymer as an elastomer, the above dyeing test is performed using an ultramicrotome equipped with a diamond knife containing water. A thin film having a thickness of 85 nm is cut out on water from a plane for cutting out a piece of slice, and the thin film is rinsed with a Cu mesh for TEM observation. The Cu mesh on which this thin film is placed is arranged on a stainless steel net. Separately, 0.1 g of ruthenium trichloride nhydrate and 1 ml of purified water are dissolved in a petri dish in a glass desiccator to obtain a solution. Thereafter, 5 ml of a sodium hypochlorite solution was added to the solution, and the stainless steel mesh on which the Cu mesh on which the thin film was placed was immediately placed. Then, the glass desiccator was covered and left for 4 minutes. Take out the mesh.

  By this dyeing operation, the hydrogenated product of the aromatic vinyl compound-conjugated diene compound copolymer is dyed and observed as black dispersed particles in the polyphenylene ether resin particles when observed with a transmission electron microscope.

  Among these dyeing operations, when the resin composition does not contain (d) an aromatic vinyl compound-conjugated diene compound copolymer as an elastomer, dyeing with osmium tetrachloride can be omitted, and the aromatic vinyl compound-conjugated diene compound copolymer can be omitted. When the polymer hydrogenated product is not included, the dyeing with ruthenium trichloride n-hydrate after the thin film slice preparation can be omitted.

  When the resin composition of this embodiment is confirmed using the above transmission electron microscope observation staining method, white to gray dispersed phase particles ((b) polyphenylene ether are contained in the black matrix phase ((a) polyamide resin). (Resin particles) are dispersed, and further, a black (b) elastomer (for example, an aromatic vinyl compound-conjugated diene compound copolymer and / or a hydrogenated product thereof) is dispersed in the dispersed phase particles. Can do.

  Further, using the transmission electron micrograph, the ratio of the dispersed area of (d) elastomer in one dispersed phase particle ((b) polyphenylene ether resin particle) and the total dispersed phase particle (total (b) polyphenylene ether) The ratio of the total cross-sectional area of the particles 2 to the total cross-sectional area of the resin particles) can be determined.

  Specifically, from the transmission electron micrograph, (b) the dispersed phase particle portion corresponding to the polyphenylene ether resin particles is cut out, and for each dispersed phase particle portion, (d) a portion where the elastomer is uniformly dispersed; (D) The ratio of the dispersed area of (d) elastomer in one dispersed phase particle ((b) polyphenylene ether resin particle) by the method of dividing into parts where no elastomer is present and measuring the weight of the part and converting it to area Can be requested. Furthermore, the total discontinuity of all dispersed phase particles (all (b) polyphenylene ether resin particles) is obtained by measuring the weight of the portion corresponding to the above-mentioned particle 2 in the total dispersed phase particle portion and the other particle portion and converting it into an area. The total area ratio of the particles 2 to the area can be obtained.

  Further, the above transmission electron micrograph is taken into a computer, and with photo retouching software, in each dispersed phase particle ((b) polyphenylene ether resin particle), (d) a portion in which the elastomer is uniformly dispersed; (d) Elastomer in one dispersed particle ((b) polyphenylene ether resin particle) by separately painting with a different color from the portion where the elastomer is not present, and obtaining the area of the separated color by the histogram calculation function Can be obtained. Further, the portion corresponding to the particle 2 in the total dispersed phase particle portion and the other particle portion are separately painted with different colors, and the area of the separated color is obtained by the histogram calculation function. The total area ratio of the particles 2 relative to the total cross-sectional area of (b) polyphenylene ether resin particles) can be determined.

<Content of each component>
In the resin composition of the present embodiment, (a) the content of the polyamide resin is 40 to 90 parts by mass, (b) the content of the polyphenylene ether resin is 5 to 50 parts by mass, and (d) the elastomer is contained. The amount is 5 to 20 parts by mass, and the content of the (c) compatibilizer is 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the total content of the components (a), (b) and (d). It is preferable that If the content of each component is within this range, a resin composition that is excellent in molding fluidity and further in balance between heat resistance, toughness (impact strength) and rigidity can be obtained.

