JP2009001746A - Polyamide resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition composed mainly of a polyamide and an ABS resin, which excels in low water absorption, dimensional stability, mechanical properties at water absorption, heat resistance, moldability and chemical resistance and also has a low specific gravity, and to provide a resin molded product consisting thereof. <P>SOLUTION: The resin composition is obtained by melt-kneading 5-20 parts by mass of an acid-modified styrene-based elastomer, 0.05-5 parts by mass of an unsaturated carboxylic acid, unsaturated dicarboxylic acid or acid anhydride thereof and 0.01-3 parts by mass of a radical generator, based on 100 parts by mass of a polyamide/ABS resin composition which consists of 40-80% by mass of a polyamide containing 0.01-20% by mass of a swelling fluorine mica type mineral, obtained by polymerizing the monomer under co-existence of the swelling fluorine mica type mineral, and 60-20% by mass of an ABS resin. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a resin composition mainly composed of a polyamide resin and an ABS resin, which are excellent in low water absorption, dimensional stability, mechanical properties during water absorption, heat resistance, moldability, chemical resistance, and low specific gravity. .

  Polyamide has excellent mechanical properties, heat resistance, and chemical resistance, but has a drawback of causing a decrease in rigidity and a dimensional change upon water absorption. In order to complement such physical properties of polyamide, many resin compositions have been proposed in combination with ABS resin having excellent water resistance and impact resistance, but having a problem in chemical resistance. However, this resin composition has a problem that the compatibility between polyamide and ABS resin is poor and impact strength is low.

  Further, a blend of polyamide and an ABS resin modified with a functional group capable of performing a chemical reaction or chemical interaction has been proposed (Patent Documents 1 and 2). However, although the moldability and impact resistance are improved to some extent by this resin composition, the improvement effect is insufficient, and the mechanical strength, heat resistance, and dimensional stability are not satisfactory.

  Furthermore, Patent Document 3 discloses a resin composition comprising polyamide, an impact resistance improving material, and a layered silicate. This resin composition was found to have excellent mechanical strength and heat resistance, but in order to disperse the layered silicate uniformly in the resin composition, a pretreatment for contacting with a swelling agent in advance. There is a problem that a process is required and the manufacturing cost increases.

The applicant of the present invention is excellent in mechanical properties, heat resistance, dimensional stability, low specific gravity and the like by blending a swellable fluoromica-based mineral mineral at the time of polymerization of polyamide and further melt-kneading with ABS resin. Although a composition (Patent Document 4) is disclosed, the impact strength is not satisfactory.
JP-A-1-294756 JP-A-2-175755 JP-A-2-29457 JP-A-8-3439

  Since the ship body or a member attached to the ship is used on the water such as the sea or river, it must be easily affected by water absorption, and must have excellent mechanical property retention and dimensional stability during water absorption. In addition, when used around the engine, it must have excellent mechanical properties at high temperatures. The present invention solves the above-mentioned problems, and is mainly composed of polyamide and ABS resin having low water absorption, dimensional stability, mechanical properties upon water absorption, heat resistance, moldability, chemical resistance, and low specific gravity. An object of the present invention is to provide a resin composition and a resin molded product comprising the same.

As a result of intensive research to solve such problems, the present inventors have determined that a resin composition composed of a polyamide resin and an ABS resin has a swellable fluoromica-based mineral mineral at the time of polymerization of the polyamide resin. It was found that a resin composition having excellent physical properties can be obtained by blending, further blending an unsaturated compound, a radical generator, and an acid-modified styrene elastomer, and kneading and kneading.

