TW201720863A - High-melt-viscosity polyamide resin composition - Google Patents

Abstract

The present invention provides a polyamide resin composition having a high melt viscosity, which is able to be molded by extrusion molding, blow molding, expansion molding or the like in addition to exhibiting good thermal aging resistance that is capable of withstanding a high temperature environment at around 200 DEG C. This polyamide resin composition contains, per 100 parts by mass of a polyamide resin, 0.5-20 parts by mass of a metal cyanide salt represented by general composition formula (Ax[M(CN)y]), 2-30 parts by mass of a thickening agent and 0-140 parts by mass of an inorganic reinforcing material. In the general composition formula, M represents a specific transition metal element, and A represents an alkali metal or an alkaline earth metal.

Description

High melt viscosity polyamine resin composition

The present invention relates to a polyamide resin composition which has a high melt viscosity and can be molded into a molded article excellent in heat aging resistance, such as extrusion molding, blow molding, and foam molding.

The polyamide resin has excellent properties such as chemical resistance and moldability, and has been widely used in various parts such as automobile parts, electric and electronic parts, and industrial machine parts. Although the polyamide resin is a resin of a class excellent in heat aging resistance, it cannot avoid deterioration due to heat and light, and it is known to add a copper halide, a potassium halide, and an evil method in order to improve heat aging resistance. A method of using an oxazole compound or the like as a thermal stabilizer (for example, Patent Document 1).

By such techniques, in the field of automotive parts or electrical and electronic parts, polyamide resin is used in parts exposed for use in a high temperature environment of about 140 °C. However, for example, in the engine room of an automobile, in recent years, with an increase in engine power and a high density of parts, the ambient temperature in the engine room has become high, and there has been a demand for heat aging resistance which has not been seen before.

On the other hand, there has been proposed a method in which polyamide is blended with fine particulate iron (Patent Document 2), a method in which a polyamide powder is dispersed in a metal powder (Patent Document 3), and two types of polycondensation having different melting points. Method for blending copper compound with iron oxide in a mixture of guanamine (Patent Document 4), method for mixing a thermal stabilizer such as copper iodide or potassium iodide, and a composite oxide of triiron tetroxide (including iron (II) oxide) (Patent Document 5) and the like, the composition is excellent in heat aging resistance even in a high temperature environment of about 200 °C. However, the method of Patent Document 2 or 3 has a risk of fire in the manufacture of the composition, and is not easy to manufacture. The method of Patent Document 4 has a drawback that only a very limited composition exhibits an effect, and the method of Patent Document 5, The stability and reproducibility of the heat aging resistance or mechanical strength are inferior, and there is room for improvement in each case. It is still not known to improve the disadvantages of these, and further, it is possible to carry out a high-melting viscosity polyamine resin composition which is formed by extrusion molding, blow molding, foam molding or the like. [Prior Technical Literature] [Patent Literature]

Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2008-527. 5: Japanese Special Open 2010-270318

[Problem to be Solved by the Invention] The present invention provides a polyamidamide resin composition which not only has heat aging resistance capable of withstanding a high temperature environment of about 200 ° C, but also has a shape for extrusion, blow molding, foam molding, and the like. High melt viscosity of forming. [Means for solving the problem]

In order to solve the problem of heat aging resistance, the inventors of the present invention have conducted intensive studies on a transition metal compound such as iron, and have studied the composition suitable for blow molding or the like. As a result, the present invention has been completed. That is, the present invention is as follows. [1] A polyamine resin composition comprising: 0.5 to 20 parts by mass of a metal cyanide salt (A) having the following general composition formula (1), and a tackifier, with respect to 100 parts by mass of the polyamide resin (B) 2~30 parts by mass and inorganic reinforcing material (C) 0~140 parts by mass; general composition formula (1)...A _x [M(CN) _y ]; In general composition formula (1), M is periodic table At least one of the transition metal elements of the 5th to 10th and 4th to 6th cycles, A is at least one of an alkali metal and an alkaline earth metal, y is an integer of 3 to 6, and x is (ym)/ The value obtained by a; here, m is the valence of M, and a is the valence of A. [2] The polyamide resin composition according to [1], wherein M of the general composition formula (1) is iron. [3] The polyamine resin composition according to [1], wherein the metal cyanide salt (A) of the general composition formula (1) is selected from the group consisting of alkali metal salts of hexacyanoferrate (II) and hexacyano One or more of the base metal (III) acid-base metal salts. [4] The polyamine resin composition according to any one of [1] to [3], wherein the copper compound is contained in an amount of 0.0001 to 1 part by mass based on 100 parts by mass of the polyamine resin composition. . [5] The polyamine resin composition according to any one of [1] to [4] wherein the tackifier (B) is selected from the group consisting of polyfunctional epoxy compounds (i), having a carboxylic acid group, and An ethylene-based copolymer (ii) of at least one of a carboxylic anhydride group, an ionic polymer (iii) of an olefin/acrylic acid/anhydride terpolymer, and a group of a styrene-based elastomer (iv) having a carboxylic anhydride group At least one of them. [Effects of the Invention]

The polyamidamide resin composition of the present invention is excellent in heat aging resistance not only in a high temperature environment of about 200 ° C, but also has high melt viscosity, so that it can be formed into a molded product, a blow molded product, a foam molded product, and the like. The formation of the product.