  Specifically, when the total content of the components (a), (b) and (d) is 100 parts by mass, the content of the (a) polyamide resin is in the range of 40 parts by mass to 90 parts by mass. (B) If the content of the polyphenylene ether resin is in the range of 5 parts by mass or more and 50 parts by mass or less, a resin composition having more excellent molding fluidity, heat resistance and rigidity can be obtained. ) If the elastomer content is in the range of 5 parts by mass or more and 20 parts by mass or less, a resin composition having more excellent heat resistance and impact resistance can be obtained. Furthermore, the content of (c) the compatibilizer is within the range of 0.1 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the total content of components (a) to (b) and (d). Thus, a resin composition having excellent toughness (impact strength) can be obtained.

  In the resin composition of the present embodiment, more preferably, (a) the content of the polyamide resin is 40 to 90 parts by mass, (b) the content of the polyphenylene ether resin is 5 to 50 parts by mass, and (d) The content of the elastomer is 5 to 20 parts by mass, and the content of the compatibilizer (c) is 0.2 to 2 parts per 100 parts by mass of the total content of the components (a), (b), and (d). 5 parts by mass. Particularly preferably (a) the content of polyamide resin is 40 to 85 parts by mass, (b) the content of polyphenylene ether resin is 10 to 50 parts by mass, (d) the content of elastomer is 5 to 20 parts by mass, The content of the (c) compatibilizer is in the range of 0.2 to 2.0 parts by mass with respect to 100 parts by mass of the total content of the components (a), (b) and (d).

≪Method for producing resin composition≫
As a manufacturing method of the resin composition of this embodiment, the method of melt-kneading and manufacturing said each component using a various melt mixer can be mentioned, for example. Examples of the melt-kneader for performing these methods include a single-screw extruder, a multi-screw extruder including a twin-screw extruder, a heat-melt kneader using a roll, a kneader, a Brabender plastograph, a Banbury mixer, and the like. Of these, a twin screw extruder is particularly preferred. Specific examples include the ZSK series manufactured by WERNER & PFLIDEERER, the TEM series manufactured by Toshiba Machine Co., Ltd., and the TEX series manufactured by Nippon Steel Works.

  The preferable aspect of the manufacturing method of the resin composition of this embodiment using an extruder is described below. The L / D (barrel effective length / barrel inner diameter) of the extruder is preferably in the range of 20 to 60, more preferably in the range of 30 to 50. The extruder has a first raw material supply port on the upstream side with respect to the flow direction of the raw material, a first vacuum vent on the downstream side, a second raw material supply port on the downstream side, and a second vacuum vent on the downstream side. Is preferred. In particular, a kneading section is provided upstream of the first vacuum vent, a kneading section is provided between the first vacuum vent and the second raw material supply port, and a knee section is provided between the second raw material supply port and the second vacuum vent. It is more preferable to provide a sectioning section. Although the raw material supply method to a 2nd raw material supply port is not specifically limited, A forced side feeder is used from an extruder side open port rather than the mere addition supply method from an extruder 2nd raw material supply port open port. A stable and preferable method. And the upper open port of the extruder 2nd raw material supply port can also be made open in order to extract the air to carry. The melt-kneading temperature and screw rotation speed at this time are not particularly limited, but can normally be arbitrarily selected from a melt-kneading temperature of 280 to 350 ° C. and a screw rotation speed of 100 to 1200 rpm.

  The method for producing the resin composition of the present embodiment includes (a) a polyamide resin, (b) a polyphenylene ether resin, and (c) a step of melt-kneading the total amount of the compatibilizer at or above the melting point of (a) the polyamide resin; After this step, it is preferable to further include (d) supplying an elastomer and (a) performing melt kneading at or above the melting point of the polyamide resin.

  In addition, the method for producing the resin composition of the present embodiment comprises the steps of: (a) polyamide resin, (b) polyphenylene ether resin, and (c) the compatibilizer are all melt-kneaded at a temperature equal to or higher than the melting point of (a) polyamide resin. And after the step, the obtained pellet and (d) the elastomer are mixed, and (a) a step of melt kneading at a melting point or higher of the polyamide resin is preferably included.

Specific examples of the method for producing the resin composition of the present embodiment include the following methods 1 to 3.
1. (A) polyamide melt, (b) polyphenylene ether resin, and (c) compatibilizer are heated and melt kneaded in a hot melt kneader set at a temperature of 280 to 350 ° C. to obtain melt kneaded pellets. Next, in the presence of the melt-kneaded product pellets obtained in the previous step, (d) a production method including a step of adding an elastomer and heating and kneading with a heating and melting kneader set at a temperature of 280 to 300 ° C.
2. The step of supplying the component (b) and the component (c) from the first raw material supply port, and then supplying the component (a) from the second raw material supply port in a melt-kneaded state to obtain a pellet by melt-kneading. Next, the manufacturing method including the process of adding the elastomer of (d) component in presence of the pellet obtained at the previous process, and heat-melt-kneading with the heat-melt kneader set to 280-300 degreeC.
3. The component (a), the component (b) and the component (c) described above are supplied from the first supply port, and then the component (d) is supplied from the second supply port in the melt-kneaded state, and the melt-kneading is continued. The manufacturing method including the process to perform.

