JP2012067150A - Reinforced polyamide resin composition for hollow molded article and hollow molded article using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition improving retention stability in extrusion- or blow-molding and capable of suppressing fuzz of reinforcing fiber, on the inside surface of the extrusion- or blow-molded articles even when the compounding amount of glass fiber is made to be more than 30 mass%.SOLUTION: There is provided a reinforced polyamide resin composition for hollow molded articles, which comprises a copolyamide resin (A) comprising (a) decane terephthalamide unit and (b) undecane amide unit or/and dodecane amide unit, a glycidyl group-containing styrene-based copolymer (B), an olefinic polymer (C) having a carboxylic acid group or/and a carboxylic acid anhydride group, and a fibrous reinforcing material (D), wherein, as properties, (α) the melt viscosity at 0.5 mm/min shear rate is 4,000-20,000 Pa s and (β) the difference of the melt mass flow rate (10 kg load, conforming to JIS K 7210), between the previously arranged melt mass flow rate (MFR) and the melt mass flow rate after 20 min retention (MFR), is within a range from -1.0 to 1.0.

Description

  The present invention relates to a reinforced polyamide resin composition capable of providing a hollow molded article having low water absorption, suitable for extrusion and blow molding, and excellent in dimensional stability without impairing the excellent physical properties and characteristics of the polyamide resin.

Polyamide resins generally have low melt viscosity, and it is difficult to hold a parison shape during extrusion or blow molding, and drawdown is likely to occur. Therefore, polyamide resins alone are not used for extrusion or blow molding. For example, polyphenylene ether resins A large amount of resins other than polyamide resins such as polyolefin resins and modified polyolefin resins are blended to improve blow moldability (for example, Patent Documents 1 and 2). For this reason, there existed a problem that characteristics, such as mechanical strength of a polyamide resin, heat resistance, and chemical resistance, would be impaired by the influence of resin other than polyamide mix | blended in large quantities.
Therefore, the present inventors previously proposed a polyamide composition in which an amorphous polyamide resin was blended to increase the content of the polyamide resin and a small amount of glycidyl group-containing acrylic copolymer was reacted (Patent Document 3). ).

  In this method, the melt viscosity and solidification rate of the reinforced polyamide resin composition can be controlled while maintaining the original strength, rigidity, chemical resistance and heat resistance of the polyamide resin, and the blow moldability is also good. However, there is room for improvement in the relatively high hygroscopicity, which is a drawback of polyamide, the dimensional change based on it, and the retention stability during molding, and the amount of glass fiber added to the reinforcing material exceeds 30% by mass. Then, there was a problem that the inner surface of the extruded or blow-molded product that did not contact the blow-molding mold was in a state in which the glass fiber was fuzzy and the unevenness was extremely rough.

JP-A-5-339495 Japanese Patent Publication No. 60-170664 JP 2009-132908 A

  Therefore, the present invention not only provides a polyamide resin composition with lower water absorption and excellent dimensional stability, chemical resistance, extrusion and blow molding properties, but also improves the retention stability during extrusion and blow molding, A reinforced polyamide resin composition capable of suppressing formation of irregularities due to fluffing of reinforcing fibers on the inner surface of an extruded or blow molded product and forming a smooth inner surface even when the blending amount of glass fiber exceeds 30% by mass It is something to be offered.

  In order to achieve the above object, the present inventor has obtained a polyamide obtained by copolymerizing 11 nylon and / or 12 nylon at a specific ratio as a copolymerization component of 10T nylon (hereinafter simply abbreviated as 10T11 copolymerized polyamide for the sake of brevity). When a specific vinyl copolymer containing a glycidyl group and a polyolefin copolymer having a specific reactive functional group are used in combination, the thickening effect is remarkably improved. It has been found that it is possible to provide a reinforced polyamide resin composition and a molded body thereof that have not only excellent blow moldability but also excellent retention stability during extrusion and blow molding, low water absorption, excellent dimensional stability, and chemical resistance. The present invention has been completed.

That is, according to the present invention,
(1). Glycidyl group-containing styrene with respect to 100 parts by mass of copolymer polyamide resin (A) comprising (a) decanterephthalamide unit 50 to 98 mol% and (b) undecanamide unit or / and dodecanamide unit 50 to 2 mol% 0.3 to 10 parts by mass of a copolymer (B), 0.1 to 10 parts by mass of an olefin polymer (C) having a carboxylic acid group or / and a carboxylic anhydride group, a fibrous reinforcing material ( A reinforced polyamide resin composition for hollow molded articles, comprising 20 to 150 parts by mass of D) and further satisfying the following characteristics (a) and (b):
(A) The melt viscosity at a shear rate of 0.5 mm / min is 4000 to 20000 Pa · s at a temperature of the melting point of the copolymerized polyamide resin + 25 ° C.
(B) The melt mass flow rate (conforming to JIS K 7210) at a load of 10 kg at a temperature of the melting point of the copolymerized polyamide resin + 25 ° C. (according to JIS K 7210) was retained for 20 minutes at the time of measuring the melt mass flow rate (MFR ₀ ). The difference from the later melt mass flow rate (MFR ₂₀ ) is in the range of −1.0 to 1.0.
(2). The hollow molding according to (1), wherein the copolymerized polyamide resin (A) comprises (a) 75 to 98 mol% of decanterephthalamide units and (b) undecanamide units or / and 25 to 2 mol% of dodecanamide units. Reinforced polyamide resin composition for body.
(3). The copolymer polyamide resin (A) is obtained from (c) a structural unit obtained from a diamine other than the structural unit (a) and a dicarboxylic acid, or an aminocarboxylic acid or lactam other than the structural unit (b). The reinforced polyamide resin composition for hollow molded bodies according to the above (1), containing a unit of up to 30 mol%.
(4). The reinforced polyamide resin composition for hollow molded bodies according to (1), wherein the glycidyl group-containing styrene copolymer (B) has an average number of glycidyl groups per molecular chain of 2 to 4.
(5). The glycidyl group-containing styrene copolymer (B) is 99 to 50 mass% of styrene polymer units, 1 to 30 mass% of glycidyl group-containing acrylic polymer units, and 0 to 40 mass% of other vinyl polymer units. The reinforced polyamide resin composition for hollow molded bodies according to the above (1), which is a copolymer comprising%.
(6). A hollow molded article obtained by using the reinforced polyamide resin composition according to any one of (1) to (5).
(7). The hollow molded body according to (6), wherein the hollow molded body is an automobile-related part.
(8). The hollow molded body according to (7), wherein the automobile-related part is an intake / exhaust system part.
(9). The hollow molded body according to (8), wherein the intake / exhaust system component is an air hose, an air duct, a turbo duct, a turbo hose, an intake manifold, or an exhaust manifold.
(10). (9) obtained by using any one hollow molding method of direct blow, 3D single blow, 3D exchange blow, suction blow, 3D suction blow, 3D exchange suction blow, injection stretch blow The hollow molded body described.

The reinforced polyamide resin composition for hollow molded bodies of the present invention not only has excellent extrudability and blow moldability, but also improves the retention stability during extrusion and blow molding, and has a glass fiber content of 30. Provided is a polyamide resin composition capable of providing a molded article having low water absorption, excellent dimensional stability and chemical resistance, without causing glass fiber fluff on the inner surface of the hollow molded article even when the amount exceeds mass%. can do.
In addition, the resulting hollow molded body can suppress the fluffing of the glass fiber on the inner surface, thereby preventing the occurrence of problems such as fouling obstructing the flow of fluid flowing through the hollow part or dropping into the fluid. Is possible.