That is, the gist of the present invention is as follows.
(1) 40-80% by mass of polyamide containing 0.01-20% by mass of a swellable fluoromica-based mineral obtained by polymerizing monomers in the presence of a swellable fluoromica-based mineral, and 60-20% by mass of an ABS resin. % Of polyamide / ABS resin composition consisting of 5% by weight of acid-modified styrene elastomer 5-20% by weight, unsaturated carboxylic acid, unsaturated dicarboxylic acid or its acid anhydride 0.05-5 parts by weight, radical generation A resin composition obtained by melt-kneading 0.01 to 3 parts by mass of an agent.
(2) The resin composition according to (1), wherein the polyamide is nylon 6.
(3) (melting point + 15 ° C.) to (melting point + 25 ° C.) of the polyamide, the melt mass flow rate measured at a load of 49 N is 40 to 100 g / 10 minutes, and measured at 220 ° C. of the ABS resin and a load of 98 N. The resin composition according to any one of (1) to (2), wherein the melt mass flow rate is 15 to 25 g / 10 min.
(4) The resin composition according to any one of (1) to (3), wherein the acid-modified styrene elastomer is an acid-modified styrene-ethylene-butylene-styrene block copolymer (SEBS).
(5) A resin molded product constituting a ship body or a member attached to the ship formed by molding the resin composition according to any one of (1) to (4).

  According to the present invention, a resin composition having low water absorption, dimensional stability, mechanical properties upon water absorption, heat resistance, moldability, chemical resistance, and low specific gravity can be obtained. And it uses as a molded object useful in the field | area of a motor vehicle, a motorcycle, a ship part, an electrical machinery electronic part, miscellaneous goods, etc. using the outstanding performance.

  Hereinafter, the present invention will be described in detail.

  The polyamide in the present invention is a polymer having an amide bond in the main chain mainly composed of aminocarboxylic acid, lactam or diamine and dicarboxylic acid (including a pair of salts thereof). Specific examples of the raw material include aminocarboxylic acid such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid and the like. Examples of the lactam include ε-caprolactam, ω-undecanolactam, and ω-laurolactam. Examples of diamines include tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 2,4- Dimethyloctamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2, There are 2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine and the like. Examples of dicarboxylic acids include adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfo Examples include isophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid. These diamines and dicarboxylic acids can also be used as a pair of salts.

  Preferred examples of such polyamides include polycaproamide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polycaproamide / polyhexamethylene adipamide copolymer ( Nylon 6/66), polyundecamide (nylon 11), polycaproamide / polyundecamide copolymer (nylon 6/11), polydodecamide (nylon 12), polycaproamide / polydodecamide copolymer (nylon 6/12), poly Hexamethylene sebamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyundecamethylene adipamide (nylon 116), polyhexamethylene isophthalamide (nylon 6I), polyhexamethylene terephthalamide (Niro) 6T), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polycaproamide / polyhexamethylene isophthalamide copolymer ( Nylon 6 / 6I), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polytrimethylhexamethylene Terephthalamide (nylon TMDT), polybis (4-aminocyclohexyl) methane dodecamide (nylon PACM12), polybis (3-methyl-4-aminocyclohexyl) methane dodecamide (Na Ron dimethyl PACM12), poly-m-xylylene adipamide (nylon MXD6), polyundecamethylene terephthalamide (nylon 11T), and mixtures thereof or copolymers thereof. Of these, nylon 6 and nylon 66 are preferable, and nylon 6 is particularly preferable.

  The swellable fluoromica mineral used in the present invention generally has a structural formula represented by the following formula.

M _α (Mg _γ Li _β ) Si ₄ O _δ F _ε
(In the formula, M represents an ion-exchangeable cation, specifically sodium or lithium. A, b, γ, δ, and ε each represent a coefficient, and 0 ≦ α ≦ 0.5, 0 ≦ β ≦ 0.5, 2.5 ≦ γ ≦ 3, 10 ≦ δ ≦ 11, 1.0 ≦ ε ≦ 2.0)
As a method for producing such a swellable fluorine mica, for example, silicon oxide, magnesium oxide and various fluorides are mixed, and the mixture is completely melted in a temperature range of 1400 to 1500 ° C. in an electric furnace or a gas furnace. A melting method in which a crystal of swellable fluorinated mica grows in the reaction vessel during the cooling process.

On the other hand, there is a method in which talc [Mg ₃ Si ₄ O ₁₀ (OH) ₂ ] is used as a starting material, and alkali metal ions are intercalated to impart swelling property to obtain a swellable fluorine mica (Japanese Patent Laid-Open No. Hei. No. 2-149415). In this method, swellable fluoromica can be obtained by heat-treating talc and alkali silicofluoride mixed at a predetermined blending ratio in a magnetic crucible at a temperature of 700 to 1200 ° C. for a short time.