  In particular, the resin composition obtained by the production method 1 is more special than the resin composition obtained by the production methods 2 and 3 above, in which the resin composition of the present embodiment has components (a) to (d). It is more preferable because it is easy to take a good morphology (dispersed form) and the compounding effect of these components is remarkably exhibited.

  Furthermore, in the method for producing a resin composition of the present embodiment, it is preferable to perform melt kneading at an actually measured resin temperature of 350 ° C. or less in order to obtain a resin composition having the above-described special morphology (dispersed form). By setting the measured resin temperature to 350 ° C. or lower, the morphology (dispersed form) can be optimized. Further, from the viewpoint of physical property deterioration due to thermal deterioration of the resin, the actually measured resin temperature is preferably 350 ° C. or lower, more preferably 340 ° C. or lower, and further preferably 335 ° C. or lower.

≪Usage≫
The resin composition obtained as described above can be suitably used as a resin molding material in each industrial field.

  The resin structural component of the present embodiment is obtained by molding the above-described resin composition. As the molding method, for example, a molding method such as injection molding, metal in-mold molding, outsert molding, hollow molding, extrusion molding, sheet molding, film molding, hot press molding, rotational molding, or lamination molding can be applied.

  And as resin-made structural parts obtained by these molding methods, home appliances / OA equipment internal parts, optical equipment mechanism parts, light source lamp surrounding parts, optical fiber connector ferrules, printer parts, copier parts, automobile radiator tank parts, etc. One or more types selected from the group consisting of automotive engine compartment components, bumper and automotive lamp components, and automotive interior components.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to this Example.

  In addition, the raw material and the measuring method which were used for the Example and the comparative example are as follows.

(A) Polyamide resin (a-1): Polyamide 6,6 [trade name: Leona 1300 manufactured by Asahi Kasei Chemicals Corporation]. The melting point of the polyamide 6,6 was 265 ° C.
(A-2): Polyamide 6 [Brand name: Ube Nylon 1013B, Ube Industries, Ltd.] The melting point of the polyamide 6 was 220 ° C.

  The melting point of (a) polyamide resin was measured by the DSC method described in JIS K7121.

(B) Polyphenylene ether resin (b-1): Polyphenylene ether resin obtained by oxidative polymerization of 2,6-xylenol. The reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) of the polyphenylene ether resin was 0.52 dl / g.

(C) Compatibilizing agent (c-1): maleic anhydride [trade name: Crystal MAN manufactured by NOF Corporation].

(D) Elastomer (d-1): Polystyrene block-hydrogenated polybutadiene-polystyrene block structure, the amount of bonded styrene is 35%, the number average molecular weight is 140,000, and the hydrogenation rate of the polybutadiene part is 99.99. 8% hydrogenated block copolymer.
(D-2): A block copolymer having a structure of polystyrene block-polybutadiene-polystyrene block, having a bound styrene content of 41% and a number average molecular weight of 80,000.
(D-3): A hydrogenated block copolymer obtained by hydrogenating the block copolymer of (d-2) and having a hydrogenation rate of 99.6% in the polybutadiene portion.

  In this example, the amount of bound styrene was measured with an infrared spectrophotometer, the number average molecular weight was measured with a gel permeation chromatography measuring device, and the hydrogenation rate of the polybutadiene portion was measured with an infrared spectrophotometer. .

[Examples 1-15, Comparative Examples 1-8]
[Production of resin composition]
Using a twin screw extruder (ZSK-40; manufactured by COPERION WERNER & PFLIDELER, Germany) set at a temperature of 280 to 330 ° C. and a screw rotation speed of 300 rpm, Tables 1 to 3 are provided from the first and second raw material supply ports of the extruder. The components (a) to (d) were supplied at the composition ratio described in (1) above, and the mixture was heated and melt-kneaded to produce a resin composition, which was obtained as pellets.

[Characteristics of resin composition]
The characteristics of the resin composition obtained above were evaluated as follows. The results are shown in Tables 1-3.