The present invention will be specifically described below. The polyamine resin of the present invention is not particularly limited, and examples thereof include a ring-opening polymer of a cyclic decylamine, a polycondensate of an aminocarboxylic acid, and a polycondensate of a dibasic acid and a diamine. Examples of the co-polymers and the like include polyhexylamine (polyamine 6), polyhexamethylene hexamethylenediamine (polyamine 66), and polytetramethylene hexamethylenediamine. (polyamido 46), polyhexamethylene decylamine (polyamide 610), polyhexamethylene dodecylamine (polyamide 612), polydodecanamide (polyamine 12) ), poly-11-aminoundecanoic acid (polyamine 11) and other aliphatic polyamines, poly(m-xylylenediamine) (polyamine MXD6), poly(hexamethylene-p-phenylene) Methotrexate (polyamide 6T), poly(hexamethylene metabenzamide) (polyamine 6I), poly (nonamethylene terephthalamide) (polyamine 9T) An aliphatic-aromatic polyamine such as poly(tetramethylene metabenzamide) (polyamine 4I) and copolymers or mixtures thereof. Particularly, as the polyamine which is suitable for the present invention, polyamine 6, polyamine 66, polyamine 6/66 copolymer, polyamide 66/6T copolymer, and polyamine 6T/12 copolymer are mentioned. , Polyamine 6T / 11 copolymer, polyamine 6T / 6I copolymer, polyamine 6T / 6I / 12 copolymer, polyamine 6T / 610 copolymer, polyamine 6T / 6I / 6 copolymer.

The above polyamine resins may be used singly or in combination of two or more. In the case where a plurality of polyamine resins are used as a combination of a polyamine resin having a low oxygen permeability, it is preferable from the viewpoint of heat aging resistance.

The molecular weight of such a polyamide resin is not particularly limited, and a polyamide resin having a relative viscosity of 1.7 to 4.5 as measured at a concentration of 1% by mass and 25 ° C in 98% (98% by mass) sulfuric acid is preferably used. The relative viscosity of the polyamide resin is preferably from 2.0 to 4.0, further preferably from 2.0 to 3.5.

The metal cyanide salt (A) of the present invention means the one represented by the following general composition formula (1). General composition formula (1)...A _x [M(CN) _y ] (In general composition formula (1), M is at least one of transition metal elements of Groups 5 to 10 and 4 to 6 cycles of the periodic table; A is at least one of an alkali metal and an alkaline earth metal, y is an integer of 3 to 6, and x is a value obtained by (ym)/a; here, m is a valence of M, and a is A Valence) Metal cyanide salt (A) can be a hydrate.

M of the above general composition formula (1) is at least one of transition metal elements of the 5th to 10th and 4th to 6th cycles of the periodic table, and examples of the ideal metal element include Fe, Co, and Cr. , Mn, Ir, Rh, Ru, V, Ni. If the valence of the metal element is also considered, it is preferably Fe(II), Fe(III), Co(III), Cr(III), Mn(II), Mn(III), Ir(III), Rh(III). , Ru(II), V(IV), V(V), Co(II), Ni(II), Cr(II), more preferably Co(II), Co(III), Fe(II), Fe (III), Cr(III), Ir(III), Ni(II), particularly preferably Fe(II), Fe(III). Two or more metals (for example, hexacyanocobalt(II) iron (II) potassium) may be present in the metal cyanide salt (A). A is at least one of an alkali metal (for example, Li, Na, K) and an alkaline earth metal (for example, Ca or Ba). y is an integer from 3 to 6, and x is selected to make the metal cyanide salt (A) electrically neutral. That is, x is the value obtained by (y-m)/a (here, m is the valence of M, and a is the valence of A). In particular, y corresponds to the coordination number of M, preferably 4 to 6, especially preferably 6. The metal cyanide salt (A) which can be used in the present invention, although not limited, is preferably potassium hexacyanoferrate, potassium hexacyanoferrate, potassium hexacyanoferrate Sodium, sodium hexacyanoferrate (III), potassium hexacyanocobaltate, potassium hexacyanocobaltate, potassium hexacyanocobaltate, potassium hexacyanocobaltate Calcium, potassium tetracyano(II) acid, potassium hexacyanochromate (III), potassium hexacyanoate (III), calcium hexacyanoferrate, calcium hexacyanocobalt (II) Potassium and lithium hexacyanocobaltate (III) are more suitable for the operability and safety, and are more preferably potassium hexacyanoferrate, potassium hexacyanoferrate or potassium hexacyanoferrate. II) Sodium, sodium hexacyanoferrate (III).