  At this time, the amount of alkali silicofluoride mixed with talc is preferably in the range of 10 to 35 mass% of the entire mixture. If it is out of this range, the yield of swellable fluorinated mica tends to decrease.

  In the present invention, there is no particular limitation on the initial particle size of the swellable fluoromica mineral. The initial particle size is a particle size of a swellable fluoromica-based mineral as a raw material used in producing the polyamide composition used in the present invention, and is different from the size of the silicate layer in the composite material. However, this particle size also has a considerable influence on the physical properties of the obtained polyamide composite material, in particular the rigidity and heat resistance. Therefore, it is desirable to take this point into consideration when selecting the mixing ratio of the swellable fluoromica mineral, and it is preferable to control the particle size by pulverizing with a jet mill or the like as necessary.

  Here, when the swellable fluoromica mineral is synthesized by the intercalation method, the initial particle size can be changed by appropriately selecting the particle size of talc as a raw material. This is a preferable method in that the initial particle diameter can be adjusted in a wider range by using in combination with pulverization.

  The polyamide obtained by polymerizing monomers in the presence of the swellable fluoromica mineral in the present invention is a polyamide matrix in which a silicate layer of a swellable fluoromica mineral is dispersed at a molecular level. Here, the silicate layer is a basic unit constituting the swellable fluoromica-based mineral, and is a plate-like inorganic crystal obtained by breaking the layer structure of the swellable fluoromica-based mineral (hereinafter referred to as “cleavage”). It is. The silicate layer in the present invention means a state in which each silicate layer or a polyamide molecular chain is inserted between the layers, but the laminated structure is not completely broken. It does not have to be cleaved to a single sheet. Also, being dispersed at the molecular level means that when the silicate layer of the swellable fluoromica mineral is dispersed in the polyamide matrix, it maintains an average interlayer distance of 1 nm or more and does not form a lump with each other. The state which is doing. Here, the lump refers to a state in which the swellable fluoromica mineral as a raw material is not cleaved at all. The interlayer distance is the distance between the centers of gravity of the silicate layers. Such a state can be confirmed by performing observation with a transmission electron microscope, for example, on the test piece of the polyamide composite material.

  As a method for producing a polyamide containing a swellable fluoromica-based mineral, there is a method in which a polyamide and a swellable fluoromica-based mineral are melt-kneaded using a general extruder, but a polyamide is formed as in the present invention. The monomer is polymerized in a state where a predetermined amount of the swellable fluoromica mineral is present with respect to the monomer to be dispersed, so that the swellable fluoromica mineral is sufficiently finely dispersed in the polyamide, and the effect of the present invention is most remarkable. appear.

  The swellable fluoromica-based mineral contained in the polyamide in the present invention needs to be 0.01 to 20% by mass, preferably 0.01 to 18% by mass, and more preferably 0.01 to 15% by mass. It is. If the swellable fluoromica-based mineral contained in the polyamide exceeds 20% by mass, the toughness is greatly lowered, which is not preferable. Further, when the swellable fluoromica-based mineral contained in the polyamide (A) is 0.01% by mass or less, the effect of improving the mechanical strength, particularly the flexural modulus, heat distortion temperature, and dimensional stability, which is the object of the present invention. Cannot be obtained.

  Examples of the ABS resin in the present invention include a terpolymer obtained by emulsion polymerization of acrylonitrile, butadiene and styrene, a mixture of acrylonitrile-styrene resin and nitrile rubber (acrylonitrile-butadiene rubber), and a graft copolymer of styrene on nitrile rubber. Although known ones such as these can be used, a terpolymer obtained by emulsion polymerization is preferably used. The copolymer composition is 15 to 80% by mass of the butadiene component, 85 to 20% by mass of the total of the acrylonitrile component and the styrene component, and a mass ratio of acrylonitrile component to styrene component of 5/95 to 50/50 is appropriate. is there.