<Create test piece>
Using the pellets of the resin composition obtained above, the pellets were supplied to a screw in-line injection molding machine set at 270 to 320 ° C., and a test piece for measuring tensile strength was produced under the condition of a mold temperature of 90 ° C. Further, the test piece was cut to prepare a load deflection temperature (DTUL) measurement test piece and a Charpy impact measurement test piece.

  Furthermore, a flat plate of 75 mm × 75 mm square−thickness 2.5 mm was prepared under the same conditions.

<Measurement of short shot pressure>
After molding the test piece for measuring the tensile strength, the injection pressure was lowered and the short shot pressure (gauge pressure) was measured. It was judged that the lower the short shot pressure, the better the molding fluidity of the resin composition.

<Measurement of load deflection temperature>
The load deflection temperature: DTUL (ISO 75: 0.45 MPa load) was measured using the load deflection temperature measurement test piece.

<Measurement of Charpy impact strength>
Using the Charpy impact measurement test piece, Charpy impact strength (ISO 179: measurement temperature 23 ° C.) was measured.

<Measurement of tensile strength and tensile elongation at break>
Tensile strength and tensile elongation at break (ISO 527: measurement temperature 23 ° C.) were measured using the test pieces for tensile strength measurement.

<Falling weight impact test>
A falling weight impact test was performed using a graphic impact tester manufactured by Toyo Seiki Seisakusho Co., Ltd. on a flat plate of 75 mm × 75 mm square−thickness 2.5 mm.

<Morphological analysis>
In order to see the resin flow direction at the center of the three test pieces for measuring tensile strength, a test piece for dyeing having a length of 5 mm, a width of 5 mm, and a thickness of 4 mm was cut out. For the lack of length, a high impact polystyrene test piece was bonded with an instantaneous adhesive to prepare a test piece for dyeing of 10 mm length × 5 mm width × 4 mm thickness. A 1 mm square plane for section cutting was prepared at the end of the test piece for staining with an ultramicrotome (ULTRACUT-N manufactured by Reichert-Nissei). This test piece for dyeing was immersed in a 10% by mass phosphotungstic acid aqueous solution in a heat-resistant container, poured into a water bath at 80 ° C. for 4 hours, pulled up, and cooled to room temperature. Thereafter, the test piece for dyeing was taken out of the heat-resistant container, washed with water and dried. Further, the above-mentioned dyeing test piece was dipped in a 2% by mass osmium tetrachloride aqueous solution in a heat-resistant container, poured into a water bath at 80 ° C. for 30 minutes in a water bath, pulled up, and cooled to room temperature. Thereafter, the test piece for dyeing was taken out of the heat-resistant container, washed with water and dried.

  Next, using the ultramicrotome equipped with a diamond knife containing water, a thin film having a thickness of 85 nm is cut out from the plane for cutting out the slice of the above-mentioned staining test piece, and the thin film is cut into Cu for TEM observation. I scooped it up with a mesh. The Cu mesh on which this thin film was placed was placed on a stainless steel mesh, and 0.1 g of ruthenium trichloride nhydrate and 1 ml of purified water were dissolved in a petri dish in a glass desiccator to obtain a solution. Thereafter, 5 ml of a sodium hypochlorite solution was added to the solution, and the stainless steel mesh was immediately placed thereon. The glass desiccator was covered and allowed to stand for 4 minutes, and then the Cu mesh was taken out.

  Furthermore, the morphology of the thin film section was observed with a transmission electron microscope (H-600A, manufactured by Hitachi, Ltd.) at an acceleration voltage of 100 kV and 10,000 times, and a photograph was taken. Next, the obtained transmission electron micrograph is taken into a computer, and (d) in one (b) polyphenylene ether resin particle using photo retouching software (manufactured by Photoshop (registered trademark) Adobe). The total area ratio of the particles 2 was determined with respect to the dispersed area ratio of the elastomer and the total cross-sectional area of all (b) polyphenylene ether resin particles. Specifically, in each (b) polyphenylene ether resin particle), (d) a portion where the elastomer is uniformly dispersed and (d) a portion where the elastomer is not present are separately colored with different colors, and histogram calculation is performed. By determining the area of the color separately applied using the function, the ratio of the dispersed area of (d) elastomer in one (b) polyphenylene ether resin particle was determined. Further, the portion corresponding to the particle 2 in the total dispersed phase particle portion and the other particle portion are separately painted with different colors, and the area of the separated color is obtained by the histogram calculation function, whereby the total (b) polyphenylene ether is obtained. The total area ratio of the particles 2 relative to the total cross-sectional area of the resin particles was determined.