In the present invention, the blending amount (content) of the metal cyanide salt (A) is from 0.5 to 20% by mass based on 100 parts by mass of the polyamide resin. The blending amount of the metal cyanide salt (A) is preferably 0.5 to 15 parts by mass, more preferably 1 to 13 parts by mass, further preferably 1 to 12 parts by mass, particularly preferably 1 to 10 parts by mass. In the case of less than 0.5 part by mass, the effect of heat aging resistance is hardly exhibited, and even if it exceeds 20 parts by mass, the effect of the heat aging resistance exhibited is not increased more. When the metal cyanide salt (A) is 20 parts by mass or less, metal particles or metal oxide particles have little adverse effect on different mechanical properties, and particularly, glass fiber breakage can be suppressed in the glass fiber reinforced composition. Almost no mechanical properties are lowered. When the metal cyanide salt (A) is a hydrate, the blending amount thereof is considered in consideration of the quality of the compound containing the water of hydration.

The reason why the above metal cyanide salt (A) exhibits an effect of improving heat aging resistance in the present invention is not clear, and it is considered that it may be because the above metal cyanide salt (A) is in the vicinity of the surface layer of the composition with the polyamide resin. Interaction, and play a barrier to inhibit oxygen transmission. Further, the metal cyanide salt (A) used in the present invention can suppress the mechanical property lowering of the blended polyamide resin composition as compared with the iron compound such as iron oxide which has been conventionally used as a heat-resistant aging compound. . The iron oxide-based mineral is a metal oxide and has a Mohs hardness of 6 and is extremely hard. In the polyamide resin composition containing glass fibers, mechanical properties are lowered due to breakage of the glass fibers. On the other hand, since the metal cyanide salt (A) is not a mineral, the glass fiber is not damaged in the polyamide resin composition containing the glass fiber, so that the mechanical properties are excellent.

In the present invention, a conventional thermal stabilizer may be used in addition to the above metal cyanide salt (A).

The copper compound which can be used in the present invention may, for example, be copper acetate, copper iodide, copper bromide, copper chloride, copper fluoride, copper laurate or copper stearate. These copper compounds may be used singly or in combination. Copper acetate, copper iodide, copper bromide, copper chloride is preferred, and copper (II) bromide is particularly preferred. The content of the copper compound is preferably 0.0001 to 1 part by mass based on the copper in the copper compound, based on 100 parts by mass of the polyamide resin. When the amount is less than 0.0001 parts by mass, the effect of preventing discoloration in a more severe environment under a high-temperature environment and ultraviolet irradiation is unsatisfactory. If more than 1 part by mass, the effect of preventing discoloration in the above-mentioned severe environment is extremely high. In addition, there are problems such as corrosion of the mold or the screw or cylinder of the extruder or the forming machine. A more desirable content is 0.0005 to 1 part by mass, and the content is further preferably 0.005 to 0.2 parts by mass.

Further, when a copper compound is added, it is preferred to use a halogenated alkali metal compound such as potassium iodide or potassium bromide. The precipitation of copper can be prevented by using these together. The method of adding the copper compound can be added at any stage of the production of the polyamide resin, and the method of addition is not limited. For example, a method of adding a raw material salt aqueous solution of polyamine, a method of injecting to a molten polyamine in the middle of melt polymerization, a polyamide pellet obtained by granulating a polymerization, and a powder of the copper compound or The method in which the master batch is mixed and then melt-kneaded using an extruder or a molding machine or the like may be any of the above methods.

Further, in the present invention, an auxiliary stabilizer such as an antioxidant such as a hindered phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, or an amine-based antioxidant, or a light stabilizer may be blended.

As the hindered phenol-based antioxidant, a conventional compound can be used. These compounds can be used singly or in combination. Among such hindered phenolic antioxidants, it is preferred that the phenol is a bifunctional or higher functional group, and triethylene glycol-bis(3-(3-tert-butyl-5-methyl-4-hydroxyl) is difficult to discolor. A semi-blocked type such as phenyl)propionate (IRGANOX245) is preferred.

When the hindered phenol-based antioxidant is blended, the blending amount (content) of the hindered phenol-based antioxidant is preferably 0.05 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the polyamide resin. When the amount is less than 0.05 parts by mass, the effect of preventing thermal discoloration is unsatisfactory. On the other hand, if it exceeds 3 parts by mass, the effect may be saturated or blooming may occur on the surface of the molded article.