  In addition to these three components, a small amount of a copolymer component such as isoprene, phenylmaleimide, methyl acrylate, or methyl methacrylate may be contained.

  The compounding amount of polyamide and ABS must be polyamide / ABS = 40/60 to 80/20% by mass, and more preferably 45/55 to 70/30% by mass, including a swellable fluoromica mineral. If the polyamide is less than 40% by mass, the heat resistance is lowered and the mechanical properties are significantly lowered. Moreover, when polyamide exceeds 80 mass%, the dimensional change by water absorption is large and is not preferable.

  In the present invention, the melt mass flow rate of polyamide and ABS must be as follows. The melt mass flow rate of polyamide (melting point + 15 ° C.) to (melting point + 25 ° C.) measured at a load of 49 N is 40 to 100 g / 10 min, and the ABS resin has a melt mass flow rate of 220 ° C. and a load of 98 N. Must be 15-25 g / 10 min. If it is out of this range, mixing of the polyamide and ABS resin is insufficient, and the desired mechanical strength and heat distortion temperature cannot be obtained.

  The acid-modified styrene elastomer used in the present invention may be a hydrogenated or non-hydrogenated styrene / butadiene copolymer, or a hydrogenated or non-hydrogenated styrene / isoprene copolymer, which are random copolymers. Any of block copolymers, graft copolymers, and the like may be used, and a polymerizable monomer having a functional group is introduced into a part of the polymer. Examples of the polymerizable monomer having a functional group used herein include aliphatic carboxylic acids such as acrylic acid, methacrylic acid, maleic acid and itaconic acid, and aliphatic carboxylic anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride. Hydroxyl anhydrides such as acid, phthalic anhydride, trimellitic anhydride, hydroxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, lactone-modified hydroxyethyl (meth) acrylate and other hydroxyl-containing materials, glycidyl (meth) acrylate And epoxy group-containing vinyls such as methyl glycidyl (meth) acrylate, etc., and two or more of these may be used in combination. There is no problem even if some of them do not react with these polymerizable monomers. Among these acid-modified styrene elastomers, an acid-modified styrene-ethylene-butylene-styrene block copolymer (SEBS) is preferably used. When acid-modified styrene elastomer is not used, or when unmodified styrene-ethylene-butylene-styrene block copolymer and polyolefin elastomer are used instead of acid-modified styrene elastomer, both when water is not absorbed and when water is absorbed A sufficient Izod impact strength cannot be obtained.

  These acid-modified styrene-based elastomers need to be blended in an amount of 5 to 20 parts by mass, more preferably 5 to 15% by mass with respect to 100 parts by mass of the polyamide / ABS resin composition. If the amount is less than 5 parts by mass, the improvement in toughness is poor, and if it exceeds 20 parts by mass, the mechanical strength, particularly the flexural modulus and the heat distortion temperature are greatly decreased.

  Specific examples of the unsaturated carboxylic acid, unsaturated dicarboxylic acid or acid anhydride thereof used in the present invention include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, quitic acid, and oleic acid, maleic acid, and itaconic acid. , Chloromaleic acid, citraconic acid, butenyl succinic acid, tetrahydrosuccinic acid, and anhydrides thereof, and one or more of these can be used. Of these, maleic anhydride is particularly preferred for economic reasons. These unsaturated carboxylic acid, unsaturated dicarboxylic acid or acid anhydride thereof needs to be blended in an amount of 0.05 to 5 parts by mass with respect to 100 parts by mass of the polyamide / ABS resin composition. If the amount is less than 0.05 parts by mass, the compatibility between the polyamide and the ABS resin is poor, and the mechanical strength is lowered. If the amount exceeds 5 parts by mass, the material becomes brittle and the mechanical strength is lowered.