  This operation was performed for 3 points per sample, and the average value was calculated.

From these results, in the resin composition containing the polyamide resin, the polyphenylene ether resin, the compatibilizing agent and the elastomer, the resin composition in which the morphology is controlled within the range of the present embodiment has the same blending ratio and the morphology is the present embodiment. It was clarified that the resin composition is more excellent in the balance between molding fluidity, toughness (impact strength) and rigidity as compared with the resin composition outside the above range.

  The resin composition of the present invention is an excellent resin composition with excellent heat resistance and a balance between toughness (impact strength) and rigidity, so that it is a home appliance / OA device internal component, an optical device mechanism component, a light source lamp peripheral component, Optical fiber connector ferrules, laser beam printer internal parts, printer parts such as ink jet printer internal parts, copier parts such as copier internal parts, automobile engine compartment parts such as automobile radiator tank parts, automobile lamp parts, automobile internal parts It can be used as at least one part of a molded product such as

Claims (11)

(A) a polyamide resin, (b) a polyphenylene ether resin, (c) a compatibilizing agent and (d) an elastomer,
(B) the polyphenylene ether resin is present as the following particles 1 and the following particles 2, and (b) the polyphenylene ether resin particles have a morphology dispersed in the (a) polyamide resin,
The resin composition in which the ratio of the total cross-sectional area of the following particles 2 is 5 to 50% with respect to the total cross-sectional area of all (b) polyphenylene ether resin particles;
Particle 1: (b) In a cross-sectional area of one polyphenylene ether resin particle, (d) a particle in which the elastomer is dispersed at a ratio of 80 to 100%,
Particle 2: (b) Particle in which (d) elastomer is dispersed at a ratio of 0 to 20% in the cross-sectional area of one polyphenylene ether resin particle.   The resin composition according to claim 1, wherein the total cross-sectional area of the particles 2 is 5 to 30% with respect to the total cross-sectional area of all (b) polyphenylene ether particles.   (A) The polyamide resin is at least one selected from the group consisting of polyamide 6, polyamide 6,6, polyamide 6 / 6,6, polyamide 6,12 and polyamide 6,6 / 6, I. 2. The resin composition according to 2.   The resin composition according to any one of claims 1 to 3, wherein the (b) polyphenylene ether resin is 100% by mass of polyphenylene ether or polyphenylene ether / styrene resin = 30 to 99% by mass / 70 to 1% by mass. object.   The resin composition according to any one of claims 1 to 4, wherein (c) the compatibilizing agent is at least one selected from the group consisting of citric acid, maleic acid, itaconic acid, and anhydrides thereof.   (D) a block copolymer in which the elastomer contains at least one block mainly composed of an aromatic vinyl compound and at least one block mainly composed of a conjugated diene compound, and / or the block copolymer The resin composition according to claim 1, which is a hydrogenated product.   (A) Polyamide resin content is 40 to 90 parts by mass, (b) Polyphenylene ether resin content is 5 to 50 parts by mass, and (d) Elastomer content is 5 to 20 parts by mass. The content of the (c) compatibilizer is 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the total content of the components (a), (b) and (d). 2. The resin composition according to item 1. (A) polyamide resin, (b) polyphenylene ether resin, and (c) a step of melt-kneading the total amount of the compatibilizer above (a) the melting point of the polyamide resin;
The method for producing a resin composition according to any one of claims 1 to 7, further comprising (d) supplying an elastomer and (a) performing melt kneading at a melting point or higher of the polyamide resin after the step. (A) polyamide resin, (b) polyphenylene ether resin and (c) a step of obtaining pellets by melting and kneading the total amount of the compatibilizer at or above the melting point of the polyamide resin;
The resin composition according to any one of claims 1 to 7, further comprising: after the step, mixing the obtained pellet and (d) the elastomer, and (a) performing melt kneading at a melting point or higher of the polyamide resin. Manufacturing method.   A resin structural part obtained by molding the resin composition according to claim 1.   1 selected from the group consisting of home appliance / OA equipment internal parts, optical equipment mechanism parts, light source lamp surrounding parts, optical fiber connector ferrule, printer parts, copier parts, automobile lamp parts, automobile engine compartment parts, and automobile interior parts The resin structural component according to claim 10, wherein the resin structural component is a seed or more.