The phosphorus-based antioxidant is at least one selected from the group consisting of inorganic and organic phosphorus-based antioxidants. Examples of the inorganic phosphorus-based antioxidant include hypophosphites such as sodium hypophosphite, phosphites, and the like. As the organic phosphorus-based antioxidant, a commercially available organophosphorus-based antioxidant of a phosphite system can be used, and an organic phosphorus-containing compound which does not generate phosphoric acid by thermal decomposition is preferable. As the organic phosphorus-containing compound, a conventional compound can be used.

When the phosphorus-based antioxidant is blended, the blending amount (content) of the phosphorus-based antioxidant is preferably 0.05 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the polyamide resin. When the amount is less than 0.05 parts by mass, the effect of preventing thermal discoloration is unsatisfactory. On the other hand, if it exceeds 3 parts by mass, flashing may occur in the molded article. In the present invention, if an inorganic or organic phosphorus-based antioxidant is used in combination, the amount of the antioxidant to be blended can be reduced, which is preferable.

As the amine-based antioxidant which can be used in the present invention, a conventional compound can be used. Further, examples of the amine-based antioxidant include a secondary arylamine. The second-stage arylamine refers to an amine compound containing two carbon radicals chemically bonded to a nitrogen atom, and at least one of them is preferably an aromatic hydrocarbon.

When the amine-based antioxidant is blended, the amount (content) of the amine-based antioxidant is preferably 0.05 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the polyamide resin. When the amount is less than 0.05 parts by mass, the effect of preventing thermal discoloration is unsatisfactory. On the other hand, if it exceeds 3 parts by mass, the effect may reach saturation or bloom may occur on the surface of the molded article.

As the sulfur-based antioxidant which can be used in the present invention, a conventional compound can be used.

When the sulfur-based antioxidant is blended, the blending amount (content) of the sulfur-based antioxidant is preferably 0.05 to 3 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the polyamide resin. When the amount is less than 0.05 parts by mass, the effect of preventing thermal discoloration is unsatisfactory. On the other hand, if it exceeds 3 parts by mass, the effect may be saturated or blooming may occur on the surface of the molded article.

The light stabilizer which can be used in the present invention is preferably one or more hindered amine type light stabilizers (HALS). HALS is preferably a compound derived from a substituted piperidine compound, especially from an alkyl substituted piperidine or piperidine. a piperazinone compound, and a compound derived from an alkoxy-substituted piperidine compound. For such compounds, conventional compounds can be used.

In the present invention, a mixture of a 2-stage arylamine and a HALS can be used. An ideal embodiment is an auxiliary stabilizer comprising at least two, at least one selected from the group consisting of a arylamine of the order of 2, and at least one selected from the group of HALS. When the auxiliary stabilizer mixture is blended, the total blending amount (total content) of the auxiliary stabilizer mixture is preferably 0.5 to 10 parts by mass, more preferably 0.5 to 3 parts by mass, based on 100 parts by mass of the polyamide resin. When the amount is less than 0.5 part by mass, the effect of improving the heat aging resistance is insufficient. On the other hand, if it exceeds 10 parts by mass, the effect is saturated or the surface of the molded article is frosted.

The tackifier (B) of the present invention is not particularly limited as long as it can act on the polyamide resin to increase the melt viscosity of the polyamide resin, and can be bonded to the terminal amine group and terminal of the polyamide resin. Carboxyl or guanamine-based polyfunctional epoxy compound, polyfunctional isocyanate compound, polyfunctional carbodiimide compound, polyfunctional A polyfunctional compound such as an oxazoline compound, a polyfunctional carboxylic acid or a carboxylic anhydride compound.

For the polyfunctional epoxy compound, a polyepoxy propyl ether compound (for example, "SR-TMP" manufactured by Sakamoto Pharmaceutical Co., Ltd., "Denacol EX-521" manufactured by Nagase ChemteX Corporation, etc., etc., may be mentioned. ), a polyfunctional epoxy compound containing polyethylene as a main component (for example, "BONDFAST E" manufactured by Sumitomo Chemical Co., Ltd.), and a polyfunctional epoxy compound containing an acrylate resin as a main component (for example, "RESEDA GP" manufactured by Toagosei Co., Ltd. -301", "ARUFON UG-4000" manufactured by Toagosei Co., Ltd., "METABLEN KP-7653" manufactured by Mitsubishi Rayon Co., Ltd.), and polyfunctional epoxy compound containing acrylate resin and styrene copolymer as main components (For example, "Joncryl-ADR-4368" manufactured by BASF Corporation, "ARUFON UG-4040" manufactured by Toagosei Co., Ltd., "ARUFON UH-4070" manufactured by Toagosei Co., Ltd.), and an anthrone/acrylate resin copolymer as a main component. A polyfunctional epoxy compound (for example, "METABLEN S-2200" manufactured by Mitsubishi Rayon Co., Ltd.) and a polyfunctional epoxy compound containing polyethylene glycol as a main component (for example, "Epiol E" manufactured by Nippon Oil Co., Ltd. -10 00", etc.).