  Specific examples of the radical generator used in the present invention include organic peroxides such as ketone oxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, such as parachlorobenzoyl peroxide. Oxide, 2,4-dichlorobenzoyl peroxide, tertiary butyl cumyl peroxide, ditertiary butyl peroxide, dicumyl peroxide, benzoyl peroxide, 2,5-dimethyl-2,5-di (tertiary butyl peroxide ) Hexin-3,2,5-dimethyl-2,5-di (tertiary butyl peroxy) hexane, tertiary butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydropa Oxide, acetyl peroxide, octanoyl peroxide, and the like can be used 3,5,5-trimethyl hexanoyl peroxide. The blending amount of these radical generators needs to be 0.01 to 3 parts by mass with respect to 100 parts by mass of the polyamide / ABS resin composition. Less than 0.01 parts by mass is not preferable because radical generation is small and the unsaturated carboxylic acid does not react efficiently. Moreover, even if it mixes exceeding 3 mass parts, since an effect does not change, it is economically unpreferable.

  In the present invention, the resin composition is produced by melt-kneading the constituent components. In that case, as a melt-kneading apparatus used for producing the resin composition, a Banbury mixer, a roll mixer, a kneader, a single-screw extruder, a multi-screw extruder, or the like can be used.

  In addition, as a method for supplying the components constituting the resin composition of the present invention to the melt-kneading apparatus, first, the ABS resin, the unsaturated carboxylic acid compound and the radical generator are supplied from the supply port on the far side as viewed from the tip of the extruder. There is a method of supplying the polyamide and the acid-modified styrenic elastomer from a supply port on the side close to the tip. If this method is used, a resin composition having better performance can be obtained.

  As long as the characteristic is not impaired significantly, you may mix | blend another polymer with the resin composition of this invention as needed. In this case, the blending amount is desirably 30% by mass or less with respect to the resin composition. Such polymers include styrene polymers, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, polyetherimide, polyphenylene sulfide, polyphenylene ether, PMMA, polyvinyl chloride, phenoxy resin, liquid crystal polymer, polyolefin elastomer and the like can be mentioned.

  In addition, pigments, heat stabilizers, antioxidants, weathering agents, flame retardants, plasticizers, mold release agents, other reinforcing materials, etc. should be added to the resin composition of the present invention as long as the properties are not significantly impaired You can also. Examples of such heat stabilizers and antioxidants include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, and copper compounds. Common benzophenones and benzotriazoles are used as the weathering agent. As the flame retardant, a general phosphorus flame retardant or a halogen flame retardant is used. Examples of reinforcing materials include clay, talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, aluminum hydroxide, Calcium hydroxide, barium sulfate, potassium alum, sodium alum, iron alum, glass balloon, carbon black, zinc oxide, antimony trioxide, boric acid, borax, zinc borate, zeolite, hydrotalcide, metal fiber, metal Examples include whisker, ceramic whisker, potassium titanate whisker, boron nitride, mica, graphite, glass fiber, and carbon fiber.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the physical-property measurement of the molded article in an Example and a comparative example was performed as follows.
<Measurement method>
(1) Specific gravity: Measured according to ASTM D297-93-16.
(2) Equilibrium water absorption and change in water absorption dimension: Using a square test piece with a thickness of 3 mm and a side of 20 mm, the equilibrium water absorption is determined from the change in weight when the equilibrium water absorption is reached under the conditions of 23 ° C. and 50% relative humidity. Further, the dimensional change in the flow direction and the perpendicular direction during molding was measured, and the average value was taken as the dimensional change. A water absorption dimensional change of 0.15% or less was accepted.
(3) Flexural modulus: Measured according to ASTM D790 using a test piece having a width of 12.5 mm, a length of 125 mm, and a thickness of 3.2 mm. Further, water was absorbed up to equilibrium water absorption under the conditions of 23 ° C. and relative humidity 50%, and the same measurement was performed. A value after water absorption of 1.8 GPa or more was considered acceptable.
(4) Izod impact strength: Measured according to ASTM D256 using a test piece similar to (3). Further, water was absorbed up to equilibrium water absorption under the conditions of 23 ° C. and relative humidity 50%, and the same measurement was performed. A value after water absorption of 80 J / m or more was considered acceptable.
(5) Melt mass flow rate (MFR): Measured according to JIS K7210.
(6) Melting point: Measured using a DSC (DSC22 manufactured by Seiko Denshi Kogyo Co., Ltd.) at a heating rate of 20 ° C./min in a nitrogen atmosphere.
(7) Heat distortion temperature (HDT): Measured with a load of 0.45 MPa according to ASTM D648 using the same test piece as in (3).
<Raw material>