It is explanatory drawing (photograph) which showed the measurement location of the shape seen from the upper surface, the outline of a dimension, and pipe thickness about the pipe shape | molded for moldability evaluation. It is a figure (photograph) which shows the inner surface of the cut pipe, and shows the observation location of fluff. It is a figure (photograph) which shows the state without the fluff of glass fiber on the inner surface of the cut pipe. It is a figure (photograph) which shows the state with the fluff of glass fiber on the inner surface of the cut pipe.

Hereinafter, the reinforced polyamide resin composition for hollow molded bodies of the present invention will be described in detail.
The copolymerized polyamide resin (A) used in the present invention contains the component (a) corresponding to 10T nylon and the component (b) corresponding to 11 nylon and / or 12 nylon in a specific ratio. Not only is the moldability and impact resistance, which are the disadvantages of nylon, improved, but it also has a feature that low water absorption is highly satisfactory.

  The component (a) corresponds to 10T nylon obtained by polycondensing 1,10-decanediamine (10) and terephthalic acid (T) in an equimolar amount, and specifically, the following formula ( I).

  The component (a) is a main component of the copolymerized polyamide resin (A) used in the present invention, and imparts excellent heat resistance, low water absorption, chemical resistance, slidability, etc. to the copolymerized polyamide. Have The blending ratio of the component (a) in the copolymerized polyamide is 50 to 98 mol%, preferably 50 to 90 mol%, more preferably 55 to 85 mol%. When the blending ratio of the component (a) is less than the above lower limit, 10T nylon, which is a crystalline component, is subject to crystal inhibition by the copolymer component, and may cause deterioration of moldability and high temperature characteristics, while when exceeding the above upper limit, This is not preferable because workability and impact resistance are significantly reduced.

  The component (b) corresponds to 11 nylon or 12 nylon obtained by polycondensation of 11-aminoundecanoic acid, 12-aminododecanoic acid, undecane lactam, or lauryl lactam. Those represented by formulas (II) and (III). These may be used alone or in a mixture.

  The component (b) is for improving the drawbacks of the component (a) and has a role of improving all of the impact resistance, workability and low water absorption of the copolymerized polyamide. The blending ratio of the component (b) in the copolymerized polyamide is 50 to 2 mol%, preferably 50 to 10 mol%, more preferably 45 to 15 mol%. When the blending ratio of the component (b) is less than the above lower limit, the impact resistance of the copolymer polyamide is not improved, and the effect of reducing water absorption is insufficient. When the above upper limit is exceeded, the crystallinity of the copolyamide is greatly reduced, the crystallization rate is slowed, the moldability is deteriorated and the impact resistance may be deteriorated, and the component (a) corresponding to 10T nylon This is not preferable because the amount of the resin is reduced, and heat resistance and slidability may be insufficient.

  In particular, when heat resistance is required, the copolymerized polyamide resin (A) contains (a) 75 to 98 mol% of decanterephthalamide units, and (b) undecanamide units or / and dodecanamide units 25 to 25%. A polyamide resin composed of 2 mol% is preferred.

  In addition to the components (a) and (b), the copolymerized polyamide resin (A) used in the present invention is obtained from an equivalent molar salt of (c) a diamine other than the structural unit of (a) and a dicarboxylic acid. Or a structural unit obtained from an aminocarboxylic acid or lactam other than the structural unit (b) may be copolymerized at a maximum of 30 mol%. As component (c), other properties not obtainable with 10T nylon, 11 nylon, and 12 nylon are added to copolymer polyamide (A), and properties obtained with 10T nylon, 11 nylon, and 12 nylon are further improved. Have a role to play.

  Specific examples of the copolymer component used in (c) include the following copolymer components. As the amine component, 1,2-ethylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 2-methyl-1,5-pentamethylenediamine, 1,6 -Hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 2-methyl-1,8-octamethylenediamine, 1,10-decamethylenediamine, 1 , 11-Undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-tridecamethylenediamine, 1,16-hexadecamethylenediamine, 1,18-octadecamethylenediamine, 2,2,4 (or 2,4,4) -aliphatic diamines such as trimethylhexamethylenediamine, piperazine Cyclohexanediamine, bis (3-methyl-4-aminohexyl) methane, bis- (4,4′-aminocyclohexyl) methane, cycloaliphatic diamine such as isophoronediamine, metaxylylenediamine, paraxylylenediamine, para Examples thereof include aromatic diamines such as phenylenediamine and metaphenylenediamine, and hydrogenated products thereof. As the acid component of the polyamide, the following polyvalent carboxylic acids or acid anhydrides can be used. Examples of the polyvalent carboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, and 2,2′-diphenyl. Aromatic dicarboxylic acids such as dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 5-sulfonic acid sodium isophthalic acid, 5-hydroxyisophthalic acid, fumaric acid, maleic acid, succinic acid, itaconic acid, adipic acid, azelaic acid, Sebacic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1,18-octadecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid 1,2-cyclohexanedicarboxylic acid, 4-methyl-1,2-cyclohex Njikarubon acid, and an aliphatic or alicyclic dicarboxylic acids such as dimer acid. Further, lactams such as ε-caprolactam and aminocarboxylic acids having a structure in which they are ring-opened can be mentioned.

Specific examples of the component (c) include polycaproamide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyundecamethylene adipamide (nylon 116). ), Polymetaxylylene adipamide (nylon MXD6), polyparaxylylene adipamide (nylon PXD6), polytetramethylene sebacamide (nylon 410), polyhexamethylene sebacamide (nylon 610), polydecamethylene Adipamide (nylon 106), polydecamethylene sebamide (nylon 1010), polyhexamethylene dodecamide (nylon 612), polydecamethylene dodecamide (nylon 1012), polyhexamethylene isophthalamide (nylon 6I), poly Tetramethylene terephthalate Amide (nylon 4T), polypentamethylene terephthalamide (nylon 5T), poly-2-methylpentamethylene terephthalamide (nylon M-5T), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene hexahydroterephthalamide ( Nylon 6T (H)) Polynonamethylene terephthalamide (nylon 9T), Polyundecamethylene terephthalamide (nylon 11T), Polydodecamethylene terephthalamide (nylon 12T), Polybis (3-methyl-4-aminohexyl) methane terephthalate Amide (nylon PACMT), polybis (3-methyl-4-aminohexyl) methane isophthalamide (nylon PACMI), polybis (3-methyl-4-aminohexyl) methandecamide (Nai Down PACM12), and the like polybis (3-methyl-4-amino-hexyl) methane tetra deca (nylon PACM14).
Among the structural units, examples of a preferable component (c) include polydodecamethylene terephthalamide (nylon 12T) and polydecamethylene sebacamide (nylon 1010) for improving processability, low water absorption, and impact resistance. And polydecamethylene dodecamide (nylon 1012). The blending ratio of the component (c) in the copolymerized polyamide is preferably up to 30 mol%, more preferably 5 to 20 mol%. When the proportion of the component (c) exceeds the above upper limit, the amount of the essential component (a) or component (b) decreases, and the originally intended effect of the copolymerized polyamide (A) used in the present invention is reduced. May not be sufficiently exhibited, which is not preferable.
The copolymerized polyamide resin (A) used in the present invention is not greatly different in properties, but it is preferable to use a plant-derived raw material in order to achieve a low carbon society and environmental harmony. Specifically, it is preferable to use a castor oil-derived raw material that does not compete with food, decanediamine in component (a) in the present invention, aminoundecanoic acid in component (b), and sebacic acid in component (c) It is preferable to use plant-derived materials. Preferable resin compositions of the present invention include nylon 10T / 11 and nylon PA10T / 1010/11, which use these plant materials and exhibit a very high plant-derived material ratio.