The polyfunctional isocyanate compound may, for example, be a monomer MDI (MDI: methylenebis(4,1-phenylene) diisocyanate) or a polymeric MDI (for example, "Millionate MR-200" manufactured by Nippon Polyurethane Industries Co., Ltd., "Lupranate M20S" manufactured by BASF Co., Ltd.), aromatic polyisocyanate (for example, "Millionate MT" manufactured by Nippon Polyurethane Industry Co., Ltd.), and the like.

Examples of the polyfunctional carbodiimide compound include aromatics; polycarbodiimides (for example, "STABAXOL P" manufactured by Rhein Chemie Corp., "STABAXOL P-400", etc.), and aliphatic (alicyclic) compounds. Polycarbodiimide (for example, "Carbodilite LA-1" manufactured by Nisshinbo Co., Ltd.).

Multifunctional As the oxazoline compound, 1,3-phenylene-bis Aromatic polycondensation Oxazoline A polymer of oxazoline (for example, "Epocros" manufactured by Nippon Shokubai Co., Ltd.).

Examples of the polyfunctional carboxylic acid and the carboxylic anhydride-based compound include pyrogallic anhydride, diphenyl ketone tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, and diphenyl sulfonium tetracarboxylic dianhydride. An ethylene-based copolymer of at least one of a carboxylic acid group and a carboxylic acid anhydride group, an ionic polymer of an olefin/acrylic acid anhydride/anhydride terpolymer, a styrene-based elastomer having a carboxylic acid anhydride group, or the like.

Among these, in consideration of the reactivity with the terminal group of the polyamide resin, it is preferably selected from the above-mentioned polyfunctional epoxy compound (i), and at least one of a carboxylic acid group and a carboxylic acid anhydride group. A group of the copolymer (ii), an ionic polymer (iii) of an olefin/acrylic acid/anhydride terpolymer, and a styrene elastomer (iv) having a carboxylic anhydride group.

In the ethylene-based copolymer (ii) having at least one of a carboxylic acid group and a carboxylic anhydride group, the carboxylic acid or an anhydride thereof is preferably selected from the group consisting of maleic acid, fumaric acid, itaconic acid, acrylic acid, crotonic acid, A C1 to C4 alkyl half ester of maleic acid, and a group of such anhydrides or derivatives starting with maleic anhydride. The reaction of the acid anhydride with the amine is very fast. When the ethylene-based copolymer having an acid anhydride functionality is mixed with the polyamine, the anhydride functionality of the ethylene-based copolymer reacts with the amine end of the polyamine. An ideal tackifier is an ethylene-based copolymer modified with maleic anhydride. Specifically, a maleic anhydride-modified ethylene-butene copolymer (for example, "TAFMER MH-5020" manufactured by Mitsubishi Chemical Corporation) or the like can be mentioned. The preferred tackifier for the polyamine resin composition of the present invention comprises maleic anhydride grafted EPDM (0.2% to 6%, preferably 0.5 to 3% maleic anhydride); grafted with maleic anhydride And get EP (0.5% ~ 6%, preferably 1 ~ 3% of maleic anhydride); maleic anhydride grafted low density polyethylene (0.2% ~ 6%, preferably 0.5 ~ 3% of maleic anhydride) And ethylene butyl acrylate (0.2% to 6%, preferably 0.5 to 3% maleic anhydride) obtained by grafting maleic anhydride.

In the ionic polymer (iii) of the olefin/acrylic acid/anhydride terpolymer, the olefin (a) is selected from the group consisting of ethylene, butene, propylene, and the like, and the acrylic acid (b) is selected from the group consisting of acrylic acid and methacrylic acid. a group of such mixtures, and the anhydride (c) is selected from the group consisting of C1 to C4 alkyl half esters of maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride, and maleic acid. And the group consisting of such a mixture of dicarboxylic acid monomers, the terpolymer contains (b) 2 to 25% by mass, and (c) 0.1 to 15% by mass. The terpolymer to be used in the composition of the polyamide resin of the present invention is an ethylene/methacrylic acid/maleic anhydride ionic polymer (containing 0.5 to 12% by mass, preferably 2 to 6% by mass of maleic anhydride) . The ionic polymer can neutralize the carboxylic acid unit in the terpolymer by a divalent metal ion selected from the group consisting of zinc, magnesium, manganese, and a mixture thereof, or in combination with sodium or lithium ions. The total number is about 5 to 90% to form. The terpolymer may further contain 40% by mass or less of a C1-C8 alkyl acrylate monomer unit.