(1) Swellable fluorine mica To talc pulverized so as to have an average particle diameter of 4.0 μm by a ball mill, sodium silicofluoride having an average particle diameter of 10 μm was mixed so that the total amount was 15% by mass. This was put in a magnetic crucible and reacted at 850 ° C. for 1 hour in an electric furnace to obtain a swellable fluorine mica (M-1) having an average particle size of 4.0 μm. The composition of this swellable fluorinated mica was Na _0.60 Mg _2.63 Si ₄ O ₁₀ F _1.77 and the cation exchange capacity was 110 meq / 100 g.
The cation exchange capacity was determined on the basis of the bentonite (powder) cation exchange capacity measurement method (JBAS-106-77) by the Japanese Bentonite Industry Association standard test method.

(2) Polyamide 1) Polyamide (N-1):
500 g of swellable fluorine mica was added to a solution obtained by mixing 1 kg of ε-caprolactam and 500 g of water, and stirred at room temperature for 1.5 hours using a homomixer. The total amount of this dispersion was charged in an autoclave with an internal volume of 30 liters that had been previously charged with 9 kg of ε-caprolactam and melted at 95 ° C., heated to 260 ° C. with stirring, and pressurized to 0.7 MPa. Thereafter, while gradually releasing water vapor, the temperature of 260 ° C. and the pressure of 0.7 MPa were maintained for 1 hour, and the pressure was released to normal pressure over 1 hour, followed by polymerization for 30 minutes while allowing nitrogen to flow. When the polymerization was completed, the reaction product was discharged into a strand shape, cooled, solidified, and then cut to obtain a pellet made of a polyamide resin composition. Next, this pellet was refined with hot water at 95 ° C. for 8 hours and then dried to obtain polyamide (N-1). The obtained polyamide (N-1) had a relative viscosity of 2.5, MFR of 65 g / 10 min (250 ° C., 49 N), and a melting point of 226 ° C.
2) Polyamide (N-2):
150 kg of 3 kg of water and 500 g of swellable fluorinated mica are mixed with 10 kg of nylon 66 salt, and the mixture is placed in a reaction vessel having an internal volume of 30 liters. Polymerization was performed to obtain a reinforced nylon 66 resin composition. The polymerization reaction was performed as follows. That is, while stirring at 230 ° C., heating was performed until the internal pressure reached 18 kg / cm ² . After reaching the pressure, the pressure was maintained by heating while gradually releasing water vapor. When the temperature reached 280 ° C., the pressure was released to normal pressure, and polymerization was further performed for 2 hours. When the polymerization was completed, the reinforced nylon 66 resin composition was dispensed, cut, and dried to obtain polyamide (N-2). The obtained polyamide (N-2) had a relative viscosity of 2.6, MFR of 60 g / 10 min (280 ° C., 49 N), and a melting point of 264 ° C.
3) Polyamide (N-3): Nylon 6 (Nylon 6 resin manufactured by Unitika A1030BRL, relative viscosity 2.5, MFR 90 g / 10 min (250 ° C. 49 N), melting point 226 ° C.)
4) Polyamide (N-4): nylon 66 (nylon 66 nylon 66 resin A125, relative viscosity 2.8, MFR 40 g / 10 min (280 ° C. 49 N), melting point 264 ° C.)

(3) ABS resin 1) ABS resin (A-1):
Acrylonitrile-styrene-butadiene copolymer (Techno ABS 110, MFR 23.0 g / 10 min, manufactured by Technopolymer)
2) ABS resin (A-2):
Acrylonitrile-styrene-butadiene copolymer (Techno ABS 130, MFR 18.0 g / 10 min, manufactured by Technopolymer Co., Ltd.)