  The melting point (Tm) of the copolymerized polyamide resin (A) used in the present invention is preferably 220 to 315 ° C, more preferably 240 to 300 ° C. When Tm exceeds the above upper limit, the processing temperature required for molding the copolymerized polyamide by blow molding or the like becomes extremely high, so that it decomposes during processing, resulting in a decrease in molecular weight due to target physical properties and deterioration. Formability may not be obtained. On the other hand, when Tm is less than the above lower limit, the crystallization speed becomes slow, and molding becomes difficult in all cases. Moreover, 50-120 degreeC is preferable and, as for glass transition temperature (Tg), More preferably, it is 60-100 degreeC. When Tg exceeds the above upper limit, when the copolymer polyamide is molded by a blow molding method or the like, not only the required mold temperature becomes high and molding becomes difficult, but also in the cycle of blow molding, it is sufficient. In some cases, crystallization does not proceed, and the thermal deformation temperature is lowered. In later use, crystallization proceeds at a high temperature and deformation due to secondary shrinkage becomes a problem. On the other hand, when Tg is less than the above lower limit, problems such as a large decrease in physical properties and inability to maintain physical properties after water absorption occur.

  Examples of the catalyst used for producing the copolymerized polyamide resin (A) used in the present invention include phosphoric acid, phosphorous acid, hypophosphorous acid or a metal salt, ammonium salt and ester thereof. Specific examples of the metal species of the metal salt include potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony. As the ester, ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester, stearyl ester, phenyl ester and the like can be added. Moreover, it is preferable to add sodium hydroxide from the viewpoint of improving the melt residence stability.

  The relative viscosity (RV) measured at 20 ° C. in 96% concentrated sulfuric acid of the copolymerized polyamide resin (A) used in the present invention is preferably 0.4 to 4.0, more preferably 1.0 to 3.5, More preferably, it is 1.5-3.0. Examples of a method for setting the relative viscosity of the polyamide within a certain range include a means for adjusting the molecular weight.

  The copolymerized polyamide resin (A) used in the present invention is prepared by adjusting the molar ratio between the amino group and the carboxyl group to perform polycondensation or adding a terminal blocking agent. Can be adjusted. When polycondensation is performed at a constant ratio of the molar ratio of the amino group and the carboxyl group, the molar ratio of all diamines to all dicarboxylic acids used is diamine / dicarboxylic acid = 1.00 / 1.05 to 1.10 / It is preferable to adjust to the range of 1.00.

  Examples of the timing for adding the end-capping agent include raw material charging, polymerization initiation, polymerization late, or polymerization termination. The end capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the end of the polyamide, but acid anhydrides such as monocarboxylic acid or monoamine, phthalic anhydride, Monoisocyanates, monoacid halides, monoesters, monoalcohols and the like can be used. Examples of the end capping agent include aliphatic monoacids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid. Alicyclic monocarboxylic acids such as carboxylic acid and cyclohexanecarboxylic acid, benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid and other aromatic monocarboxylic acids, maleic anhydride Acid, phthalic anhydride, acid anhydrides such as hexahydrophthalic anhydride, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, etc. Aliphatic monoamines, Examples thereof include alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine.

The acid value and amine value of the copolymerized polyamide resin (A) used in the present invention are preferably 0 to 200 equivalents / 10 ⁶ g and 0 to 200 equivalents / 10 ⁶ g, respectively. When the terminal functional group is 200 equivalents / 10 ⁶ g or more, not only gelation and deterioration are promoted during melt residence, but also problems such as coloring and hydrolysis occur in the use environment. On the other hand, when a reactive compound such as glass fiber or maleic acid-modified polyolefin is compounded, the acid value and / or amine value is preferably 5 to 100 equivalent / 10 ⁶ g in accordance with the reactivity and the reactive group.

  The copolymerized polyamide resin (A) used in the present invention can be produced by a conventionally known method. For example, decanediamine, terephthalic acid, which is a raw material monomer of component (a), and component (b) are used. Raw material monomers selected from the group consisting of 11-aminoundecanoic acid, 12-aminododecanoic acid, undecane lactam, lauryl lactam, and mixtures thereof, and (c) diamines other than the structural unit of (a) and dicarboxylic acid as necessary. It can be easily synthesized by a co-condensation reaction with an equimolar salt or a raw material monomer obtained from an aminocarboxylic acid or lactam other than the structural unit of (b). The order of the copolycondensation reaction is not particularly limited, and all the raw material monomers may be reacted at once, or a part of the raw material monomers may be reacted first, followed by the remaining raw material monomers. Although the polymerization method is not particularly limited, the process from raw material preparation to polymer production may proceed in a continuous process. After the oligomer is produced once, the polymerization is advanced by an extruder or the like in another process, or the oligomer is solidified. A method of increasing the molecular weight by phase polymerization may be used. By adjusting the charging ratio of the raw material monomer, the proportion of each structural unit in the copolymerized polyamide to be synthesized can be controlled.

  The glycidyl group-containing styrene copolymer (B) used in the present invention is obtained by polymerizing a monomer mixture containing a glycidyl group-containing acrylic monomer and a styrene monomer, or glycidyl. It is obtained by polymerizing a monomer mixture containing a group-containing acrylic monomer, a styrene monomer and other vinyl monomers. Examples of the glycidyl group-containing acrylic monomer include (meth) acrylic acid glycidyl, (meth) acrylic acid ester having a cyclohexene oxide structure, and (meth) acrylic glycidyl ether. A preferred glycidyl group-containing acrylic monomer is highly reactive glycidyl (meth) acrylate. As the styrene monomer, styrene, α-methylstyrene, or the like is used.

  Other vinyl monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( (Meth) acrylic acid having an alkyl group having 1 to 22 carbon atoms such as cyclohexyl (meth) acrylate, stearyl (meth) acrylate, methoxyethyl (meth) acrylate, etc. (the alkyl group may be linear or branched) Alkyl ester, (meth) acrylic acid polyalkylene glycol ester, (meth) acrylic acid alkoxyalkyl ester, (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid dialkylaminoalkyl ester, (meth) acrylic acid benzyl ester, ( Meth) acrylic acid phenoxyalkyl ester , (Meth) acrylic acid isobornyl ester, and (meth) acrylic acid alkoxysilyl alkyl ester. (Meth) acrylamide, (meth) acrylic dialkylamide, vinyl esters such as vinyl acetate, vinyl ethers, aromatic vinyl monomers such as (meth) allyl ethers, and α-olefin monomers such as ethylene and propylene It can be used. These can be used by appropriately selecting one kind or two or more kinds.

In the glycidyl group-containing styrene copolymer (B) in the present invention, the styrene polymer unit, the glycidyl group-containing acrylic polymer unit and the other vinyl polymer units are 99 to 50% by mass and 1 to 30% by mass, respectively. % And 0 to 40% by mass are preferable, 95 to 50% by mass, 5 to 20% by mass, and 0 to 40% by mass are more preferable, and 93 to 60% by mass, 7 to 15% by mass, and 0 to 30% by mass are further included. preferable.
If the content of the styrenic polymer unit is less than 50% by mass, the miscibility with the copolymerized polyamide (A) tends to be poor and the gel tends to be gelled, which may reduce the rigidity of the composition. Moreover, when content of a glycidyl group containing acrylic polymer unit exceeds 30 mass%, it will become easy to gelatinize.
Specific examples include styrene / glycidyl (meth) acrylate, styrene / glycidyl (meth) acrylate / methyl (meth) acrylate, styrene / glycidyl (meth) acrylate / butyl (meth) acrylate, and the like. However, it is not limited to these.