The styrene-based elastomer (iv) having a carboxylic anhydride group is preferably a styrene-based copolymer: styrene/ethylene-butylene/styrene modified with maleic anhydride, or modified with maleic anhydride. And get styrene / isoprene.

The tackifier (B) of the present invention can be used singly or in combination of two or more. The combination of the above polyamine resin and one or more of the above-mentioned tackifiers makes it easy to achieve the melt strength required for blow molding. Further, the addition of the above tackifier also improves the elongation of the molten parison in the blow molding step. The presence of the tackifier improves the viscoelastic properties of the polymer composition. For example, after the high temperature polyamine trim is extruded in the blow molding step, the preform can be broken and blown to a larger diameter. This is particularly important in the blow molding step when blow molding a fiber-reinforced polymer composition which is easily broken into a large article. The melt flow index (measured by the melting point of the polyamide resin + 10 ° C, the load of 2.16 kg) of the polyamide resin composition used in the application for blow molding is 1 The range of ~90 g/10 minutes is more preferably in the range of 3 to 30 g/10 minutes.

The amount (content) of the tackifier (B) is 2 to 30 parts by mass, preferably 5 to 25 parts by mass, more preferably 5 to 20 parts by mass, per 100 parts by mass of the polyamide resin. If the amount is less than 2 parts by mass, the viscosity-increasing effect is small, and if it exceeds 30 parts by mass, extrusion becomes difficult.

In the present invention, strength, rigidity, heat resistance and the like can be greatly improved by adding an inorganic reinforcing material (C). Examples of such an inorganic reinforcing material include glass fiber, carbon fiber, metal fiber, asbestos, potassium titanate whisker, ash stone, glass flake, glass beads, talc, mica, clay, calcium carbonate. , barium sulfate, titanium oxide, aluminum oxide, etc., of which a short-cut type glass fiber is preferably used. When blended, the blending amount (content) is preferably from 5 to 140 parts by mass, particularly preferably from 5 to 100 parts by mass, per 100 parts by mass of the polyamide resin. When it is less than 5 parts by mass, it is difficult to exhibit the effect of strengthening, and if it exceeds 140 parts by mass, the blow moldability may be inferior.

Further, in the polyamine resin composition of the present invention, an ultraviolet absorber (for example, resorcin, salicylic acid) may be added to 100 parts by mass of the polyamide resin insofar as the object of the present invention is not impaired. One or more kinds of usual additives such as esters, benzotriazoles, diphenyl ketones, lubricants, mold release agents, nucleating agents, plasticizers, antistatic agents, and coloring agents including dyes and pigments The mass is around. The polyamine resin composition of the present invention may contain the components described above, and the polyamide resin, the metal cyanide salt (A), and the tackifier (B) are removed from the composition of the inorganic reinforcing material. The total amount should preferably be 90% by mass or more, and more preferably 95% by mass or more.

The polyamine resin composition of the present invention has a tensile strength retention ratio of 80% or more after heat treatment at 200 ° C for 1,000 hours in the heat aging test described in the item of the examples. The polyamine resin composition of the present invention can achieve such characteristics by having the composition described above.

The method for causing the polyamide resin to contain the metal cyanide salt (A), the tackifier (B), and other additives in the present invention is not particularly limited and may be carried out by any method. For example, a method of kneading in an extruder or a kneader after mixing all the components in advance, or a pellet obtained by kneading any of a plurality of components in an extruder or a kneader in advance, further Ground mixing and other methods of blending other ingredients.

In the polyamine resin composition of the present invention, in order to produce a extruded product, a conventional extrusion method may be employed, and in order to manufacture a blow molded article, a conventional blow molding method such as suction blow molding or injection may be employed. The blow molding method for blow molding, in order to manufacture a foamed molded article, a chemical foaming method using a chemical foaming agent, and a core retreat using a carbon dioxide or nitrogen gas in a supercritical state as a foaming agent can be used. -back) foaming method, etc.

An example of the use of the molded body comprising the polyamide resin composition of the present invention is, for example, a valve, a suction pipe (air pipe), and particularly an exhaust system component such as an exhaust pipe, and cooling in the field of automobiles and vehicles. Exhaust systems such as liquids and water pumps, heaters, joint components, and silencers. [Examples]

Hereinafter, the present invention will be specifically described using examples, but the present invention is not limited to the examples. Among them, the measured values described in the examples were obtained by the following methods.