(4) Elastomer 1) Elastomer (E-1):
Acid-modified styrene-ethylene-butadiene-styrene block copolymer (Tuftec M1943 manufactured by Asahi Kasei Chemicals)
2) Elastomer (E-2):
Styrene-ethylene-butadiene-styrene block copolymer (Tuftec H1041 manufactured by Asahi Kasei Chemicals)
3) Elastomer (E-3):
Acid-modified polyolefin elastomer copolymer (Tafmer MH7020 manufactured by Mitsui Chemicals)

(5) Unsaturated carboxylic acid compound (M-1):
Maleic anhydride (special grade reagent)

(6) Radical generator (R-1):
2,5-dimethyl-2,5-bis (tertiary butyl peroxy) hexyne-3 (Nippon Yushi Co., Ltd. perhexine 25B-40)

Examples 1-7, Comparative Examples 1-10
After mixing the raw materials with the formulation shown in Table 1 in both Examples and Comparative Examples, the mixture was melt-kneaded and pelletized with a twin screw extruder (TEM-37, manufactured by Toshiba Machine Co., Ltd.). The extrusion temperature was 280 ° C. for Example 2 and Comparative Example 4, and 260 ° C. for the others. After drying the obtained pellets, a test piece was molded using an injection molding machine (IS-80G manufactured by Toshiba Machine Co., Ltd.) with the cylinder temperature being the same as the extrusion temperature and the mold temperature being 80 ° C. Various performance evaluations were performed using the obtained test pieces. The results are listed in Table 2.

  Examples 1 to 7 were excellent in mechanical properties, mechanical properties during water absorption, and dimensional stability.

Since Comparative Example 1 did not use an acid-modified styrene elastomer, the Izod impact strength before and after water absorption was low. In Comparative Example 2, since the blending amount of the polyamide exceeded the range of the present invention, the dimensional stability during water absorption was poor. In Comparative Example 3, since the blending amount of the polyamide was less than the lower limit of the range of the present invention, the flexural modulus and heat deformation temperature before and after water absorption were inferior. Since Comparative Example 4 and Comparative Example 5 used nylon 6 containing no swellable fluorine mica, the dimensional stability during water absorption, the flexural modulus after water absorption, and the heat distortion temperature were inferior. In Comparative Example 6, a large amount of acid-modified styrene elastomer was blended beyond the scope of the present invention, so that the flexural modulus after heat absorption and the heat distortion temperature were inferior. Since the comparative example 7 used the styrene-type elastomer which is not acid-modified, the Izod impact strength before and after water absorption was low. Since the comparative example 8 used the polyolefin-type elastomer, the Izod impact strength before and after water absorption was low. In Comparative Example 9, since maleic anhydride and 2,5-dimethyl-2,5-bis (tertiary butyl peroxy) hexyne-3 were not blended, bending elastic modulus before and after water absorption, Izod impact strength, thermal deformation The temperature was inferior. Comparative Example 10 is more than the scope of the present invention, and since 2,5-dimethyl-2,5-bis (tertiarybutylperoxy) hexyne-3 was blended, it became brittle and the mechanical strength was greatly reduced. did.

Claims (5)

It consists of 40 to 80% by mass of a polyamide containing 0.01 to 20% by mass of a swellable fluoromica based mineral obtained by polymerizing monomers in the presence of a swellable fluorinated mica-based mineral, and 60 to 20% by mass of an ABS resin. 5 to 20 parts by mass of an acid-modified styrenic elastomer, 0.05 to 5 parts by mass of an unsaturated carboxylic acid, an unsaturated dicarboxylic acid or an acid anhydride thereof, and 100% by mass of a polyamide / ABS resin composition. A resin composition obtained by melt-kneading 01 to 3 parts by mass. The resin composition according to claim 1, wherein the polyamide is nylon 6. The melt mass flow rate of the polyamide (melting point + 15 ° C.) to (melting point + 25 ° C.) measured at a load of 49 N is 40 to 100 g / 10 min, and the ABS resin has a melt mass flow of 220 ° C. and a load of 98 N. The resin composition according to claim 1, wherein the rate is 15 to 25 g / 10 minutes. The resin composition according to any one of claims 1 to 3, wherein the acid-modified styrene elastomer is an acid-modified styrene-ethylene-butylene-styrene block copolymer (SEBS). The resin molded product which comprises the member attached to a ship main body or a ship formed by shape | molding the resin composition in any one of Claims 1-4.