The glycidyl group-containing styrene copolymer (B) used in the present invention preferably contains 2 to 4 glycidyl groups on average per molecular chain. If the number of glycidyl groups per molecular chain is less than 2, the thickening is insufficient, and if the number of glycidyl groups per molecular chain exceeds 4, gelation of the composition tends to occur, resulting in poor stability of the composition.
When indicating the concentration of the glycidyl group in the epoxy value, preferably 300～1,200 is equivalent / 10 ⁶ g, more preferably from 400 to 1,000 equivalent / 10 ⁶ g, more preferably 500 to 1, 000 equivalent / 10 ⁶ g.
If the epoxy value is less than 300 equivalents / 10 ⁶ g, the reactivity with the polyamide resin may be insufficient and the thickening effect may be insufficient. On the other hand, if it exceeds 1,200 equivalent / 10 ⁶ g, gelation or the like may occur, which may adversely affect the appearance of the molded product and the moldability.

  The weight average molecular weight of the glycidyl group-containing styrenic copolymer (B) is preferably 500 to 20,000, more preferably 700 to 10,000, and still more preferably 1000 to 10,000. If the weight average molecular weight is less than 500, the unreacted reactive acrylic copolymer may bleed out on the surface of the molded product and cause contamination of the surface of the molded product. On the other hand, when it exceeds 20,000, the compatibility with the polyamide resin is deteriorated, phase separation and gelation may occur, and the appearance of the molded product may be adversely affected.

  The addition amount of the glycidyl group-containing styrenic copolymer (B) is 0.3 to 10 parts by mass, preferably 1 to 8 parts by mass with respect to 100 parts by mass of the polyamide resin. The optimum addition amount varies depending on the epoxy value. If the epoxy value is high, the addition amount may be small, and if the epoxy value is low, the addition amount needs to be increased. If the amount is less than 0.3 parts by mass within the range of the epoxy value, the thickening effect is low, and if it exceeds 10 parts by mass, gelation or the like partially occurs and the appearance of the molded product and the moldability are adversely affected. In a short time in the extruder, the reaction does not proceed sufficiently, and the remaining epoxy groups react in the molding machine to change the viscosity and make the molding unstable.

The olefin polymer (C) having a carboxylic acid group or / and a carboxylic acid anhydride group used in the present invention (hereinafter sometimes simply referred to as a modified olefin polymer (C)) is a carboxylic acid. It is an α-olefin polymer or copolymer in which a monomer having a group or / and a carboxylic acid anhydride group is contained in a polymer molecular chain by copolymerization or graft polymerization.
Specific examples of the olefin polymer include homopolymers such as polyethylene, polypropylene, polybutene-1, polypentene-1, and polymethylpentene, ethylene, propylene, butene-1, pentene-1, and 4-methylpentene-1. , Α-olefins such as hexene-1, octene-1, isobutylene, 1,4-hexadiene dicyclopentadiene, 2,5-norbornadiene, 5-ethylidene norbornene, 5-ethyl-2,5-norbornadiene, 5- (1 Mention may be made of polyolefins obtained by radical polymerization of at least one non-conjugated diene such as' -probenyl) -2-norbornene using a normal metal catalyst or a metallocene-based high-performance catalyst.

  The diene elastomer is an AB type or ABA 'type block copolymer elastic body composed of a vinyl aromatic hydrocarbon and a conjugated diene, and the end blocks A and A' are the same or different. And thermoplastic homopolymers or copolymers derived from vinyl aromatic hydrocarbons, where the aromatic moiety may be monocyclic or polycyclic, examples of such vinyl aromatic hydrocarbons include Styrene, α-methylstyrene, vinyltoluene, vinylxylene, ethylvinylxylene, vinylnaphthalene and mixtures thereof. The intermediate polymer block B is composed of a conjugated diene hydrocarbon, and examples thereof include polymers derived from 1,3-butadiene, 2,3-dimethylbutadiene, isoprene, 1,3-pentadiene, and mixtures thereof. In the present invention, those obtained by subjecting the intermediate polymer block B of the block copolymer to a hydrogenation treatment are also included.

  Specific examples of the polyolefin copolymer include an ethylene / propylene copolymer, an ethylene / butene-1 copolymer, an ethylene / hexene-1 copolymer, an ethylene / propylene / dicyclopentadiene copolymer, and an ethylene / propylene / copolymer. 5-ethylidene-2-norbornene copolymer, unhydrogenated or hydrogenated polybutadiene, unhydrogenated or hydrogenated styrene / isoprene / styrene triblock copolymer, unhydrogenated or hydrogenated styrene / butadiene / styrene triblock copolymer A polymer etc. are mentioned.

A method for introducing a carboxylic acid group or / and a carboxylic acid anhydride group is not particularly limited, and a method such as copolymerization or graft introduction to a non-modified polyolefin using a radical initiator can be used. In the case of copolymerization, these functional group-containing components are introduced in an amount of 0.1 to 20 mol%, preferably 0.5 to 12 mol%, based on the total olefin monomer in the modified polyolefin. In such a case, the content is suitably in the range of 0.1 to 10% by mass, preferably 0.5 to 6% by mass, based on the mass of the modified polyolefin.
When the introduction amount of the functional group-containing component is less than the above range, thickening becomes insufficient, and when it exceeds the above range, the stability of the melt viscosity may be impaired.

Specific examples of the modified polyolefin polymer (C) particularly useful in the present invention include maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, and copolymers thereof. Some or all of the carboxylic acid moiety in the polymer is salted with sodium, lithium, potassium, zinc, calcium, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / methacryl Methyl acid copolymer, ethylene / ethyl methacrylate copolymer, ethylene / ethyl acrylate-g-maleic anhydride copolymer ("g" represents graft, the same applies hereinafter), ethylene / methyl methacrylate-g -Maleic anhydride copolymer, ethylene / propylene-g-maleic anhydride copolymer Ethylene / butene-1-g-maleic anhydride copolymer, ethylene / propylene / 1,4-hexadiene-g-maleic anhydride copolymer, ethylene / propylene / dicyclopentadiene-g-maleic anhydride copolymer , Ethylene / propylene / 2,5-norbornadiene-g-maleic anhydride copolymer, hydrogenated styrene / butadiene / styrene-g-maleic anhydride copolymer, hydrogenated styrene / isoprene / styrene-g-maleic anhydride And a copolymer.
Among these, a polymer or copolymer having a carboxylic anhydride group having high reactivity with an amine in polyamide is preferable.

  The addition amount of the olefin polymer (C) having a carboxylic acid group or / and a carboxylic anhydride group is 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyamide resin, and 0.3 to 5 parts by mass. preferable. If the amount is less than 0.1 parts by mass, the thickening effect is small.

In addition, a compound other than the glycidyl group-containing styrene-based copolymer (B) and the modified olefin-based polymer (C) can be arbitrarily added as long as gel or the like is not generated due to advanced crosslinking.
The functional group possessed by the compound other than the glycidyl group-containing styrenic copolymer (B) may be any as long as it reacts with an amino group or a carboxyl group during melt extrusion. In addition, different types of functional groups may be present in one molecule. Examples thereof include functional groups such as glycidyl group, carboxyl group, carboxylic acid metal salt, ester group, hydroxyl group, amino group and carbodiimide group, and further functional groups that undergo ring-opening addition such as lactone, lactide, and lactam. Among these, preferred functional groups include a glycidyl group or a carbodiimide group from the viewpoint of reaction speed.