(1) Raw materials and polyamide 66: Relative viscosity RV = 3.6, T-660X-1 manufactured by Toyobo Co., Ltd. ・ Polyamidoamine 6T/12: Relative viscosity RV = 2.5, Toyobo Co., Ltd. (6T/12= 65/35 (Morbi)) ・ Potassium ferrocyanide·3 hydrate (potassium hexacyanoferrate (potassium sulphate)·3 hydrate): purity of 99% by Wako Pure Chemical Co., Ltd. ・Potassium ferricyanide (six Potassium cyanoferrate (III): purity of 99% by Wako Pure Chemical Co., Ltd. ・Sodium ferrocyanide·10 hydrate (sodium hexacyanoferrate (I) hydrate): purity by Wako Pure Chemical Co., Ltd. 99% ・Anhydrous ferric chloride (III): 99% pure by Wako Pure Chemical Co., Ltd. ・Indigo iron (II): 98.0% pure by Wako Pure Chemical Co., Ltd. ・Iron oxide (II): manufactured by Wako Pure Chemical Co., Ltd. (III): phenolic antioxidants manufactured by Wako Pure Chemical Co., Ltd.: IRGANOX245 manufactured by BASF Corporation ・ Copper (II) bromide: 99.9% pure by Wako Pure Chemical Co., Ltd. ・ARUFON UG4070: Polyfunctional epoxy compound manufactured by Toago Chemical Co., Ltd., TAFMER MH-5020: Maleic anhydride-modified ethylene-butene copolymer manufactured by Mitsubishi Chemical Corporation, glass fiber: T-275H, manufactured by Nippon Electric Glass Co., Ltd.

(2) Test method, tensile strength, tensile elongation at break: Using Toshiba Machine Co., Ltd., IS-100, the cylinder was set to 280 ° C (320 ° C when using polyamide 6T/12), and the mold temperature was 90 ° C. After obtaining a molded article under the conditions, the measurement was carried out in accordance with ISO527-1 and 2.

• Thermal aging test: The test piece was heat-treated in a recirculating air oven (NH-401S, a hot air circulating dryer manufactured by NAGANO SCIENCE CO. LTD.) in accordance with the procedure detailed in ISO 2578. The heat treatment was carried out at 200 ° C for a predetermined test time (500 hours, 1000 hours), the test piece was taken out of the oven and cooled to room temperature, and sealed in a bag lined with aluminum before the test was prepared. Then, according to ISO527-1, 2, tensile strength and tensile elongation at break were measured. The average value obtained from the three test pieces was used.

The retention of tensile strength and tensile elongation at break is the retention after heat treatment for 500 hours and 1000 hours when the initial value without heat treatment is set to 100%.

In the resin compositions described in the examples and the comparative examples, the raw materials were each blended using a biaxial extruder (STS35 manufactured by Coperion Co., Ltd.) at a ratio (mass ratio) shown in Tables 1 and 2. The pellets were melted and kneaded to obtain pellets (about 2.5 mm in diameter × about 2.5 mm in length). The obtained pellets were dried by a hot air circulation dryer at 100 ° C for 4 hours or more. The evaluation results are shown in Tables 1 and 2.

The pellet obtained above was dried at 100 ° C for 4 hours or more by a hot air circulation dryer using a 2-layer blow molding machine manufactured by FONG KEE INTERNATIONAL MACHINERY Co., Ltd., and then the resin temperature was 280 ° C (when polyamine 6T/12 was used) The blow molding time was carried out at 320 ° C), the blow molding time was 18 seconds, and the temperature control of the mold was not performed, and the blow moldability was evaluated by the following criteria. ○: Blow molding *: Blow molding is not possible (the molded product is cracked, or the parison is down-drawed and cannot be blow molded)

[Table 1]

[Table 2]

Examples 1 to 4 exhibited good blow moldability, tensile strength at the initial (before heat treatment), tensile elongation at break, and tensile strength retention after heat treatment at 200 ° C for 500 hours and 1000 hours. The tensile elongation at break retention rate is also a high value. Example 5 is an example of polyamine 6T/12, exhibiting good blow moldability and high tensile strength and tensile elongation at break (before heat treatment), and heat treatment at 200 ° C for 500 hours and 1000 hours. The tensile strength retention ratio and the tensile elongation at break retention ratio are also high. Example 6 is an example which does not contain a copper-based stabilizer, exhibits good blow moldability and has high tensile strength and tensile elongation at break (before heat treatment), and is heat-treated at 200 ° C for 500 hours and 1000 hours. The tensile strength retention ratio and the tensile elongation at break retention ratio are also high. Example 7 is an example in which the amount of glass fibers is large, exhibiting good blow moldability and high tensile strength and tensile elongation at break (before heat treatment), and after heat treatment at 200 ° C for 500 hours and 1000 hours. The tensile strength retention ratio and the tensile elongation at break retention ratio are also high values. Examples 8, 9, and 10 are examples in which an organic stabilizer (phenol-based antioxidant) is not contained, and good blow moldability is exhibited, and tensile strength and tensile elongation at break of the initial (before heat treatment) are also high, and The tensile strength retention ratio and the tensile elongation at break retention ratio after heat treatment at 200 ° C for 500 hours and 1000 hours were also high.