The fibrous reinforcing material (D) used in the present invention is the one that most effectively improves physical properties such as strength, rigidity and heat resistance. Specifically, glass fiber, carbon fiber, aramid fiber, alumina fiber. , Fibrous materials such as silicon carbide fibers and zirconia fibers, whiskers such as aluminum borate and potassium titanate, acicular wollastonite, milled fibre, etc., but are not limited thereto. .
In particular, glass fiber, carbon fiber and the like are preferably used. These fibrous reinforcing materials are preferably pretreated with a coupling agent such as an organosilane compound, an organotitanium compound, an organoborane compound, and an epoxy compound, and a carboxylic acid group or / and a carboxylic acid. Those that are easily reactive with anhydride groups are particularly preferred. A polyamide-based resin composition containing glass fibers treated with a coupling agent is preferable because a molded product having excellent mechanical characteristics and appearance characteristics can be obtained. In addition, other fibrous reinforcing materials can be added after use if the coupling agent is not yet treated.
As the glass fiber, a chopped strand having a fiber length of about 1 to 20 mm can be preferably used. As the cross-sectional shape of the glass fiber, a glass fiber having a circular cross section and a non-circular cross section can be used. As the cross-sectional shape of the glass fiber, a glass fiber having a non-circular cross-section is preferable in view of physical properties. Non-circular cross-sectional glass fibers include those that are substantially elliptical, substantially oval, or substantially saddle-shaped in a cross section perpendicular to the length direction of the fiber length, and have a flatness of 1.5 to 8 It is preferable that Here, the flatness is assumed to be a rectangle with the smallest area circumscribing a cross section perpendicular to the longitudinal direction of the glass fiber, the length of the long side of the rectangle is the major axis, and the length of the short side is the minor axis. It is the ratio of major axis / minor axis. The thickness of the glass fiber is not particularly limited, but the minor axis is about 1 to 20 μm and the major axis is about 2 to 100 μm. The addition amount of the fibrous reinforcing material may be selected as an optimum amount, but it is possible to add 20 to 150 parts by mass with respect to 100 parts by mass of the copolyamide (A), but the blending amount is 150 masses. If it exceeds the part, the elongation at the time of melting is lost, and a hole may be opened when air is blown. Moreover, if it is less than 20 mass parts, the effect of a reinforcing material may not fully be exhibited.

The reinforced polyamide resin composition of the present invention has a melt viscosity of 4,000 to 20,000 Pa · s measured at a shear rate as low as 0.5 mm / min at a temperature 25 ° C. higher than the melting point. Preferably it is 5,000-20,000 Pa.s, More preferably, it is 7,000-15,000 Pa.s, and it is excellent in a moldability and productivity by being in these ranges.
Generally, parison molding at the time of extrusion or blow molding is extruded at a relatively low shear rate, so if the melt viscosity is less than 4,000 Pa · s, the parison discharged from the nozzle can be drawn down by its own weight and cannot be molded. The thickness of the product may be uneven. On the other hand, if the melt viscosity exceeds 20,000 Pa · s, the melt viscosity is too high, and a load is applied to the molding machine or the extruder motor, which may damage the molding machine.
Further, the reinforced polyamide resin composition of the present invention has a predetermined melt mass flow rate (MFR ₀ ) and melt mass flow rate measurement at a temperature 25 ° C. higher than the melting point and a melt flow index (based on JIS K 7210) at a load of 10 kg. The difference from the melt mass flow rate (MFR ₂₀ ) after retaining for 20 minutes is in the range of −1.0 to 1.0. Here, the “predetermined melt mass flow rate” indicates that measurement was performed according to JIS K 7210. The difference between MFR ₀ and MFR ₂₀ is (MFR ₀ -MFR ₂₀ ), and the unit is g (grams).
If the difference between MFR ₁ and MFR ₂₀ is not within the range of -1.0 to 1.0, the suppression of fuzz on the inner surface of the hollow molded article becomes insufficient. The difference between MFR ₀ and MFR ₂₀ is preferably as small as possible, and is preferably in the range of -0.9 to 0.9, more preferably -0.7 to 0.7.

  In the reinforced polyamide resin composition of the present invention, the copolymerized polyamide resin (A) preferentially reacts with the olefin polymer (C) having a carboxylic acid group or / and a carboxylic anhydride group, and then the glycidyl group is converted. Since the styrene copolymer (B) containing two or more has a large amount of aromatic rings and 2 to 4 glycidyl groups and a relatively high molecular weight, the copolymerized polyamide resin (A ) Is well dispersible and well dispersed, and both the copolymerized polyamide resin (A) and the olefin polymer (C) react via glycidyl groups. Since a branched structure is generated, it is considered that the melt viscosity of the polyamide-based resin composition is increased. The combination of the copolymerized polyamide resin (A), the glycidyl group-containing styrene-based copolymer (B) and the olefin-based polymer (C) is unclear for details, but the fibrous reinforcing material (D) and It is considered that the fuzziness by the fibrous reinforcing material (D) on the inner surface of the molded product at the time of blow molding can be suppressed.

  In addition to the above, various additives for conventional polyamide can be used in the reinforced polyamide resin composition of the present invention. Additives include fillers, stabilizers, impact modifiers, flame retardants, mold release agents, slidability improvers, colorants, plasticizers, crystal nucleating agents, and copolymerized polyamides (A) used in the present invention. Are different polyamides, thermoplastic resins other than polyamide, and the like.

  As fillers (fillers), reinforcing fillers, conductive fillers, magnetic fillers, flame retardant fillers, thermal conductive fillers and the like are listed according to purpose. Specifically, glass beads, glass flakes, glass balloons, silica, talc , Kaolin, wollastonite, mica, alumina, hydrotalcite, montmorillonite, graphite, carbon nanotube, fullerene, zinc oxide, indium oxide, tin oxide, iron oxide, titanium oxide, magnesium oxide, aluminum hydroxide, magnesium hydroxide, Examples thereof include red phosphorus, calcium carbonate, potassium titanate, lead zirconate titanate, barium titanate, aluminum nitride, boron nitride, zinc borate, aluminum borate, barium sulfate, and magnesium sulfate. These fillers may be used not only alone but also in combination of several kinds. An optimum amount of the filler may be selected, but it is possible to add a filler of 250 parts by mass or less, preferably 20 to 150 parts by mass with respect to 100 parts by mass of the copolyamide. Moreover, in order to improve the affinity with the polyamide resin, the fibrous reinforcing material and the filler are preferably used in combination with a coupling agent-treated or coupling agent. As the coupling agent, a silane coupling agent is used. Any of titanate coupling agents and aluminum coupling agents may be used, and among them, aminosilane coupling agents and epoxysilane coupling agents are particularly preferable.

  Stabilizers include organic antioxidants such as hindered phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, heat stabilizers, light stabilizers such as hindered amines, benzophenones, and imidazoles. Examples include ultraviolet absorbers, metal deactivators, and copper compounds. Copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cupric chloride, cupric bromide, cupric iodide, cupric phosphate, cupric pyrophosphate, Copper salts of organic carboxylic acids such as copper sulfide, copper nitrate, and copper acetate can be used. Further, as a component other than the copper compound, an alkali metal halide compound is preferably contained. Examples of the alkali metal halide compound include lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, bromide. Examples thereof include sodium, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide and the like. These additives may be used alone or in combination of several kinds. Although the addition amount of a stabilizer should just select the optimal quantity, it is possible to add 0-5 mass parts with respect to 100 mass parts of copolyamide.

  A thermoplastic resin other than polyamide may be added to the reinforced polyamide resin composition of the present invention as long as the effects of the present invention are not impaired. Polymers other than polyamide include polyphenylene sulfide (PPS), liquid crystal polymer (LCP), aramid resin, polyetheretherketone (PEEK), polyetherketone (PEK), polyetherimide (PEI), thermoplastic polyimide, polyamideimide (PAI), polyether ketone ketone (PEKK), polyphenylene ether (PPE), polyether sulfone (PES), polysulfone (PSU), polyarylate (PAR), polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene Phthalate, polycarbonate (PC), polyoxymethylene (POM), polypropylene (PP), polyethylene (PE), polymethylpentene (TPX), polystyrene ( S), polymethyl methacrylate, acrylonitrile-styrene copolymer (AS), acrylonitrile-butadiene-styrene copolymer (ABS), and if compatibility is poor, add compatibilizers such as reactive compounds and block polymers Alternatively, it is important to modify a polymer other than polyamide (particularly acid modification is preferred). These thermoplastic resins can be blended in the melted state by melt kneading. However, even if the thermoplastic resin is made into a fiber or particle and dispersed in the copolymerized polyamide resin (A) used in the present invention. good. The optimum amount of the thermoplastic resin may be selected, but 0 to 50 parts by mass can be added to 100 parts by mass of the copolyamide resin.

  As a flame retardant, a combination of a halogen flame retardant and antimony is good, and as a halogen flame retardant, brominated polystyrene, brominated polyphenylene ether, brominated bisphenol type epoxy polymer, brominated styrene maleic anhydride polymer, Brominated epoxy resins, brominated phenoxy resins, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, perchlorocyclopentadecane, brominated cross-linked aromatic polymers, etc. are preferred. Antimony compounds include antimony trioxide and antimony pentoxide. Sodium antimonate and the like are preferable. Among these, a combination of dibromopolystyrene and antimony trioxide is preferable from the viewpoint of thermal stability. Non-halogen flame retardants include melamine cyanurate, red phosphorus, phosphinic acid metal salts, and nitrogen-containing phosphoric acid compounds. In particular, a combination of a phosphinic acid metal salt and a nitrogen-containing phosphoric acid compound is preferable, and examples of the nitrogen-containing phosphoric acid compound include melamine or a melamine condensate such as melam and melon and polyphosphoric acid reactive organisms or those. A mixture of At that time, addition of a hydrotalcite-based compound is preferable for preventing metal corrosion of a mold or the like. Although the addition amount of a flame retardant should just select an optimal quantity, it is possible to add 0-50 mass parts with respect to 100 mass parts of copolyamide.

  Examples of the release agent include long chain fatty acids or esters thereof, metal salts, amide compounds, polyethylene wax, silicon, polyethylene oxide, and the like. The long chain fatty acid preferably has 12 or more carbon atoms, and examples thereof include stearic acid, 12-hydroxystearic acid, behenic acid, and montanic acid. Partial or total carboxylic acid is esterified with monoglycol or polyglycol. Or a metal salt may be formed. Examples of the amide compound include ethylene bisterephthalamide and methylene bisstearyl amide. These release agents may be used alone or as a mixture. The addition amount of the release material may be selected as an optimum amount, but 0 to 5 parts by mass can be added to 100 parts by mass of the copolymer polyamide.

  Examples of the sliding property improving material include high molecular weight polyethylene, acid-modified high molecular weight polyethylene, fluorine resin powder, molybdenum disulfide, silicon resin, silicon oil, zinc, graphite, mineral oil, and the like. The resin slidability improving material can be added in a range not impairing the characteristics of the present invention, for example, in the range of 0.05 to 3 parts by mass.

The production method of the reinforced polyamide resin composition of the present invention is not particularly limited, and any method known to those skilled in the art is possible, and a single screw extruder, a twin screw extruder, a pressure kneader, a Banbury mixer, etc. are used. can do. Among these, it is preferable to use a twin screw extruder.
The glycidyl group-containing styrene copolymer (B) and the modified olefin polymer (C) can be added to the polyamide resin after the completion of polymerization. For example, a method in which an additive is directly mixed and kneaded with a molten polyamide resin immediately after leaving the polymerization machine, or an additive to a solidified polyamide resin (for example, powder, pellets, etc.) And then melt melting and kneading.
In the former method, since the polyamide resin is in a molten state, the addition of the additive increases the melt viscosity as it is. However, in the latter method, the polyamide resin in which the additive is uniformly dispersed and mixed has a high melt viscosity. In order to be remelted by heating.

The conditions of the twin screw extruder vary depending on various factors such as the type of polyamide resin, the type and amount of additives, and cannot be uniquely determined. The melting point of the polyamide resin is in the range of 170 to 320 ° C., and the processing temperature may be set around the melting point + 25 ° C. It may be considered that the reaction time is within 10 minutes, for example, 1 to several minutes, and the target melt viscosity is sufficiently reached.
As for the screw configuration, it is preferable to incorporate several needing disks having excellent kneading. The high melt viscosity polyamide resin prepared by mixing and melting the reactive group-containing acrylic copolymer in this way is uniform and has high viscosity stability in the molten state, and has flow characteristics particularly suitable for extrusion molding and blow molding. ing.

In the reinforced polyamide resin composition of the present invention, it is useful to add a heat-resistant agent for the heat stability of the polyamide resin composition when it is retained for a long time in a molten state at a high temperature during extrusion or blow molding. In addition, copper compounds such as copper halides such as copper acetate, copper iodide, copper chloride, and copper bromide should be used as long-term heat aging inhibitors effective in a high temperature environment of 120 ° C or higher. Is preferred. The addition amount of the copper compound is preferably 0.005 to 0.5 parts by mass, more preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the reinforced polyamide resin composition.
The copper compound is also effective in combination with an alkali halide such as potassium iodide, potassium chloride or sodium iodide. As other heat-resistant agents, it is preferable to use phosphorus antioxidants, hindered phenol compounds, phosphite compounds, thioether compounds, and the like as antioxidants and antioxidants within a known range.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, the measured value described in the Example is measured by the following method.

(1) Raw material, raw material adjustment method and measurement method [relative viscosity]
0.25 g of polyamide resin was dissolved in 25 ml of 96% sulfuric acid and measured at 20 ° C. using an Ostwald viscometer.
[Melting point (Tm) and glass transition temperature (Tg)]
10 mg of the polyamide dried under reduced pressure at 105 ° C. for 15 hours was weighed in an aluminum pan (TA Instruments, product number 900793.901) and sealed with an aluminum lid (TA Instruments, product number 900794.901). After preparing the sample, use a differential scanning calorimeter DSCQ100 (manufactured by TA INSTRUMENTS) to raise the temperature from room temperature to 20 ° C./min, hold at 350 ° C. for 3 minutes, take out the measurement sample pan, soak in liquid nitrogen, and quench rapidly I let you. Thereafter, the sample was taken out from the liquid nitrogen, allowed to stand at room temperature for 30 minutes, and then heated again from room temperature at 20 ° C./minute using a differential scanning calorimeter DSCQ100 (manufactured by TA INSTRUMENTS) and held at 350 ° C. for 3 minutes. . The endothermic peak temperature due to melting at that time was defined as the melting point (Tm). The glass transition temperature (Tg) is the intersection of the base line extension below the glass transition point and the tangent line indicating the maximum slope from the peak rising portion to the peak apex in the second temperature rising process. Determined by temperature.