Comparative Example 7 is an example in which only a phenol-based antioxidant and copper (II) bromide were added, and although the blow moldability was good, the tensile strength retention rate and the tensile elongation at break after 500 hours and 1000 hours at 200 ° C were obtained. The degree of retention is greatly reduced. Comparative Example 1 is an example in which the amount of potassium hexacyanoferrate (III) acid added is small, and although the blow moldability is good, the tensile strength retention rate and the tensile elongation at break after 500 hours and 1000 hours at 200 ° C. The retention rate is greatly reduced. Comparative Example 2 is an example in which the amount of potassium hexacyanoferrate (III) acid added is excessive, and although the blow moldability is good, the tensile strength retention rate and the tensile elongation at break after 500 hours and 1000 hours at 200 ° C. The retention ratio was not improved as compared with Example 4, and the initial tensile strength and tensile elongation at break were also lowered. Comparative Example 3 is an example in which iron oxide (II) was added, and the blow moldability was good. Although the tensile strength retention rate and the tensile elongation at break after 500 hours and 200 hours at 200 ° C were relatively high, This is because the initial tensile strength and tensile elongation at break were lower than those of Example 1, and the tensile strength and tensile elongation at break after heat treatment were lower than those in Example 1. Comparative Examples 3, 4, 5, and 6 are examples in which iron (II) oxide, iron (III) oxide, iron (II) chloride, and indigo iron (II) are added, and the blow moldability is good, but the blow moldability is good. In particular, the tensile strength retention ratio and the tensile elongation at break retention after 1000 hours at 200 ° C were greatly lowered. Comparative Example 8 is an example in which only a phenolic antioxidant and copper (II) bromide were added to the polyamine 6T/12, and the blow molding property was good, but the tensile strength after 500 hours and 1000 hours at 200 ° C was obtained. The retention ratio and the tensile elongation at break retention ratio are drastically lowered. Comparative Example 9 is an example in which only a phenolic antioxidant was added to the polyamide 66, and although the blow moldability was good, the tensile strength retention and the tensile elongation at break after 500 hours and 200 hours at 200 ° C were maintained. The rate is greatly reduced. Comparative Example 10 is an example in which a large amount of tackifier was added, and although the heat aging resistance was excellent, the blow moldability was poor. Comparative Example 11 is an example in which no tackifier was added, and although the heat aging resistance was excellent, the blow moldability was poor. [Industrial use]

The polyamidamide resin composition of the present invention is excellent not only in heat aging resistance in a high temperature environment of about 200 ° C, but also has a high melt viscosity, and can be molded into a molded article, a blow molded article, a molded article such as a foamed molded article. It can be used as a part for automobiles and electrical and electronic products that may be exposed to an environment of 200 ° C.

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Claims (5)

A polyamidamide resin composition comprising: 0.5 to 20 parts by mass of a metal cyanide salt (A) having the following general composition formula (1), and a tackifier (B), based on 100 parts by mass of the polyamide resin 2~30 parts by mass and inorganic reinforcing material (C) 0~140 parts by mass; general composition formula (1)...A _x [M(CN) _y ]; In general composition formula (1), M is the fifth in the periodic table At least one of the transition metal elements of the ~10 group and the 4th to 6th cycles, A is at least one of an alkali metal and an alkaline earth metal, y is an integer of 3 to 6, and x is obtained by (ym)/a The value obtained; here, m is the valence of M, and a is the valence of A. The polyamine resin composition of claim 1, wherein M of the general composition formula (1) is iron. The polyamine resin composition of claim 1, wherein the metal cyanide salt (A) of the general composition formula (1) is selected from the group consisting of alkali metal hexacyanoferrate (II) and hexacyano One or more of the base metal (III) acid-base metal salts. The polyamine resin composition according to any one of the first to third aspects of the present invention, wherein the copper compound is contained in an amount of 0.0001 to 1 part by mass based on 100 parts by mass of the polyamine resin composition. The polyamidamide resin composition according to any one of claims 1 to 4, wherein the tackifier (B) is selected from the group consisting of polyfunctional epoxy compounds (i), having a carboxylic acid group and a carboxylic anhydride An ethylene-based copolymer (ii) of at least one of the groups, an ionic polymer (iii) of an olefin/acrylic acid/anhydride terpolymer, and a group of styrene-based elastomers (iv) having a carboxylic anhydride group At least one.