[Synthesis of polyamide 10T11 (A-1)]
Decamethylenediamine 8.26 kg, terephthalic acid 7.97 kg, 11-aminoundecanoic acid 6.43 kg, sodium diphosphite 9 g, terminal adjuster 40 g acetic acid and 17.52 kg ion-exchanged water in a 50 liter autoclave First, the pressure was increased from normal pressure to 0.05 MPa with N ₂ , the pressure was released, and the pressure was returned to normal pressure. This operation was performed 3 times, and after N ₂ substitution, the mixture was uniformly dissolved at 135 ° C. and 0.3 MPa with stirring. Thereafter, the solution was continuously supplied by a liquid feed pump, heated to 240 ° C. with a heating pipe, and heated for 1 hour. Thereafter, the reaction mixture was supplied to a pressure reaction can, heated to 290 ° C., and a part of water was distilled off so as to maintain the internal pressure of the can at 3 MPa to obtain a low-order condensate. Thereafter, this low-order condensate is directly supplied to a twin-screw extruder (screw diameter 37 mm, L / D = 60) while maintaining a molten state, and the resin temperature is 330 ° C. while water is being removed from three vents. Polycondensation proceeded under melting to obtain a copolymerized polyamide. The obtained copolymer polyamide had a composition of 10T / 11 = 60/40 (molar ratio), a melting point of 250 ° C., a relative viscosity of 2.6, and a glass transition temperature of 75 ° C.

[Synthesis of polyamide 10T11 (A-2)]
Same as Synthesis Example (A-1) except that the amount of decamethylenediamine was changed to 11.01 kg, the amount of terephthalic acid was changed to 10.62 kg, and the amount of 11-aminoundecanoic acid was changed to 3.22 kg. Thus, a copolymerized polyamide was synthesized. The obtained copolymer polyamide had a composition of 10T / 11 = 80/20 (molar ratio), a melting point of 289 ° C., a relative viscosity of 2.6, and a glass transition temperature of 93 ° C.
[Synthesis of polyamide 10T12 (A-3)]
A copolymer polyamide was synthesized in the same manner as in Synthesis Example (A-2) except that 3.22 kg of 11-aminoundecanoic acid was changed to 2.93 kg of undecane lactam. The obtained copolyamide had a composition of 10T / 12 = 80/20 (molar ratio), a melting point of 288 ° C., a relative viscosity of 2.4, and a glass transition temperature of 92 ° C.

[Production of styrene polymer (B-1)]
The oil jacket temperature of a 1 liter pressurized stirred tank reactor equipped with an oil jacket was kept at 200 ° C. On the other hand, 89 parts by mass of styrene (hereinafter referred to as St), 11 parts by mass of glycidyl methacrylate (hereinafter referred to as GMA), 15 parts by mass of xylene and ditertiary butyl peroxide (hereinafter referred to as DTBP) as a polymerization initiator A monomer liquid mixture consisting of 5 parts by mass was charged into a raw material tank. Continuous supply from the raw material tank to the reactor at a constant supply rate (48 g / min, residence time: 12 minutes), and the reaction liquid is continuously supplied from the outlet of the reactor so that the content liquid mass of the reactor becomes constant at about 580 g. Extracted. At that time, the internal temperature of the reactor was kept at about 210 ° C. After 36 minutes have passed since the temperature inside the reactor has stabilized, the extracted reaction solution is continuously removed by a thin film evaporator maintained at a reduced pressure of 30 kPa and a temperature of 250 ° C. The polymer (B-1) not contained was recovered.
The obtained polymer (B-1) had a mass average molecular weight of 8,500 and a number average molecular weight of 3,300 according to GPC analysis (polystyrene conversion value). The epoxy value was 670 equivalents / 10 ⁶ g, and the epoxy value (the average number of epoxy groups per molecule) was 2.2.

[Production of styrene polymer (B-2)]
The polymer (B-1) was prepared in the same manner as in the production of the polymer (B-1) except that a monomer mixed solution consisting of St77 parts by mass, GMA23 parts by mass, xylene15 parts by mass, and DTBP0.3 parts by mass was used. -2) was manufactured.
The obtained polymer (B-2) had a mass average molecular weight of 9700 and a number average molecular weight of 3300 according to GPC analysis (polystyrene equivalent value). The epoxy value was 1400 equivalent / 10 ⁶ g, and the epoxy value (average number of epoxy groups per molecule) was 4.6.

[Olefin polymer (C)]
A maleic anhydride-modified ethylene / butene-1 copolymer (Mitsui Chemicals, Tuffmer MH7020) was used.
[Fibrous reinforcement (D)]
Glass fiber: T-275H (coupling agent: aminosilane compound) manufactured by Nippon Electric Glass Co., Ltd. was used.

As other additives, the following were used.
[Other additives]
Stabilizer 1: Cupric bromide (manufactured by Nacalai Tesque, reagent)
Stabilizer 2: Irganox B1171 (manufactured by Ciba Specialty Chemicals)
Mold release agent: WE40 of Montanate ester wax (manufactured by Clariant Japan)
Black pigment: EPC8E313 (manufactured by Sumika Color)

(2) [Methods for producing reinforced polyamide resin compositions of Examples and Comparative Examples]
Examples 1-6, Comparative Examples 1-3
Each raw material described above was weighed according to the blending ratio shown in Table 1 (the other additives are the following contents with respect to the composition), and the cylinder temperature was set to polyamide with a 35φ twin screw extruder (manufactured by Toshiba Machine Co., Ltd.). In the case of 10T11 and 10T12, the temperature was set to 300 ° C., and in the case of polyamide 6, the temperature was set to 250 ° C. and melt kneading was performed at a screw rotation speed of 100 rpm. Raw materials other than glass fibers were mixed in advance and charged from the main hopper, and glass fibers were charged by side feed from the vent port. The strand discharged from the extruder was cooled in a water tank, pelletized with a strand cutter, dried at 125 ° C. for 5 hours, and subjected to various evaluations.
Other additives (stabilizer 1: 0.06% by mass, stabilizer 2: 0.3% by mass, mold release agent: 0.4% by mass, black pigment: 0.8% by mass).
The pellets of the obtained reinforced polyamide resin composition were molded with respective evaluation samples with an injection molding machine, and the characteristics were evaluated.

(3) [Evaluation method of reinforced polyamide resin composition]
[Formation of evaluation sample]
Using Toshiba Machine's injection molding machine EC-100, the cylinder temperature was set to the melting point of the resin + 20 ° C. As the mold, a mold for producing a flat plate having a length of 100 mm, a width of 100 mm, and a thickness of 3 mm was used. The mold temperature was set to 130 ° C., and the molding was performed at an injection speed of 50 mm / second, a holding pressure of 30 MPa, an injection / holding time of 10 seconds, and a cooling time of 15 seconds.

[Water absorption and dimensional change rate]
To evaluate the 95% RH water absorption rate, a flat plate having a length of 100 mm, a width of 100 mm, and a thickness of 3 mm was prepared. When there was no change in the weight, it was regarded as equilibrium water absorption, and the weight and dimensions were measured and obtained from the following formula.
95% RH water absorption (%) = (weight when 95% RH absorbs water−weight when dried) / weight when dried with 95% RH × 100
95% RH dimensional change rate (%) = (95% RH water absorption-dry size) / dry size × 100
However, the dimensions were 95% RH and the average value in the flow direction and the reverse flow direction of the resin both during drying.

[Melt Mass Flow Rate (MFR ₀ , MFR ₂₀ )]
First, in a melt mass flow rate (conforming to JIS K 7210) at a load of 10 kg at a temperature of the melting point of the polyamide resin + 25 ° C. (according to JIS K 7210), first, from a predetermined melt mass flow rate (MFR ₀ : discharge mass per minute (g) per 10 minutes) The discharge weight (g) was calculated). Next, after leaving for 20 minutes after removing the load, a load of 10 kg was applied again to measure the melt mass flow rate (MFR ₂₀ : the discharge weight (g) per 10 minutes was calculated from the discharge mass (g) per minute). .
Each sample was charged into the apparatus in a dry state with a moisture content of 0.03% or less to prevent MFR fluctuations due to moisture.

[Melt viscosity]
Using a capillary rheometer (Toyo Seiki Co., Ltd. Capillograph IC), measurement was performed at a shear rate of 0.5 mm / min at a temperature of the melting point of the polyamide resin composition obtained by DSC + 25 ° C.

[Formability evaluation method]
The extrusion moldability of the parison and the drawdown of the parison were measured as follows.
Using a blow molding machine (FKI Co., 45φ 2-layer direct blow molding machine) with a die φ32mm and mandrel φ22mm, without using an accumulator, the cylindrical shape (pipe shape) shown in FIG. A parison having a uniform thickness that is not attached was extruded, and the formability of the parison (solidification / elongation state), the drawdown state, and the fluffing of the glass fiber inside the molded product were evaluated according to the following criteria. The molding conditions were set such that the cylinder temperature was set in the same manner as in injection molding, and the mold temperature was 130 ° C. in all cases. The blowing of air was performed 3 seconds after clamping and the spraying time was 20 seconds.
<Parison drawdown>
Thickness difference between part A and part B shown in FIG. 1 ≦ 0.5 mm: ○
Drawdown is remarkable and cannot be molded: ×
<Extrusion moldability of parison>
Spraying part (disposable bag) and product part: No tearing / perforation: ◎
Spraying part (discarded bag): with holes, product part: without tearing / holes: ○
Spraying part (disposable bag) and product part: with tears and holes: ×
<Glassiness of glass fiber on the inner surface of molded product>
The molded product was observed when it was continuously molded without stopping molding (no stagnation) and immediately after the molding was stopped for 20 minutes (stagnation 20 minutes).
No fuzz is recognized: ○
Some fuzz is observed: △
Fluffing and irregularities are noticeable: ×
The evaluation results are shown in Table 1.
The observation part of the molded product is the part shown in FIG. Moreover, the observation figure (photograph) of Example 3 is shown in FIG. 3, and the observation figure (photograph) of the comparative example 3 is shown in FIG.

As is apparent from Table 1, the reinforced polyamide resin compositions of Examples 1 to 6 were prepared from the olefin-based polymer in which the copolymerized polyamide resin (A) had a glycidyl group-containing styrene copolymer (B) and an acid anhydride group. Since it contains the coalescence (C), a synergistic effect of both can be obtained, a melt viscosity suitable for blow molding can be realized with a small amount of blending, and it has excellent retention stability, and the inner surface of the hollow molded product It can be seen that glass fiber fluff can be suppressed.
Only the glycidyl group-containing styrenic copolymer (B) of Comparative Example 1 requires a large amount of blending in order to obtain a melt viscosity suitable for blow molding, and the residence stability is poor, and the residence time is 20 minutes. After the treatment, fluffing of the glass fiber on the inner surface of the hollow molded product occurred. The olefin polymer (C) of Comparative Example 2 alone had a low thickening effect even when blended in a large amount, and the drawdown of the parison was remarkable, and a predetermined molded product could not be obtained. In the polyamide 6 system that does not use the copolymerized polyamide resin (A) of Comparative Example 3, the extrusion molding property of the parison is inferior and the fluffing of the glass fiber on the inner surface of the molded product is remarkable even if the fluctuation of the melt mass flow rate due to residence is small. Met.

  The reinforced polyamide resin composition of the present invention can stably produce an extrusion-molded product or a blow-molded product having low water absorption, excellent dimensional stability and chemical resistance. For this reason, it is useful for manufacturing the intake / exhaust system parts of automobiles.

Claims (10)

Glycidyl group-containing styrene with respect to 100 parts by mass of copolymer polyamide resin (A) comprising (a) decanterephthalamide unit 50 to 98 mol% and (b) undecanamide unit or / and dodecanamide unit 50 to 2 mol% 0.3 to 10 parts by mass of a copolymer (B), 0.1 to 10 parts by mass of an olefin polymer (C) having a carboxylic acid group or / and a carboxylic anhydride group, a fibrous reinforcing material ( A reinforced polyamide resin composition for hollow molded articles, comprising 20 to 150 parts by mass of D) and further satisfying the following characteristics (a) and (b):
(A) The melt viscosity at a shear rate of 0.5 mm / min is 4000 to 20000 Pa · s at a temperature of the melting point of the copolymerized polyamide resin + 25 ° C.
(B) The melt mass flow rate (conforming to JIS K 7210) at a load of 10 kg at a temperature of the melting point of the copolymerized polyamide resin + 25 ° C. (according to JIS K 7210) was retained for 20 minutes at the time of measuring the melt mass flow rate (MFR ₀ ). The difference from the later melt mass flow rate (MFR ₂₀ ) is in the range of −1.0 to 1.0.   The hollow molded article according to claim 1, wherein the copolymerized polyamide resin (A) comprises (a) 75 to 98 mol% of decanterephthalamide units and (b) 25 to 2 mol% of undecanamide units or / and dodecanamide units. Reinforced polyamide resin composition.   The copolymer polyamide resin (A) is obtained from (c) a structural unit obtained from a diamine other than the structural unit (a) and a dicarboxylic acid, or an aminocarboxylic acid or lactam other than the structural unit (b). The reinforced polyamide resin composition for hollow molded bodies according to claim 1, comprising a unit of up to 30 mol%.   The reinforced polyamide resin composition for a hollow molded article according to claim 1, wherein the glycidyl group-containing styrene copolymer (B) has an average number of glycidyl groups per molecular chain of 2 to 4.   The glycidyl group-containing styrene copolymer (B) is 99 to 50 mass% of styrene polymer units, 1 to 30 mass% of glycidyl group-containing acrylic polymer units, and 0 to 40 mass% of other vinyl polymer units. The reinforced polyamide resin composition for a hollow molded article according to claim 1, which is a copolymer comprising%.   The hollow molded object obtained using the reinforced polyamide resin composition in any one of Claims 1-5.   The hollow molded article according to claim 6, wherein the hollow molded article is an automobile-related part.   The hollow molded body according to claim 7, wherein the automobile-related part is an intake / exhaust system part.   9. The hollow molded body according to claim 8, wherein the intake / exhaust system component is an air hose, an air duct, a turbo duct, a turbo hose, an intake manifold, or an exhaust manifold.   10. The method according to claim 9, which is obtained using any one of hollow molding methods of direct blow, three-dimensional single blow, three-dimensional exchange blow, suction blow, three-dimensional suction blow, three-dimensional exchange suction blow, and injection stretch blow. Hollow molded body.